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Proceedings of the

First International

Symposium on

Water Desalination

WASHINGTON, D.C.

OCTOBER 3-9, 1 965

U.S. DEPARTMENT OF THE INTERIOR


Office of Saline Water
WATER RESOURCES
CENTER
ARCHIVES
OF
THE UNIVERSITY
OF CALIFORNIA
RETURN WATER RESOURCES CENTER ARCHIVES
" North Gate Hall 642-2666
r_
Proceedings of the

First International

Symposium on

Water Desalination

WASHINGTON, D.C.

OCTOBER 3-9, 1965

U.S. DEPARTMENT OF THE INTERIOR


STEWART L. UDALL, Secretory

Kenneth Holum, Assistant Secretary


For Water and Power Development
Frank C. Di Luzio, Director
Office of Saline Water
For sale by the Superintendent of Documents, U.S. Government Printing Office
Washington, D.C., 20402 - Price $4
INTRODUCTION

This volume includes all the papers pertaining to engineering


development. Most of these papers were presented at the Symposium,
however, a few were submitted for publication only and are so designated.
After each paper presented at the Symposium is a summary of the dis
cussion period held following their presentation. Each of the papers is
followed by abstracts in French, Russian, and Spanish languages.
CONTENTS

Page

Some Problems and Research in the Multistage


Flash Distillation Process 1
Influence of Membrane Phenomena on
Electrodialysis Operation 13
Scale Control in Sea Water Distillation 25
Saline Water Distillation—Scale Prevention
by Polymer Additives 39
Heat and Mass Transfer in Flash Distillation
without Metallic Interfaces 57
A New Ion-Exchange Desalination Technique 69
Survey of Water Desalination in Israel 87
The "Sirotherm" Demineralization Process 103
An Appraisal of Scale Control Methods at the O.S.W.
Flash Evaporator Plant in San Diego, California 139
s. Improvement in Fabrication Techniques for
Reverse Osmosis Desalination Membranes 159
Vapor Compression Evaporation with Direct
Contact Heat Transfer 181
Evaporation of Sea Water in Solar Stills and
Its Development for Desalination 193
Thin Film Distillation 205
Some Phenomena Associated with Concentration
Polarization in Electrodialysis 219
Desalination by Liquid-Liquid Extraction 239
Ion-Exchange Pretreatment 251
Aspects of Two-Phase Flow and Heat Transfer
in Distillation Type Conversion Processes 275
General Review of the Work of the Sea Water Conversion
Laboratory of the University of California 301
Methods for Scale Control in Flash Systems 317
An Engineering Evaluation of the Vertical
Tube Falling-Film Distillation Process 337
Design Criteria for Reverse Osmosis Desalination Plants 367
A Survey of Electrodialysis Developments
in the United States 389
Some British Achievements in Desalination 407
A Simple Calculation Method for the Vapor Reheat Process 415
Solar Powered Humidification Cycle Desalination 429
The Limitations of Electrodialytic Water Desalting
with Permselective Membranes and the
Requirements for Electrodialytic Equipment 461
Utilization of Desalinated Water in Japan 475
Conversion of Sea Water by Evaporation 481
Objectives of the United Kingdom Research
and Development Programs 493
—' Low Capacity Nuclear Desalination Plants 499
Desalination of Saline Water by Electrodialysis 511
Intensification of Heat Exchange in Evaporator Installations 523
Slit and Point Corrosion (Pitting) of Stainless Steel in
Chloride Solutions at Temperatures up to 100°C 531
Prevention of Scale Formation in Distillation
Desalination Plants by Means of Seeding 539
Corrosion Resistance of Materials in Sea Water 549
Use of Ion-Exchange Membranes for Water Desalination 561
Water Desalination by the Ion-Exchange Method 575
Dropwise Condensation 589
Solar Distillation—A Review of the Battelle Experience 609
Solar Distillation in Greece 627
The Freezing Processes for Water Conversion
in the United States 641
Operational and Future Aspects of Vapor
Compression Distillation 659
Removal of Scale Formers with Byproduct Recovery 697
A Pilot Plant Design Based upon a Direct Contact Flash
Distillation Process with Liquid-Liquid Heat Exchange 717
The Multiple-Phase Ejector as a Vapor Compressor
in Distillation Desalination Systems 735
On the Freezing Process 753
The Koppers Hydrate Process 771
\ Multieffect/Multistage Flash Distillation 781
Desalination in Spain 799
"Las Marinas" Solar Conversion Pilot Plant (Spain) 819
Index 829

vi
Some Problems and Research in the

Multistage Flash Distillation Process

R. S. Silver, M.A., D.Sc., M.I. Mech.E., F.Inst.P., F.R.S.E.

Scotland

INTRODUCTION
First of all let me express my thanks to Technology by the arrangements which
the VS. Office of Saline Water for its invita came into force in April 1965.
tion to give a paper at this Symposium, and The range of work considered in this
to the U.K. authorities for sponsoring me as paper excludes many aspects which are
a member of the British Delegation. important in the realization of multistage
Some will be familiar with my previous flash distillation in practice. It is limited to
papers on desalination. Many of these have what may be termed the hydrodynamic and
been primarily concerned with economic thermodynamic aspects of sea water distilla
aspects and hence with overall system de tion. Hence, we shall not discuss in detail
sign: some have been review papers. At the the construction materials in which such
First European Symposium in Athens in processes must be made to occur or the cor
1962. a brief discussion was given (ref. 1) rosive and erosive actions to which mate
or characteristic problems in distillation but rials are prone. Moreover, we shall ignore
no precise scientific development was pre the presence of scale-forming constituents
sented. The object of this paper is to fill in the sea water—unless they alter its ther
that blank in some respects. It will have modynamic properties—and omit reference
special reference to the research work being to scale deposition or its prevention. Some
done in the Mechanical Engineering De arbitrary selection is needed to delimit a
partment of Heriot-Watt College, Edin paper, and in justification of our particular
burgh, Scotland. choice it can be urged that discussions of
scale, materials, and corrosion are already
This work was initially sponsored by the abundant in desalination literature. But the
Department of Scientific and Industrial Re basic science of distillation itself is nowhere
search, by a grant commencing in 1964. and in great evidence. It is to this that the
is being continued under the Ministry of Heriot-Watt program is directed.

BASIC CHARACTERISTICS OF FLASH DISTILLATION


The distinguishable parts of the flash dis 4. Free level flow of brine and of product
tillation process as such are: distillate, at near saturation tempera
1. Heat transfer from tube walls to ture and pressure conditions, from
liquid brine in heat input and recov stage to stage.
ery sections and to sea water in heat 5. Flashing of vapor from brine, and
rejection sections. from product distillate, in the stages
2. Heat transfer, usually from steam, to and perhaps also in interstage passages.
tube walls in the heat input section. 6. Flow of flashed vapor to and through
3. Heat transfer, by condensation of prod condensing regions.
uct vapor, to tube walls in the heat 7. Entrainment and disentrainment of
recovery and heat rejection sections. brine droplets in the vapor flow.
8. Pumping of brine with suction condi proper design and minimization of capital
tions near saturation temperature and cost for a given energy consumption may
pressure. be achieved. (N.B. The optimization of
While these characteristic events are dis water cost is a separate issue, dealt with
tinguishable and are suitable for separate in general economic studies, where overall
and independent scientific study, it should cost is minimized by an appropriate choice
be emphasized here that their interaction of energy and capital costs. Lowering of
and interdependence in an actual flash dis water cost must ultimately depend however
tillation plant is incredibly complex. on getting the lowest capital cost for any
The pressure in the r" stage counting given energy consumption.)
from the highest pressure, is determined by In the above list, item 1 can be consid
the rate of brine flow into it and by the ered well understood, since the brine is kept
performance of the condensing surface alio under sufficient pressure to avoid any vapor
cated to it. The rate of brine inflow is formation. The literature and practical ex
determined by the pressure of the (r — l),b perience regarding heat transfer to liquids
stage and by the pressure of the r,h stage flowing inside tubes is sufficient to provide
itself, and by the design of interstate passage accurate and reliable heat transfer and flow
and extent of flash occurring therein. The resistance data.
performance of the condensing surface is When we turn to items 2 and 3, however,
determined not only by the heat transfer we are concerned with condensation heat
characteristics of the kind considered in transfer, and this is by no means in such a
items 1 and 3 above, but by the inlet satisfactory state. Multistage flash distilla
temperature of the circulated brine, and tion can ill afford pressure drop across con
that depends on the whole behavior of the densing surfaces and is particularly subject
(r -)- l),h stage. The theory of that inter
to the presence of noncondensable gases.
dependence has already been published Neither of these correlates of condensation
(ref. 2). heat transfer is well understood. Hence, the
The energy consumption of a flash distilla condensation process was chosen as one of
tion plant is critically dependent upon all our specific fields of research activity.
the design saturation temperatures in all
the stages being satisfactorily obtained. The Our other field of research is obvious.
capital cost depends critically upon the Items 4 to 8 inclusive are all dependent on
amount and disposition of heat transfer a knowledge of flow of equilibration be
surface and the provision of the equipment havior of saturated liquid and liquid vapor
in which the phenomena have to occur. mixtures.
The object of a research program concerned In the following sections an account is
with items 1 to 8 is, therefore, to establish, presented of some of our work under the
if possible (where it does not already exist) , two headings of "Condensation" and "Flash
sufficient understanding of each item so that ing Flow and Equilibration".

CONDENSATION
In 1964 a paper was published on "An tion of velocity as mass flow rate is reduced
Approach to a General Theory of Sur by condensation. Clearly, just as the recov
face Condensers" (ref. 3) . The chief new ery of kinetic energy to pressure in a dif
feature of this work was the exploitation fuser depends on the rate of enlargement,
of the concept of Reynolds Flux to discuss it is to be expected that equivalent criteria
the behavior of the steam side flow friction will exist to determine the actual recovery
and heat transfer. Two important predic with condensation over tube banks. Silver's
tions were made. theory (ref. 3) showed that critical condi
The first was that the occurrence of con tions should exist which would determine
densation should modify the frictional re whether or not the reduction of frictional
sistance, reducing it below that which would resistance combined with reduction of vel
occur in a noncondensing fluid of the same ocity (both due to condensation) would
physical properties at the same velocity in give a pressure rise. The deduction was that
the same configuration of tubes. It was pressure rise should occur provided m>efm.
shown that the amount of this reduction where m is the condensation rate per unit
should be sufficient to give a net pressure surface area and efm is the Reynolds Flux,
rise, instead of a pressure drop. The origin in the presence of condensation at rate m.
of the rise is of course in the Bernoulli A theory was also offered to describe the
recovery of kinetic energy due to the reduc functional relationship between ttm, m, and
íf„ where efo is the normal Reynolds Flux wall. A wide range of velocities was covered,
without condensation. The relationship de and it was established that pressure recovery
rived was rather complicated but had the did in fact occur to a degree which was
characteristic that m = «,„ when m = 0.61 dependent on rate of mass extraction, and
€,„. Since «,„ is easily obtained from noncon- that frictional resistance was reduced. The
densing flow over the same configuration, criterion for positive pressure recovery over
the conclusion could be tested. a wide range of velocities was found to be,
The second important prediction was that with small scatter,
the effect of noncondensable gases present m > OJW «,. (S.l)
in condensing vapor could also be under This compares surprisingly well with Silver's
stood in terms of the m and ef(> relation predicted value of 0.61 ef0 mentioned above.
ships. According to the theory developed, Wallis showed that a possible deduction
if m tended to 2<(> the back diffusion of from his results is that the relationship be
noncondensable gases from the surface tween tim. m, and Cf„ is the very simple one.
would become impossible, and gas blanket ft. = ft. — 0.7m (3.2)
ing would occur. Hence in fact m would
be reduced and must stop below the value from which efm = m when m =
2«f.. Thus condensation at a rate greater 1.7
m
than 2eto was predicted as impossible- i.e., when — — 0.59.
fro
whatever the temperature difference avail Hence the condition for pressure recovery
able—and the detailed effects of noncon agrees with Silver's general formula, m >
densable gases were, in principle, calculable. et„, although this occurs at a different value
Again it was possible to test these conclu of m/cf.-
sions. Clearlv Equation (3.2) would have e,m
Since «t„ is primarily a function of the becoming zero at -Ш— — 1.43 as against
Reynolds Number of the flow and the tube Cf.
configuration, these arguments were obvi Silver's prediction of Ш — 2. In view of
ously of potential importance to the design (fa
of condensing plants. They are of even the effect on noncondensable gases, this
greater potential importance to the con difference is potentially important.
densers in flash distillation, because of the In view of this. Silver and Wallis (ref. 5)
considerable temperature and heat exchange made another attack on the theoretical
value of even a small pressure recovery in problem. It was first shown that a very
relation to the total temperature difference crude approach, assuming that the Rey
available in a plant with a large number nolds Flux had a uniform lateral velocity,
of stages. Moreover noncondensable gases gave
f(m = «fo — 0.5 m (3.3)
are unavoidably present in greater propor
tion in sea water distillation plants than This linear expression is much simpler than
in condensers for the very pure water of Silver's original form, but has the same
a steam power cycle. Hence the first objec limit at m =2. It would give the pressure
tives of our research program at Heriot- ft*
VVatt College were to test the validity of recovery criterion as m = 0.66. Silver and
these conclusions.
The first experiments were done by Wallis Wallis (loe. cit.) then took a more sophis
(réf. 4), while assigned to Heriot-Watt as ticated approach allowing for a turbulent
Senior Visiting Fellow from Dartmouth Col velocity distribution in the Reynolds Flux.
lege, New Hampshire. He set out to check This led to -m/2«f.
the behavior with minimal form drag. One
of the problems discussed by Silver (ref. 3) tfm = ио e (3.4)
was that in a bank of tubes, the total drag This solution is more satisfactory in prin
consists not only of friction but also of form ciple since efm does not actually become
drag. The Reynolds Flux theory applied zero and m/ef0 may increase indefinitely.
only to the former, and while some argu The effect on noncondensable gases is that
ments suggest that form drag would also their concentration at the condensing sur
be reduced, their validity was not obvious. face is increased over that in the main
Wallis, therefore, tested the axial flow stream by a factor which does not now
along the inside of a straight tube since, become infinite unless m/t(0 also becomes
apart from entrance loss, form drag is neg infinite. This factor is
ligible. All his experiments were with air m/2ef„
instead of steam, condensation being simu -^--1 + — e (3.5)
lated by extraction of air through a porous t-io «Го
From Equation (4) the critical condition a lower pressure and, therefore, a lower
for pressure recovery occurs when m = temperature difference on the first rows of
0.748. ITT tubes. Clearly an optimization is needed,
The net result of Wallis' experiments and for this purpose, information of the
was to confirm that effects of the kind sug type we are studying is essential.
gested by Silver probably exist. Work has The magnitude of the effects can be
therefore gone ahead on banks of tubes. shown from the following simple theory.
Drummond (ref. 6) operated a porous tube Ideally, the pressure change is related to
air analog on the same basis as Wallis but I he velocity change by the basic relations
used air flow external to banks of porous '«■)- = - V dp (3.6)
tubes. His conditions are therefore closer
to actual condensing practice, and form If we are dealing with saturated steam
drag becomes important. This work is still we may substitute for dp in terms of dT,
in progress, but it has already been con the change in saturation temperature, via
firmed that both form drag and friction the Clapeyron equation. Hence
drag are reduced by extraction for certain
tube configurations. It has yet to be found
whether or not a net pressure recovery is (3.7)
obtainable, but certainly pressure drop can
be reduced. It will be understood that since For the flow of saturated vapor during
form drag enters the problem, results are condensation (assuming that the condensed
bound to be related to tube arrangements liquid has been separated to the tube walls
and this work will necessarily be more or is falling under its own dynamics) , we
protracted. can put V = V.; and, since the pressure
Simultaneously, we have constructed a with which we are concerned is Vw «V„
test section for actual steam condensation we have to a good approximation
experiments. The intention here is to check (3.8)
in actual condensation tests such arrange
ments as are indicated as the most promis Over our range, L and T (its absolute
ing from the air analogs. value) are nearly constant at values of the
One of the most important aspects of this order 1,000 Btu/lb and 660° R, respec
work in relation to desalination is as fol tively. Hence every degree Fahrenheit of
lows. The distillation plant designer is temperature fall corresponds to about 1.5
faced with the problem of an inevitable Btu/lb of velocity energy increment, and
pressure reduction due to vapor velocity vice versa. Starting from zero velocity, this
increase on entering a bank of tubes. Trying corresponds to about 270 ft/sec for 1° F,
to keep this velocity low requires a wide and the relationship is then proportional
tube plate. If this velocity can be increased to V A T. For multistage flash distillation
and the kinetic energy recovered as pressure, with high performance ratio, we need so
this can not only help maintain the tem many stages that nominal terminal tempera
perature difference but also introduce new ture differences may be below 5° F. Hence,
possibilities of tube plate dimensioning. The these velocity and pressure relationships
higher entrance velocity will of course mean cannot be neglected.

FLASHING FLOW AND EQUILIBRATION


When a mass of liquid at temperature The term V» (p„ — p,) is always much
T„ is reduced to a pressure p, at which the less than Cw (T. — T,) in the range
saturation temperature T, is less than T0. with which we are concerned. The ratio
a proportion of it must eventually become V. (P. - P.)
vapor. The final equilibrium proportions C (T. - TO
q. of vapor and 1 — q, of liquid are gov varies from order 10-' at 270°F to 10"' at
erned by the relationship 100°F.
Hwo = (1 -q,)Hwl + q. H., q r~f t\
= Hwl + q, L, (4.1) Hence effectively q, = "" ° .
La (4 .a)
Since the volume of the liquid is Manv of the characteristic problems of the
not appreciably affected by small pressure flash distillation process are related to the
changes, we have essentially word "eventually" in the above enunciation.
C. (T. - TQ + V. (p. - p.) The formation of the vapor cannot occur
q, - instantaneously. It requires that heat flow
occur from zones still liquid to zones of be the causes of the difference. Hence the
evaporation and that the vapor be cooled by previous work of Benjamin and Miller
this heat flow to the new equilibrium tem gives very little guidance on the large flows
perature. The zones of evaporation require occurring in multistage flash distillation.
an interface surface between liquid and More recently, Simpson and Silver (ref.
vapor; and if such a surface does not exist, 9, 1962) gave a more sophisticated account
it must be created as bubbles or drops. of flashing flow theory, but this is exceed
The equilibrium value of q is usually ingly complex and is unlikely to be suitable
small in multistage flash distillation. For a for the scale of events in flash distillation.
4"F drop between stages, it is only of order What is required is a fairly simple theoreti
0.004. But at a temperature in the normal cal scheme, defining concepts and param
flash range, say 150°F, the ratio of V. to eters which may be measured in experiments,
Vw is 6,000. Hence that small proportion in pilot plants, and in actual plants and
of flash vapor has a volume of 24 times the whose trends may be established so that
liquid from which it has come. This ratio, new designs can be improved or made
for a 4°F drop, varies from i2 at 250°F larger. The following is a brief development
to 88 at 100°F. In flash distillation the showing the ideas which we believe will be
reduction of pressure on the liquid has to useful and which will be the subject of
be used to cause brine flow through some experimental investigation at Heriot-Watt
control area or passage between stages. College.
Hence even a small proportion of flash Equations (4.1) and (4.2) discuss even
vapor occurring in that area or passage is tual isenthalpic equilibrium. Under ideal
liable to occupy a substantial proportion velocity generating conditions we should be
of the area. These control areas cannot be concerned instead with isentropic equili
designed to allow the correct quantity ol brium. This would be obtained from
brine to flow with the correct pressure dif S„„ = (1 - q) Swl + q S„
ference unless the extent of flash in the
passage can be predicted. -S^ + qi?. (4.3)
It might be thought that there is one
easy way. If the control area is in the form Since Swo — SWJ — C. log —1- T we have
of a sharp-edged orifice, there should be no
time for flash to occur, and even saturated q= C. log -li- (4.4)
liquid flow rates through such an orifice
should be the same as cold water flow. That Now with T. — T, of order 4°F and T,
this is nearly true for pure water and for T
small circular sharp orifices at fairly high of order 600°R,-=^-is of order 1.007. Hence
pressures where the volume change is small Ti
was proved in 1941 by Benjamin and log-=^-is T to a very good approximation equal
Miller (ref. 7) . But sea water brine in a Ti
distillation plant unavoidably has minute to —- f f from which
solid particles in it which promote nucle-
ation to some extent, and the scale of
flow is such that the orifices must be large
and noncircular. The approach flow even Hence in the range with which we are
to a sharp-edged orifice is, therefore, almost dealing, we see by comparing Equations
certain to be disturbed; and there is good (4.5) and (4.2) that q is not distinguishable
evidence to indicate that flashing may com from q„ i.e., the isentropic equilibrium q
mence in front of such an orifice and cause for any pressure drop is not appreciably
restriction. Silver (ref. 8) confirmed the different from the isenthalpic q..
results of Benjamin and Miller but ex However, we have to consider the isen
tended the experiments to include short tropic change from another point of view
nozzles. A theory based on surface evapora
tion from the interface created by the inner if we want to evaluate the maximum vel
ocity energy which is available—because of
nozzle wall was found to correspond reason
ably well to experimental results for nozzles course
ocity
isenthalpic conditions give zero vel
energy. The equation for horizontal
or orifices below i/2 inch diameter, but flow of any fluid, excluding frictional re
above that size it was apparent that more
flashing was occurring than could be ac sistance, is
counted for on that surface basis. Preflash d = - V dp (4.6)
in the nozzle entrance and nucleation
within the body of liquid were presumed to For a mixture of liquid and vapor in
the respective proportions, 1 — x and x Now while Equation (4.14) is the end
thus become result of this analysis, it is instructive to
consider it in a slightly different form. If
d (-^-) = - V. dp _ x(V. _ V.) dp we multiply the third term above and
g (4-7) below by L., we obtain
ftC. (T. - T,) ■ u
Vw dp is the term which would be found
for the liquid alone, i.e., it is the increment 2L, T.
of velocity energy which cold water would which is equal to
have. MT.-TQ
x (V. - Vw) dp 2T„
We saw in discussing Equation (S.8) that,
(4.8) for a small range of integration over which
We may again use Clapeyron's equation L and T may be regarded as nearly constant,
to substitute for dp in terms of dT and L(T.-TQ
obtain T.
d(£)=dG?)-x*-dT (49) is the velocity energy which would be
obtained by saturated vapor alone in the
Now if the flow had started from satu pressure fall from p„ to p.. Moreover /3q is
rated liquid at T„ and the temperature of the actual amount of vapor formed. Hence
the liquid had reached T, the value of x the term has the simple significance of the
would be q. We now introduce the fact product of the total actual vapor quantity
that equilibrium is not always achieved by and the velocity energy obtainable from
using a concept of the "fraction of equili half the pressure drop. This is effectively
bration". This we shall define as follows. the average kinetic energy obtainable from
The pressure of the system has now the vapor.
reached p, for which T is the saturation This fact allows us to regard Equation
temperature. But if equilibration is nol (4.14) in a different light. It indicates that
complete, the mean liquid temperature will the total kinetic energy per unit weight
have some value T1 which is higher than T. obtainable in isentropic expansion can be
The "fraction of equilibration" will be simply expressed as the "cold water" kin
termed p and is defined as etic energy, plus the mean kinetic energy
_ T„ - T available from the actual vapor formed
by the end of the expansion. This appar
T„ (4.10) ently simple and satisfying conclusion has
Then we have important consequences which may now be
x _ C. (T„ - T») pointed out. As is well-known, much of the
L difficulty in discussing two-phase flow phen
= 0q omena is associated with the problem of
C. (T. - T) determining how the actual velocity is dis
= P (4.11) tributed between the two phases. The earl
ier work of Benjamin and Miller, Silver,
and Simpson and Silver all assumed homog
- 0CW V* ~ ^ dT eneous flow—i.e., that the velocity of each
(4.12) phase was the same and was given by an
analysis of the same type as Equation (4.14)
Integration of Equation (4.12) for the —while fully conscious of the probable limi
starting condition p„, T„ and finishing at tations of that assumption. Many other in
p., T„ gives vestigators of two-phase flow have discussed
v* v* T separate velocities in terms of "slip factors",
- = ^+,C.T0.og- and correlations of experimental results of
-pC„ (T. - TO (4.13) nonadiabatic flow are known on such a
basis. The interpretation we have given of
In discussing Equation (4.4) we noted Equation (4.14) now becomes helpful be
that T„ — T_ is small compared with T„ cause we need not be committed to inter
or T,. Hence we can expand log T. preting v as a homogeneous velocity, but
T, v»
in this case to the second difference term instead think only of —— as the kinetic
to give, after manipulation, 2g
energy available for distribution between
^,= y peer. -tq' the phases. Writing it. therefore, as E» we
2g 2g T 2T„ 1 ' have
2îl ßCw (T. - TQ» and hence dissipation cannot make any
(4.15) appreciable difference to the value of q.
2g 2 T.
v«' PqLÇr.-TQ This is important in considering Equations
2 T. (4.14) and (4.15) . Although the direct
thermal effect of dissipation does not pro
In general we may assume that the actual duce appreciably more vapor, since q il
liquid phase velocity is v. and that of the unaffected, its indirect effect can in prin
vapor is v.. Then ciple be important. Dissipation may well
E*=J^ (»-л)+ -^-/sq (<-16) produce more interfacial surface and more
nucleation, and hence may give a higher
value of ß. Under dissipation conditions, we
The cross-sectional area occupied by liquid would have to write for the actual available
°— ■ WV (1 — 0q) while that occupied energy for flow
v. U=I¿. gC(T.-T,)>
WffqV.
by vapor How is Thus the total 2g + 2T. "*
(4.15)1
cross-sectional area is
WV, (l-0q)
„ ,+—
WV. Thus we have the interesting situation
A= — that if dissipation increases the value of ß
(4.17) sufficiently, the extra energy made available
may more than offset the dissipation itself,
Now for a given pressure drop in a given and hence the actual kinetic energy of flow
passage we may regard Л and q as fixed. If may be higher with dissipation than with
we assume ß constant, we also have ¥.t fixed out it. There is no contradiction with any
from Equation (4.15) . Hence vw and v. basic thermodynamic law in this conclusion
become, in principle, determinable from because the situation arises essentially from
Equations (4.16) and (4.17). A quarlic equa the lack of equilibrium.
tion has to be solved and this can be done Among the items of our experimental re
for various values of ß. Hence, the flow rate search is the investigation of dissipative de
per unit area—which is the essential thing vices with the goal of obtaining more rapid
to know for design purposes—can be investi equilibration and perhaps also improving
gated. Actual values of ß. which are un flow. The possible importance of such stud
known, may be determined by experiment. ies is indicated by considering the order of
Another interesting aspect to which atten magnitude of the terms in Equation (4.15)
tion should be drawn concerns the effect of for some typical flash distillation tempera
dissipation by turbulence and by frictional tures as shown in Table I. We see that the
forces generally. These are always present in coefficient of ß is usually much larger than
practice. But as we have seen, the value of *Л
q is negligibly different from that of q., 2R
TABLE I. Typical Hash Distillation Temperatures
Ti'F 100 160 200
(T. — Ti)'F 1 S 6 1 8 6 1 2 «
Vc1 ft lb 0.072 0.216 0.431 1.386 0.6 8.61
0.281 0.693 1.81
"¡7 л
C.(T. - Ti)» ft lb 0.68 6.11 24.7 0.68 6.69 22.76 0.68 6.26 21
2 T. lb

In the present flash distillation plant, it entrainment and of separation. Separators


is probable that the values of ß in the introduce pressure drop with loss of avail
actual flow control areas or passages do not able temperature difference. Our studies are
exceed 0.1 and hence the bulk of the avail concerned with the possibility of obtaining
able kinetic energy from the subsequent utility from the available energy shown in
equilibration is released in the actual flash Table 00. The starting point is work done
chamber and is dissipated in agitation of some years ago under the auspices of G. &
the brine. Such agitation undoubtedly as J. Weir, Ltd. (ref. 10) . In these experiments
sists the completion of equilibration but is flashing water was made to flow upward in
also a primary cause of ejection of droplets a vertical passage, in which was placed a
of brine, giving rise to the problems- of three-dimensional grid. Such grids could be
tried in various forms. The intention was the time it was possible to meet design re
to use frictional dissipation and the me quirements without such devices and the
chanical creation of interfacial surface work was discontinued. In the context of
caused by such a grid to increase the value today it is well worth following up and is.
of p, and yet prevent the available kinetic therefore, included in our work at Heriot-
energy from causing undue agitation. The Watt.
experiments were fairly promising but at

CONCLUSION
The grant to Heriot-Watt College for to other interested parties. Moreover, one
desalination studies provides not only for of his former students is working with us
the work on condensation and two-phase on thermoeconomics of steam power plant.
Sow but also for basic investigations on the None of our work in this field except the
thermoeconomic aspects. These are impor point made by Silver (ref. 2) regarding ex
tant in relation to ultimate judgments and traction steam temperature in mixed power
evaluations. The objective here is funda and water installations is yet ready for
mental studies and not the direct economic publication.
appraisal of particular installations, al It is also well-known that Tribus has
though these must be used as applications made important contributions to the de
of any general theory which may be devel velopment of engineering statistics. We be
oped. The lines of work are those cited in lieve that some of these techniques will be
the early studies by Tribus (ref. 11) and of considerable value in dealing with our
by Simpson and Silver (ref. 12) . It is condensation and two-phase flow studies,
pleasant to record a further example of and in particular with entrainment investi
trans-Atlantic cooperation, in that Dean gation.
Tribus not only agreed to have Dr. Wallis I hope that this account of what we have
of his staff at Dartmouth come to Heriot- done and are doing proves of interest. I
Watt last year to assist in our condensation think that it shows that there are many
work, but has himself participated in our matters in distillation technology which
work as Senior Visiting Fellow for the provide scope for good scientific engineer
month of September 1965. In this capacity ing research, the results of which may main
he has not only examined, supervised, and tain the position of distillation as a viable
given advice on our activities, but has also method of desalination.
given a series of lectures which were open

ACKNOWLEDGEMENTS
My thanks are due to the Department of ernors and Principal H. B. Nisbet of the
Scientific and Industrial Research, the College for enthusiastic support and en
Science Research Council, and the United couragement. Finally, I wish to acknowledge
Kingdom Atomic Energy Authority, for the permission granted by G. & J. Weir,
initial sponsoring and continued support Ltd., to refer to some work done on their
of the desalination research at Heriot-Watt behalf.
College. I am also indebted to the Gov

REFERENCES
1. Silver, R. S.: "Review of distillation air flowing in porous tubes with uni
processes for fresh water production form extraction at the walls," J.Mech.
from the sea," First European Sym Eng.Sc. in press (probably Sept. 1965) .
posium on Fresh Water from the Sea,
(Athens, 1962) Dechema Monographien 5. Silver, R. S.; Wallis, G. B.: "A simple
no. 47, pp. 19-42. theory of condensation pressure drop,"
2. Silver, R. S.: Nominated Lecture, Ptoc. J.Mech.Eng.Sc. in press (probably Sept.
l.Mech.E. no. 179, p. 1S5, (1964-65) . 1965).
3. Silver, R. S.: "An approach to a gen 6. Drummond, G.: Heriot-Watt Fellowship
eral theory of surface condensers." Ptoc. thesis (in preparation).
l.Mech.E. no. 178, p. 539, (1965-64) . 7. Benjamin, M. W.; Miller, J. G.: Trans.
4. Wallis, G. B.: "Pressure gradients for A.S.M.E., no. 65, p. 419, (1941) .
8. Silver, R. S.: "Temperature and pres 11. Tribus. M.: "Therraoeconomic con
sure phenomena in the flow of saturated siderations in the preparation of fresh
fluids," Proc. Roy. Soc. A. no. 194, p. water from sea water," First European
464. (1948). Symposium on Fresh Water from the
9. Simpson, H. C: Silver, R. S.: "Theory Sea, (Athens. 1962) Dechema Mono
of one dimensional two-phase homoge graphien no. 47, pp. 45-70.
nous non-equilibrium flow," /. Mech. E. 12. Simpson. H. C; Silver, R. S.: "Tech
Symp. on Two-Phase Flow, London, nology of sea water desalination," paper
(Teb. 1962) . given to American National Academy
10. Silver, R. S.: Internal report, G. & J. of Söence/O.S.W. Conference, Wood's
Weir, Ltd. (1957). Hole, Massachusetts (June 1961).

ALPHABETICAL LIST OF SYMBOLS


A cross-sectional flow area P absolute pressure
Cm concentration of noncondensable gas at isentropic equilibrium vapor weight
the surface of condensation fraction
concentration of noncondensable gas in isenthalpic equilibrium vapor weight
the main stream fraction
specific heat of saturated water S specific entropy
E. specific energy dissipated in flow T absolute temperature
E, specific kinetic energy of flow velocity of flow
velocity of flow of cold water for same
H specific enthalpy pressure difference
L latent heat of evaporation V specific volume
m condensation rate weight per unit time w rate of flow, weight per unit time
per unit surface area general vapor weight fraction

SUFFIXES
w saturated liquid phase s saturated vapor phase

GREEK
ß Fraction of equilibration »r- Frictional Reynolds Flux with conden-
if. Frictional Reynolds Flux in absence of sation at rate m.
condensation

SUMMARY OF DISCUSSION
It was asked whether fully introduced It was commented that a new concept in
hydrophobic areas can be used and whether engineering is being developed and that
the use of these areas has been studied. The engineers are looking to the possibility of
reply was that nothing of interest has been obtaining utility of kinetic energy from
found concerning this. When asked if geom- flashing steam. Another comment was that
etrv of flash chambers has been studied, the reduction in friction in the condensation
author stated that it is hoped that geometry phenomenon is being studied and that if
can be put into practice; high water has mass flux is increased, the momentum flux
been studied, however, the main objective with small amounts of liquid on the wall
is to get knowledge first and then to deter will be increased.
mine how to use it.
Quelques Problèmes et Travaux de

Recherche Concernant le Procède de

Distillation Instantanée en Etages

Multiples

R. S. Silver, M.A., D.Sc., M.I. Mech.E., F. Inst.P., F.R.S.E.

Ecosse

La présente communication se borne à ténuer la chute de pression ou même de


examiner les aspects scientifiques fonda rétablir la pression et d'augmenter ainsi
mentaux du procédé de distillation et, dans l'efficacité de l'échange de chaleur. On ob
ce cadre, les caractères particuliers des tient également une notion plus claire des
aspects hydrodynamiques et thermody effets produits par les gaz non conden-
namiques. Les travaux dont nous indiquons sables, ce qui devrait contribuer à une
les grandes lignes sont effectués par le amélioration utile de la conception de ces
bureau d'études industrielles du Heriot- installations.
Watt College d'Edimbourg, Ecosse, au titre L'auteur présente une analyse de la
d'une subvention accordée par le Conseil circulation adiabatique instantanée fonda
de la Recherche scientifique du Royaume- mentale qui définit certains concepts utili
Uni. sables pour des études expérimentales et
Les résultats expérimentaux mentionnés utilisables comme paramètres pour les
confirment quelques travaux récents sur la ingénieurs d'étude. On démontre qu'il
théorie de la condensation. Ils permettent existe des possibilités d'utilisation de l'éner
d'espérer que l'on pourra mettre au point gie libérée au cours de la vaporisation
du matériel de condensation pour le procédé instantanée et on indique quelques direc
de distillation instantanée permettant d'at tives sur la marche à suivre.

10
Некоторые Проблемы и Исследовательская

Работа в Области Многоступенчатого

Процесса Мгновенной Дистилляции

Р. С. Силвер, Магистр искусств, Доктор наук, Член Института инженер-


механиков, Член Пет. Института, Член Эдинбургского королевского
общества

Шотландия

Эта статья ограничивается рассмо пад давления или даже приведет к ре


трением основной теории дистилляци- генерации давления, благодаря чему
онного процесса и входящих в нее спе повысится коэффициент полезного дей
цифических характеристик гидродина ствия теплопередачи. Понимание дей
мических и термодинамических сторон. ствия газов, не поддающихся конден
Описанная в общих чертах работа ве сации, тоже возросло, а это должно
дется в Инженерно-механическом от привести к усовершенствованию кон
деле университетского колледжа им. струкции.
Гериот-Уатт в г. Эдинбурге, Шотландия, Представлен анализ основного пото
с помощью субсидии со стороны На ка с адиабатическим мгновенным вски
учно-исследовательского совета Соеди панием, уточняющий полезные идеи
ненного Королевства. для экспериментальных исследований,
В доклад входят результаты опытов, применимые в качестве параметров
которые служат вспомогательным осно проектирования. Отмечено, что суще
ванием для некоторых последних до ствуют возможности использовать
стижений теории конденсации. Они энергию, освобождаемую во время
дают надежду на возможность скон мгновенного вскипания, и намечены
струировать такое конденсационное пути, по которым должно идти экспе
оборудование для процесса мгновенной риментирование.
дистилляции, которое уменьшит пере

11
Algunos Problemas e Investigaciones

Sobre el Proceso de Destilación

Instantánea de Etapas Multiples

R. S. Silver, M.A., D.Se., M.I.Mech.E., F.Inst.P., F.R.S.E.

Escocia

Este trabajo se limita a considerar la modo de reducir la caída de presión o aun


ciencia básica del proceso de destilación y lograr recuperación de presión y de esa
dentro de ella, los rasgos particulares de los manera mejorar la eficiencia de la transfe
aspectos hidrodinámicos y termodinámicos. rencia de calor. El conocimiento de los
El trabajo señalado se desarrolla en el De efectos de los gases no condensables también
partamento de Ingeniería Mecánica del se ha visto profundizado y esto debería
Colegio Heriot-Watt, Edinburgo, Escocia, conducir a beneficiosas mejoras de diseño.
bajo una donación del Consejo de Investiga Se presenta un análisis del flujo instan
ciones Científicas del Reino Unido. táneo básico adiabático en el que se definen
Se informa sobre los resultados experi conceptos adecuados para trabajos experi
mentales que ofrecen pruebas en apoyo de mentales y para ser usados como parámetros
algunos desarrollos recientes de la teoría de de diseño. Se muestra que existen posibili
condensación. Estos resultados dan lugar a dades para utilizar la energía liberada en el
la esperanza de lograr el diseño de equipo proceso de destilación instantánea y se
de condensación para el proceso de destila indican vías de experimentación.
ción instantánea (flash distillation) de tal

12
Influence of Membrane Phenomena

on Electrodialysis Operation

G. S. Solt, B.Sc., A.M.I.Chem.E.

United Kingdom

GENERAL
On paper the electrodialysis process of de these lines must continue.
salination is an elegant and simple concept Much more serious than the engineering
and its economics are highly favorable in difficulty was the fact that, in spite of a vast
the lower salinity ranges. While economic literature on membrane phenomena, one
limitations generally restrict electrodialysis vital aspect was very imperfectly under
to the conversion of brackish waters below stood. The dynamic performance of the
10,000 or even 5,000 ppm, there are many membrane is the essential core of the proc
cases where electrodialysis has an apparent ess, and the behavior of the membrane-
economic place for treating sea water when solution interface is an important factor in
used in conjunction with one of the other this performance. If a membrane fails to
processes (réf. 1) . Now that reverse osmosis meet design requirements, the failure is
is receiving so much publicity, it may be of basic; unlikç engineering failure, it cannot
interest to point out in passing that reverse be overcome by ad hoc means.
osmosis of sea water yields an intermediate We have come to realize that quite differ
product at about 2.000 ppm level, and that ent membrane properties are required for
it may well prove more economical to pro different applications. The electrodialysis
duce potable water by electrodialysis than process is being used for three major types
by a second reverse osmosis stage. of applications. In Japan the process has
So far. however, the process has not reallv been developed for the enrichment of sea
fulfilled these high expectations. In prac water to yield strong brine. For this pur
tice, these have been two obstacles to their pose the membrane resistance and selec
realization. The first is that the process has tivity are by far the most important criteria.
brought novel engineering problems which Another group of purposes is found in vari
could only be solved with time and experi ous process applications, and in these the
ence. It is fair to say that 15 years ago the problems are manifold. Most commonly,
general level of engineering technology, was however, it will be found that the tempera
simply inadequate to meet the stringent and ture and chemical resistance of a membrane
manifold demands made by the process. For are of prominent importance. At this Sym
instance, neither plastics fabrications for posium we are concerned only with desalin
slack internals nor suitable materials for ation of brackish water to yield potable
electrodes were available at that time. In water. For this purpose we have found that
deed there is still room for progress in such the kinetic properties of a membrane are
matters, and the development effort along frequently the controlling factor.

THE PROPERTIES OF ION-EXCHANGE MEMBRANES


Membranes of widely differing types are properties. These include such parameters
hieing marketed by various manufacturers as ion-exchange capacity, selectivity, water
who specify a large number of membrane permeability, electrical resistance, and vari
ous mechanical properties such as burst and water field; all available membranes are at
tensile strength. Unfortunately the desirable least good enough for a workable plant.
properties of these parameters are no guar On the other hand, the physical prop
antee that a membrane will give good per erties of most nonreinforced membranes are
formance in actual operation. Indeed, this not really adequate for satisfactory opera
stricture applies to an exhaustive list of 27 tion on a large scale. Ion-exchange resins
tests summarized by the Office of Saline are essentially gel structures. As such, they
Water (ref. 2) . None of these tests measure are bound to show dimensional change be
the kinetic properties which provide the tween different ionic forms and concentra
basis for the behavior of membranes on tions. On a membrane length of 150 cms,
polarization. Since we conclude that at sal changes of 2 per cent or over are difficult to
inities below 100 meq/1. the economic de accommodate. We have also found a tend
sign of a plant, even with kinetically good ency toward plastic deformation under com
membranes, is controlled by polarization pression which is probably inherent to this
criteria, this is a serious lacuna (ref. 3) . type of material. These mechanical short
Before passing on to a discussion of polari comings can certainly be tolerated if no
zation experience, which is the major pur alternative reinforced membrane is avail
pose of this paper, it can be stated that able, but they inevitably increase the rate
except in this respect most commercially of membrane writeoff. This rate is already
available membranes would be adequate for one of the major running cost factors in
brackish water work. The membrane resist any realistic pricing, hence the mechanical
ance properties and the selectivity of mem properties of membranes are extremely
branes are not overcritical in the brackish important.

POLARIZATION THEORY AND PRACTICE


The more fundamental aspects of this cept "X" at zero diluate resistivity is equiva
subject have been dealt with in Dr. Cooke's lent to the total resistance (in ohms cm*)
paper at this Symposium (ref. 4) to which of two membranes and of the concentrate
the present paper is in part a sequel. Dr. cell, all of which are held constant in this
Cooke has drawn attention to the fact that experiment. The slope of the line repre
even in the most idealized compartment, sented by the angle 8 is, from dimensional
the local conditions for mass transfer are analysis, in units of cms. In fact it repre
not uniform. The situation is especially sents the equivalent thickness of the diluate
complex when liquid flows through narrow cell. Our normal apparatus has a 1.3 milli
compartments which are provided with meter cell, so that the theoretical value for
spacers to support the membranes and to tan 0 is 0.13. This is the value which would
promote mixing (refs. 6, 7). be obtained from an otherwise empty cell
In order to obtain an overall estimate of containing diluate at the recorded concen
polarization phenomena for practical pur tration, without any of the factors which
poses, we have devised a simple kinetic test. normally add to the resistance of the cell.
The test uses a small laboratory stack In practice there is the additional effect
usually composed of about 20 cell pairs, of the separator mesh which lies within the
nominal size 25 cms x 10 cms- Platinum cell and directly obscures a part of the
electrodes are inserted to monitor the volt membrane area. This effect can lie meas
age drop across 10 cell pairs in the center ured directly by determination of the a-c
of the experimental stack. A batch of brack resistance of the cell, which in our design
ish water is recirculated through this appa is found to be 20 to 40 per cent higher than
ratus at constant potential across the 10 test the theoretical value. The d-c resistance,
cell pairs. The concentration of the diluate i.e., the resistance which results when ion
stream and the current density are allowed transport actually takes place, is greater
to vary while all other parameters are kept again because of the diffusion films on the
constant. The current flowing and the dilu membrane surfaces. In this context the non
ate conductivity are recorded at frequent uniform mass transfer conditions mentioned
intervals. The values thus obtained, cor above must again be borne in mind. Be
rected for leakage currents if necessary (ref. cause the value of this resistance component
5), are used to calculate the cell pair re varies with the degree of depletion of the
sistivity (in ohms cm") . When this is plotted films, it is meaningful only in the context
against the diluate resistivity (in ohms cm) , of known conditions of liquid flow and
the resulting graph is a straight line of the applied emf.
general form shown in Figure 1. The inter In practice, we find that in good opera-
CELL PAIR
RESISTANCE
II cm2/ CELL

INTERCEPT X

DILUATE RESISTIVITY -ft cm.


FIGURE 1. DILUTE RESISTIVITY-CELL PAIR
RESISTIVITY GRAPH.

tion we expect tan © to be of the order of system. This type of experience is rare. Very
02 to 022. Bearing in mind that the test is commonly, however, we have found slopes
carried out on a small-scale electrodialysis far in excess of 02 and these are almost
apparatus, the result is an overall average invariably ascribed to polarization.
over what we suppose are quite widely vari The empirical test technique described
able conditions at different points within above is cumbersome and time-consuming.
the stack. Identical results are obtained It is our belief that the overpotential test
from full size stacks, which confirms that devised by Dr. Cooke is of theoretical sig
this test is of practical value for scaling-up nificance as well as being simpler in prac
of results. tice. On the other hand, the kinetic test has
Where the test shows an anomalously the advantage of actually simulating plant
high intercept, this indicates a fault either operation.
in the membranes or in the concentrate

ANION MEMBRANE POLARIZATION


Theory leads us to expect that, all other anion membrane surface. The resulting pH
things being equal, the limiting condition within this stagnant layer can be appre
of polarization would set in on the cation ciably higher than the pH of the bulk
membranes before the anion membranes. In liquid of the concentrate cell. Conditions
practice, this effect is not experienced. Even for scale precipitation are thus set up at the
when polarization of a cation membrane is membrane surface. To avoid actual pre
deliberately induced, no significant trans cipitation, it is necessary to maintain the
port of hydrogen ions results. This is very bulk concentrate pH well below the precipi
unfortunate, as such an effect could be used tation level. This expedient is reflected in a
to lower the concentrate pH and provide an substantial acid consumption. Economically,
alternative to acid-dosing for scale suppres therefore, a mild degree of polarization
sion. Dr. Cooke has discussed some aspects (actual or threatened) affects the running
of this phenomenon (ref. 4) , for which a costs more by the need to suppress scale
satisfactory explanation is still lacking. deposition than by increases of stack re
In practice we are therefore concerned sistance or of coulomb losses. Where polari
only with polarization at the anion mem zation is severe, on the other hand, the stack
brane. This results in copious transport of resistance and/or the inability of the mem
OH' ions which enter the concentrate cell brane to pass more than a small useful cur
through a stagnant layer of water on the rent density become the controlling factors.

MEMBRANE PROPERTIES
Dr. Cooke has pointed out that some fusion films at their surfaces. The failure of
anion membranes are kinetically unsound actual installations led to the intensive re
even when new and has associated their be search effort reported in Dr. Cooke's paper
havior with the presence of additional dif and in this one. The symptoms were a fall
of diluate pH, sharp increase in stack re this source as intrinsically unsound and,
sistance above the expected value, and in because membranes of the same chemical
extreme cases, a total suspension of Ohm's class free of this defect (e.g., those de
Law reflected in a limiting current density veloped by I.C.I., Ltd.) are not commer
which was all but indifferent to an increase cially available, we now prefer to use mem
of applied voltage. We have found that branes of the random copolymer type
these effects appear with greater severity in reinforced with a fabric backing.
high sulphate waters than on test solutions The symptoms described were observed
of sodium chloride. This fact (which has on brand new membranes which had been
been confirmed by Dr. Cooke) provided a exposed only to synthetic brackish waters
major red herring in a problem which was made with distilled water and analytical
already confused enough. reagants. Simultaneously we began to ex
These phenomena were first observed perience trouble with natural waters con
about four years ago in plants using mem taminated with organic matter. In the light
branes of types 'A' and 'T mentioned by of the present state of experience in ion-
Dr. Cooke. The manufacturer of these mem exchange treatment of organically contam
branes (an American company) at first re inated waters, this is not surprising. We
fused to believe that their membranes, found that as a general rule, fouling was
which met all their specified requirements, particularly severe on membranes which
could fail to function satisfactorily. They already possessed an external polarizable
insisted that bad flow distribution, reten film. In such conditions our kinetic test re
tion of air bubbles in the stack, and various ported equivalent cell thicknesses of up to
other mechanical and hydraulic reasons 10 cms, i.e., an increase of 8,000 per cent.
must be responsible for the failure. At last This does not necessarily mean an eighty-
it was recognized that the fault was in fold increase of stack resistance; at high
trinsic to the membranes. The -membrane diluate concentrations the resistance of the
manufacturers and their associates tried to stack is barely affected, but at low concen
characterize and so avoid the fault; but, tration the increase would approach this
though costly, this work was unfruitful. We factor.
feel compelled to regard membranes from

EFFECT OF TEMPERATURE
In the course of one of our pilot investi tion is not a major factor, this figure is
gations we were faced with an anomalous reasonably accurate. Where it is a major
set of results which we were eventually able factor, we found a 4 per cent increase per
to correlate successfully to the temperature degree centigrade. Qualitatively, this is not
of the incoming raw water, which in this unexpected since the increased temperature
case varied rapidly and over an unusually will increase diffusion rates and so decrease
wide range. Hitherto our temperature al the degree of polarization. In the absence
lowance in calculating stack resistance had of theoretical confirmation, we would not
been 2 per cent per degree centigrade, cor wish to put this factor forward as having
responding to the increase in conductivity general validity.
of electrolyte solutions. As long as polariza

EFFECT ON LEAKAGE CURRENTS


Further difficulty resulted from the non- (ref. 5) . The major leakage path available
uniformity of these polarization-prone mem to the current actually passing through a
branes. We discovered that their charac stack is through the concentrate feed system
teristics differ widely between small areas to each cell, and may be represented by a
on a single roll of material. The resistance schematic wiring diagram as shown in Fig
of an individual membrane sheet would, ure 2a. We confirmed experimentally that
therefore, represent a summation of the the major electrical leakage path runs from
characteristics of the total surface exposed. the concentrate cells at the extreme end of
As a result the effective resistance of indi the stack, through the concentrate entry
vidual membrane sheets varies widely about ports, along the concentrate feed duct, and
a statistical mean. back into the concentrate cells at the other
The flow of nonproductive leakage cur end of the stack. With good design this
rents in electrodialysis apparatus has been leakage is harmless and economically insig
described by the author in a recent paper nificant.
<y ALL CELL PAIRS SHOWING LOW RESISTANCE

MAIN PATH OF CURRENT


b/ ONE HIGH RESISTANCE CELL PAIR.

MAIN PATH OF CURRENT


OC - CELL PAIR RESISTANCE. /3 - ENTRY PORT RESISTANCE.
5 - MAIN FLOW DUCT RESISTANCE.
FIGURE 2. LEAKAGE PATH THROUGH THE CONCENTRATE
FEED SYSTEM.

Figure 2b shows the network of a stack through the concentrate system immedi
in which one "rogue" membrane with a ately adjacent to such a membrane. These
very high resistance is placed between other large leakage currents have been known to
membranes with much lower resistances. cause local overheating in the flow ports,
Large currents are bound to be diverted resulting in their physical collapse.

CONCLUSIONS
Our conclusions therefore are these. The sign. It is therefore important to the suc
membranes offered for sale to the public cess of the electrodialysis process that a
are generally adequate with respect to the universally acceptable test technique be
normally recognized parameters. Membranes developed and kinetic characteristics in
which are not mechanically reinforced can cluded in the membrane specification. Dr.
be used, but the additional cost of rein Cooke's work is the only approach to this
forcement tends to be less than the in problem of which the author is aware,
creased running cost resulting from though perhaps other workers have also
frequent dismantling and replacement of produced suitable techniques.
torn membranes. Although a large proportion of the
No manufacturer at present offering world's brackish waters occurs in arid zones
membranes for sale offers in his specifica where organic matter is absent, there is
tion any measure of the kinetic charac increasing interest in the process from tem
teristics of his membranes. In the desalting perate regions where waters tend to be
range in which electrodialysis is accepted contaminated with organic foulants. For
as an economical proposition, the polari such waters, pretreatment by coagulation
zation criterion generally controls plant de and possibly even ion -exchange scavenging

17
may be necessary to avoid membrane foul similar problem of organic fouling in ion-
ing, though pretreatment adds substantially exchange. Manufacturers have produced
to the total cost of the process. Membranes varieties of exchange resins specifically for
vary considerably in their ability to with high fouling resistance, but they have failed
stand organic fouling. Ideally the dynamic signally to produce a reliable test method
test should cover this property also. Dr. by which this property can be accurately
Cooke has measured overpotential charac predicted. The problem lies largely in the
teristics of membranes after exposure to complexity and variety of poisoning anions,
polystyrene sulphonate and other "poison both natural and manmade, which can
ing" anions, and his findings are quali occur in waters. This experience in the ion-
tatively in good agreement with our own exchange field does not, therefore, give rise
practical experience using different types of to much optimism in the analogous prob
membrane. On the other hand, there is a lem of electrodialysis.

SOME EXAMPLES
The instances recorded below (which are of cation membrane fouling (membranes
not drawn from our experience alone) serve type 'A' and type T—150 cms x 50 cms) .
to illustrate the points made in this paper. Example 3: A very large installation was
They are given in chronological order of built at a refinery in Holland to pretreat
occurrence, and show the improved grip on River Rhine water before demineralization.
the subject which we have acquired over The design predicted a 40 per cent removal
the years. During this period, not all plants of incoming salinity. This water is heavily
had these difficulties. contaminated with organic matter, mostly
Example 1: A skid-mounted plant was built of an industrial origin, and partially chlo
for delivery to a location behind the Iron rinated at the municipal waterworks. It is
Curtain. The purchaser was very secretive a notoriously difficult water to demineralize
and we suspected that the plant was re by ion-exchange. At the low influent con
quired for paramilitary purposes. We tested centration (600 ppm) the plant design was
this plant in our own works, using chemi already approaching the limiting current
cals to make up synthetic brackish waters. density criteria for normal desalination.
While the plant fulfilled our own re Within a few hours, performance of the
quirements on all-sodium chloride solu plant had fallen to a removal of 20 per
tion, a high sulphate content reduced the cent and subsequently fell further to a
output by about half. In the absence of removal of only 10 per cent. The initial
customer information regarding the water type 'T' membranes were partially replaced
to be treated, we shipped the plant and by type 'A' membranes but without im
never heard of it again (membranes type provement. Heterogeneous membranes gave
T—100 cms X 40 cms) . a better performance, but their poor physi
Example 2: A brackish water treatment cal properties made them unworkable. This
plant was built at a British military base plant was a total failure and had to be
in North Africa and was commissioned dismantled (membranes type 'A' and type
without process difficulty. The same plant T'—100 cms x 40 cms) •
house also contained an evaporation plant Example 4: A series of trials on the labo
which had been provided with inhibited ratory scale was set up by the Central
hydrochloric acid for tube descaling. The Technical Institute (C.T.I.) -T.N.O. in
electrodialysis plant utilized commercial Holland. The experiment consisted of pass
hydrochloric acid for dosing the concen ing River Rhine water similar to that in
trate. Site staff confused the two grades of example 3 through a laboratory stack. The
acid and used the inhibited acid on the stack was made up of groups of cell pairs
electrodialysis plant. The inhibitor is a comprising most of the world's commer
long chain polyamine which, one may well cially available membranes. A parallel test
imagine, is not good for cation membranes. was set up similar in all respects except that
The resultant erratic resistance rise within the incoming water was pretreated by means
the 400-membrane stack led to the local of a highly porous anion-exchanger in the
heating effects referred to in the body of chloride form (ref. 8) . The voltage drop
the paper, and the plant became unwork at set current densities was observed for
able. Following a complete membrane re each group of cells.
placement, this plant was given a 6-months' As the effects of organic fouling became
test run and has given no further difficulty. apparent, the voltage drop across these
This is probably the only recorded case groups began to rise. In order to maintain
the desired current densities, it became water supply feeding this plant could be
necessary to remove highly fouled groups. taken at will:
The fouling behavior of individual groups (a) Directly from the river
was quite clearly shown to be dependent (b) From a partial cold lime softening
on the anion membrane component and plant
independent of the cation membranes. The (c) From the water in (b) passed
test on untreated water clearly established through a porous ion-exchange
the relative ability of definite types of scavenger.
membranes to resist organic fouling. Mem Two of the three best types of mem
branes of the type 'A' and T' proved to branes shown up by the C.T.I.-T.N.O. test
be among the worst. At the end of the test, were used. We found that over a very long
only three types of membrane remained in time, the performance of the membranes
reasonable working condition. One of these in case (c) was fully up to normal design
was a pilot sample prepared by Dr. Cooke. expectations. In case (b) the maximum
The parallel test on scavenged water current density would be reduced by about
showed a slower onset of fouling in all one-quarter and in case (a) by about one-
cases, but the same relative order of per half.
formance between types of membranes. The In this as in many other installations,
better grades remained substantially un we have found a rapid accumulation of
affected throughout the test. colloidal material electroprecipitated onto
Electrical polarity was reversed in the the membrane surfaces. Despite sand filters
course of these tests but this was not shown this was particularly serious in case (a) .
to have any long-term beneficial effect. The inference is that coagulation pretreat-
Example 5: A small plant was running on ment is essential if the water is turbid
a duty similar to that in example 3. The (membranes 100 cms x 40 cms)

SUMMARY
The electrodialysis process has had set individual cases will remain fraught with
backs due to engineering difficulties and uncertainty. Exploratory work done in the
membrane failure. Of these, membrane laboratories of I.C.I., Ltd., in England has
failure has been far more serious and has provided a straightforward basis for investi
shown that some important operating fac gating these matters. C.T.I.-T.N.O. in Hol
tors have been largely ignored in the past. land has also continued work along these
Unless and until membrane manufacturers lines. It would be highly beneficial if gen
are fully conversant with these problems eral international agreement on the validity
their measurement, and their cure, the in of this work could be reached.
stallation of electrodialysis plants in mam

REFERENCES
1. Hitchcock, A.; Minken. A. A. L.; Min- Symposium on Water Desalination,
ken, J. W.: "Nuclear powered electro- Washington, D.C. (Oct. 1965) .
dialvsis for desalination," Euronuclear 5. Solt, G. S.: "Leakage currents in elec
(Feb. 1965) . trodialysis," A.I.Ch.E./I.Chem.E. Meet
2. U.S. Office of Saline Water: "Test ing, London (June 1965) .
manual for permselective membranes," 6. Cooke, B. A.: Electrochimica Acta
R. & D. Progress Report No. 77 (Jan. No. /, (1961) , p. 179.
1964).
3. Solt, C. S.; Wegelin, E.; Chapman. 7. Cooke, B. A.; van der Walt, S. J.:
C. V. G.: "Electrodialysis as a unit Electrochimica Acta No. 5, (1961) .
operation," British Chem. Engineering p. 216.
(July 196S) . 8. Downing, D.; Hetherington, R.: "Mac-
4. Cooke, B. A.: "Some phenomena asso roreticular anion-exchange resins,"
ciated with concentration polarization International Water Conference, Pitts
in electrodialysis," First International burgh, Pa. (Oct. 1963) .

19
SUMMARY OF DISCUSSION
It was commented that in addition to was stated that experience in Israel has
attributing polarization to the quality of shown that the cell configuration has a
the water, it is also important to consider pronounced effect on polarization and that
stack geometry, velocity, and flow distribu any scaling tends to occur in or near stag
tion within the cell compartment itself. It nant flow areas.

Influence Des Phénomènes de Mem

brane Sur le Fonctionnement de

L'Electrodialyse

G. S. Soit, B.Sc. A.M.I.Chem.E.

Royaume-Uni

Le procédé d'élcctrodialyse n'a pas ré On peut s'attendre à ce que divers facteurs


pondu aux espérances du début. Les diffi contribuent en pratique à renforcer cette
cultés techniques ont été progressivement valeur théorique d'environ 50%. Les va
surmontées avec le temps, mais un aspect leurs de la pente notablement au-dessus de
important du comportement des membranes 150% de l'épaisseur de la cellule, peuvent
dans le procédé d'électrodialyse a été être attribuées à la polarisation, c'est à
jusqu'ici largement méconnu. Il s'agit de la dire au défaut de permettre le transport
faculté que possède la membrane d'y laisser normal par diffusion d'ions en quantité suf
passer les ions et de permettre leur diffu fisante pour supporter la densité du
sion. Cette faculté peut être mesurée comme courant prévue.
étant la résistance ohmique de la mem Cet essai empirique quelque peu encom
brane à diverses densités de courant con brant peut être amplifié avec d'excellents
tinu, mais elle n'est pas déterminée par la résultats et par conséquent se révèle d'une
mesure de la résistance utilisant le courant utilité immédiate.
alternatif. Il se peut que la polarisation, lorsqu'elle
Les critères retenus à l'heure actuelle se produit, résulte de la densité du courant
pour déterminer la qualité des membranes dépassant le transport d'ions permis par les
sont incomplets. Et c'est précisément à cette conditions hydrauliques de l'expérience.
insuffisance qu'il s'agit de remédier. Lorsque ce facteur ne constitue pas la cause
Ce document fait en partie suite à la de ce phénomène, la polarisation "anor
note communiquée au présent Symposium male" peut être attribuée aux propriétés
par le Dr B. A. Cooke. laquelle traite des cinétiques de la membrane. Nous avons
aspects plus fondamentaux du problème. Il trouvé que la surface de certains types de
décrit également une simple technique de membranes anioniques présente une pelli
laboratoire pour examiner les propriétés cule inerte même lorsque les membranes
cinétiques des membranes. La présente com sont neuves, ce qui retarde la diffusion a
munication décrit comment des expériences un point tel qu'une polarisation anormale
d'électrodialyse effectuées à l'échelle réduite s'ensuit.
en laboratoire peuvent être utilisées pour Nous avons en outre trouvé que les eaux
parvenir au même but. Par un contrôle contenant des matières organiques sont sus
approprié des paramètres, on peut obtenir ceptibles de former des pellicules inertes
un graphique de résistance d'une paire de sur la surface des membranes avec des
cellules par rapport à la résistivité de la résultats similaires.
solution diluée. C'est une ligne droite dont Nous avons également constaté que les
la pente est théoriquement équivalent à membranes qui, à l'origine, possèdent des
l'épaisseur de la cellule de solution diluée. propriétés anormales sont bien plus prédis
posées aux dépôts organiques que celles polarisation joue un rôle majeur, le rende
qui ne sont pas ainsi affectées. L'effet con ment de l'installation est beaucoup plus
jugué de ces deux facteurs peut donc avoir sensible aux variations de température en
des conséquences fort désastreuses. Une comparaison avec le fonctionnement dans
installation réelle dont le fonctionnement des conditions normales. La variation du
serait soumis à ces effets non seulement rendement atteint environ le double de ce
consommerait une énergie électrique exces qui se produirait normalement.
sive, mais pourrait se révéler absolument La communication se termine par un
incapable de produire de l'eau traitée ayant argument en faveur d'une recherche accrue
la salinité requise. En outre, l'installation destinée à parvenir à une parfaite compré
est plus exposée au dépôt de tartre dans hension du comportement cinétique des
les cellules du concentrât. membranes, et propose qu'un accord inter
Nous avons noté que chacune des feuilles national se fasse sur une technique d'essai
des membranes faisant partie du même permettant d'évaluer cette propriété. La
envoi avait un comportement très différent méthode du Dr Cooke parait prometteuse.
lors de sa mise en service effective, et la Ce document est accompagné d'un certain
disparité entre les cellules voisines pouvait nombre d'exemples illustrant sur la base
conduire à d'ennuyeux phénomènes de de l'expérience acquise les divers points
pertes électriques. traités dans cette communication.
Nous avons aussi trouvé que lorsque la

Влияние Явлений, Происходящих

в Мембранах, на Работу Электродиализа

Г. С. С о л т , Бакалавр наук, Член-корреспондент Института инжене


ров-химиков

Соединенное Королевство

Процесс электродиализа не выполнил носящегося к более фундаментальным


своих ранних обещаний. С течением сторонам указанной проблемы. Он там
времени технические трудности были тоже описывает простые лабораторные
превзойдены, но до сих пор совершен приемы для исследования кинетических
но игнорировалась одна из важных сто свойств мембран. Настоящий доклад
рон поведения мембраны, относящаяся касается вопроса, как применить лабо
к работе электродиализа. Этим явля раторные опыты малого масштаба в
ется способность мембраны во время области электродиализа для достиже
электродиализа диффундировать через ния той же самой цели. Посредством
себя ионы. Диффузию можно замерить, соответственного регулирования пара
как омическое сопротивление мембра метров можно получить диаграмму со
ны, при меняющихся плотностях посто противления пары ячеек по отношению
янного тока, но при переменном токе к удельному сопротивлению соленого
ее нельзя определить измерением со раствора. Она представляет собой пря
противления. Многие трудности и не мую линию, наклон которой теорети
удачи, возникающие на установках, чески эквивалентен толщине ячейки,
объясняются аномалиями этого пове через которую проходит раствор. Бла
дения. годаря различным способствующим
Сейчас критерии, которыми пользу факторам, эта теоретическая величина
ются для специфицирования качеств вероятно возрастет на практике при
мембраны, неполны и подобный недо мерно на 50%. Величины наклона, зна
статок должен быть исправлен. чительно превышающие 150% толщины
Этот доклад частично служит про стенки ячейки, могут быть приписаны
должением доклада, даваемого докто поляризации, т.е. нарушению нормаль
ром Б. А. Куком на Симпозиуме и от ного диффузионного переноса доста
точного количества ионов при ожидае ную электрическую энергию, но вооб
мой плотности тока. ще сможет потерять способность про
Это несколько громоздкое эмпири изводить опресненную воду с желае
ческое испытание можно успешно про мым солесодержанием. Кроме того, на
водить в большом масштабе, а потому установке повысится образование на
оно полезно для чисто практических кипи в ячейках концентрата.
целей. Мы нашли, что отдельные листы мем
Поляризация возникает, когда плот бран, выбранные из одной общей пар
ность тока превышает перенос ионов, тии, сильно отличались в функциональ
который допускают гидравлические ном отношении, а несоответствие меж
условия, существующие во время опы ду прилегающими ячейками способ
та. Если этот фактор не является при ствовало неприятным явлениям утечки
чиной, то сабнормальную» поляризацию электрического тока.
можно приписать кинетическим свой Мы далее открыли, что в условиях
ствам мембраны. Мы нашли, что неко сильной поляризации, производитель
торые типы даже совершенно новых ность установки гораздо более чув
мембран, имеют инертные поверхност ствительна к переменам температуры,
ные пленки, которые настолько тормо чем это бывает на работе в нормаль
зят диффузию, что за ней следует аб- ных условиях. Колебания производи
нормальная поляризация. тельности превосходят почти в два ра
Далее мы обнаружили, что воды, со за нормальный уровень.
держащие органические вещества, спо Доклад заканчивается просьбой на-
собствуют образованию инертных пле пречь исследовательские усилия для
нок на поверхностях мембран, что при полного понимания кинетического по
водит к аналогичным результатам. ведения мембран, и выработать меж
Мы также нашли, что мембраны, об дународное соглашение по вопросу
ладающие с самого начала аномальны технических испытаний, предназначен
ми свойствами, гораздо более подвер ных для определения этого свойства.
жены органическому загрязнению, чем Метод доктора Кука выглядит много
те, которые их не имеют. Поэтому сов обещающим.
местное воздействие этих двух факто Приложен ряд наглядных примеров,
ров может оказаться весьма вредным. которые иллюстрируют на основании
Им на работе подверженная установка пройденного опыта различные пункты
не только будет расходывать избыточ доклада.

Influencia de los Fenómenos de las

Membranas Sobre el Funcionamiento

de la Electrodialisis

G. S. Solí, B.Sc, Ingeniero Químico A.M.I.

Reino Unido

El Proceso de Electrodiálisis no ha cum miento. Puede medirse como la resistencia


plido su promesa inicial. Las dificultades óhmica de la membrana a distintas densi
técnicas han sido solucionadas gradualmente dades de corrientes continua pero no se
con el tiempo, pero un importante aspecto puede determinar mediciones de resistencia
del comportamiento de las membranas en el utilizando corriente alterna. Muchas dificul
funcionamiento de la Electrodiálisis ha sido tades y fallas en las plantas pueden atri
mayormente ignorado hasta el presente. buirse a anomalías en este comportamiento.
Este se refiere a la capacidad de la mem Los criterios empleados en el momento
brana de permitir la difusión iónica a para especificar la calidad de las membra
través de sí misma durante el funciona nas son incompletos, y esta situación debe

22
remediarse. dencia a formar películas inertes sobre la
Este trabajo es, en parte, una continuación superficie de las membranas con resultados
del presentado por el Dr. B. A. Cooke en este análogos.
Simposium, el cual trata los aspectos más Además, hemos descubierto que las mem
fundamentales de este problema. También branas que poseen propiedades anómalas
describe él una técnica de laboratorio sen tienen una tendencia mucho mayor al
cilla para examinar las propiedades cinéticas "envenenamiento" por materia orgánica que
de las membranas. El presente trabajo des aquéllas cuyas propiedades son normales.
cribe la forma en que puede lograrse el El efecto combinado de estos dos factores
mismo objeto mediante experimentos de puede ser, por consiguiente, completamente
Electrodiálisis en pequeña escala realizados desastroso. En la práctica, una planta cuyo
en el laboratorio. Mediante el adecuado rendimiento estuviera menguado por estos
ajuste de los parámetros, se puede obtener efectos, no sólo consumiría excesiva energía
una gráfica de la resistencia del par de eléctrica sino que podría ser totalmente in
células en función de la resistividad del capaz de producir agua tratada de la salini
diluto. Este es una recta cuya pendiente es dad deseada. La planta, además, posee una
teóricamente equivalente al espesor de la mayor tendencia a la formación de costra
célula de diluto. En la práctica, hay varios en las células de concentrado.
factores aditivos que pueden aumentar este Hemos encontrado grandes diferencias de
valor teórico en alrededor de un 50%. Los funcionamiento entre láminas de membrana
valores de la pendiente que excedan al individuales tomadas de la misma partida.
espesor celular en más de un 150% pueden De producirse esta disparidad entre células
atribuirse a la polarización—es decir, a no adyacentes, podría originar pérdidas eléc
haber permitido el transporte por difusión tricas desconcertantes.
normal de suficiente cantidad de iones para También hemos descubierto que, cuando
llevar la densidad de corriente esperada. la polarización constituye un factor de im
Esta prueba empírica, en cierto modo en portancia, el rendimiento de la planta es
gorrosa, reproduce las condiciones de trabajo mucho más sensible a los cambios de tempe
en mayor escala con considerable éxito y ratura que lo que sería de esperar en condi
por esto resulta de utilidad práctica in ciones normales de funcionamiento. La
mediata. variación en el rendimiento es aproximada
Cuando se experimenta polarización, ello mente el doble que la que se experimentaría
puede deberse a que la densidad de corrien normalmente.
te excede al transporte iónico que permiten La presentación del trabajo concluye pi
las condiciones hidráulicas del experimento. diendo se realice más investigación dirigida
Cuando este factor no es la causa, la polari hacia el alcance de una completa compren
zación "anómala" puede atribuirse a las sión del comportamiento cinético de las
propiedades cinéticas de la membrana. membranas y solicitando un acuerdo inter
Hemos descubierto que ciertos tipos de nacional sobre un método de prueba para
membranas aniónicas poseen películas su evaluar esta propiedad. El método del
perficiales inertes aun cuando son nuevas, Dr. Cooke parece ser promisorio.
las cuales retardan la difusión en grado tal Se agrega un número de ejemplos descrip
que provocan polarización anómala. tivos tomados de experiencias reales, los
También hemos observado que las aguas cuales demuestran los puntos expuestos en
que contienen materia orgánica poseen ten el texto del trabajo.

23
Scale Control in Sea WaterDistillation

Toshihiko Matsuda, Shinkitchi Akimoto, and Yoshio Taniguchi

Japan

INTRODUCTION
Distillation has been widely used for under reasonably careful control, this
obtaining potable water from the sea. The method seems to minimize scale deposition.
major troubles encountered in sea water It is reported that successful operation of
distillation are scale formation and corro a large-scale sea water distillation unit is
sion. The deposition of scale on heat trans achieved by addition of acid for pH con
fer surfaces and prevention of such deposits trol. However, acid treatment of feed water
hive been of interest for many years, both usually leads to unavoidable corrosion in
from a scientific and an economic stand all parts of the evaporator. There is a risk
point. Scale brings undesirable effects: that of serious corrosion if control is not careful.
is, it increases resistance to heat transfer. The second is a physical method in con
In general, three types of scale form in trast to the chemical method (addition of
sea water distillation: calcium sulfate, cal acid) . The principle of this method is to
cium carbonate, and magnesium hydroxide. control scale-forming constituents so that
Occurrence of these deposits depends on the deposit occurs on a surface other than
temperature, brine concentration, pH of the heating surface. An example of this
brine, and so on. Sulfate scale is usually method is the contact stabilization process
formed in the concentration of brine above proposed by Langelier (ref. 2) and his co
the solubility of calcium sulfate. The de workers, in which brine from the evapora
position of calcium carbonate and mag tor is continuously circulated through a
nesium hydroxide is primarily attributed bed of granular particles, such as sand or
to chemical equilibrium observed between limestone. Many seed-recycle processes (ref.
bicarbonate and carbonate ions in the brine 3) , in which fine crystals of scale-forming
(ref. 1) . When sea water is heated, the bi constituents (such as Mg (OH) „ CaCO„ or
carbonate ion decomposes into the carbonate CaSO,) are kept suspended in the evapora
ion and carbon dioxide. The decrease in tor, attempt to prevent scale deposition on
solubility of carbon dioxide caused by in heating surfaces. In Japan, many plants for
crease in temperature tends to drive this recovering salt from sea water have been
reaction. The carbonate ion (formed as ex running for many years without serious
plained above) may react with the calcium scaling troubles. In these plants, scale is
ion to precipitate calcium carbonate or may prevented by mixing the feed sea water
decompose with further evolution of carbon with the highly concentrated mother liquid
dioxide and formation of hydroxide ions. (ref. 4) .
The hydroxide ion may react with the The authors have developed a new scale
magnesium ion to precipitate a form of control method which combines chemical
magnesium hydroxide. Temperature level and physical features. With the new meth
primarily determines whether calcium car od, scale control can be easily carried out
bonate or magnesium hydroxide predom by adding a given amount of a scale-
inates in the deposited scale. preventing agent to feed water and keeping
In general, two methods are used for it in suspension in brine. The additive
scale control. (commercially named "Kuriverter" by the
The first is addition of arid (such as authors) consists mainly of a kind of clay.
sulfuric acid or acid salt) to feed water The additive is fine enough to remain in
to control the rise of alkalinity. If kept suspension. The particles of the scale
preventing agent accelerate the deposition forced circulation evaporator was used;
of scale-forming constituents on particles of distillation capacity of the evaporator was
the additive rather than on heating sur 30 to 50 liters per hour. Brine concentra
faces. The additive seems to act as an acid tion for the series of experiments was
in the distillation of sea water. It should maintained at 8° to 9°B£ (s.g. 1.058 to
be noted that a careful control is not 1.066 at 15°C) to avoid formation of cal
critical for addition of the additive. cium sulfate scale. The brine was kept at
The present study was made to observe about 105°C. The flash evaporator was
how the additive suppresses scale formation operated at atmospheric pressure.
in sea water distillation and how operating The study revealed an appreciable pos
conditions (i.e., brine velocity, pressure, sibility for use of "Kuriverter" as a scale-
and temperature difference) influence the preventing agent.
action of the additive. In the experiment, a

EXPERIMENTAL
DESCRIPTION OF EQUIPMENT
AND OPERATION shown in Figure 3 and Table II. The
A multitube forced circulation evapora- plant consisted mainly of a brine heater,
tor with auxiliary equipment was used as a furnace, a flash tank, and a condenser.

TABLE II. Construction Features of the Evaporation Plant

Vertical coil of tube: 700 mm D. x 2,300 mm


Heat transfer medium heater Diameter of tube: 32 mm O.D.
Type of heater: one through
Heat transfer area: 6.8 m-
Type: special gear Head: 30 m
Heat transfer medium pump Delivery pipe: 50 mm Capacity: 180 l./min
Revolution: 400 rpm Motor power: 3.7 kw
Type: multitube heat exchanger, four through
Brine heater Shell: 150 mm I D. x 1.100 mm length
Tube: 13.4 mm I.D. 810 mm length
Material of tube: aluminum-brass
Heat transfer area: 0.58 m2 (16 tubes)
Evaporator Top: cylindrical 600 mm I.D. x 700 mm
Bottom : conical
Head: 20 m Capacity: 0.33 m'/min
Brine pump Delivery pipe: 80 mm Motor power: 3.7 kw
Revolution: 1.450 rpm
Type: multitube heat exchanger, one through
Condenser Shell: 160 mm I.D. x 300 mm
Material of tube: aluminum-brass

TABLE III. Properties of Chlorinated condenser was immediately mixed with


Diphenyl Used as Transfer Medium brine in the flash tank and heated to the
temperature of the brine. Chlorinated
diphenyl was used as a heat transfer me
Temperature CO 100. 200. dium. Properties of the chlorinated diphenyl
Specific gravity 1.38 1.28 are shown in Table III. The heat transfer
Viscosity C. P. 5.7 1.0 medium was circulated through the circu
lating gear pump from the heating coil in
Specific heat Kcal/kg °C 0.293 0.326 the furnace to the brine heater. Heat was
Thermal transferred to the brine from the heat
conductivity Kcal/m-hr °C 0.083 0.079 transfer medium in the brine heater. Heated
Steam pressure mmHg 0.16 18.0 brine was evaporated in the flash tank.
The concentrated brine was returned from
Remarks: Colorless and uncorrosive the flash tank to the brine heater through
against metal at high temperature the brine pump. Part of the concentrated
brine was continuously blown down, main
Sea water was fed to the condenser. Some taining the concentration at 8°Be and a
of the feed water passing through the fixed level in the flash tank. Vapor formed
in the flash tank was cooled with the feed gage, valve, and flow meter were fitted to
water to condense in the condenser shell the pipeline serving each group. Brine ve
and collect in the fresh water tank. locity and pressure in each group could be
The brine heater consisted of 16 tubes, controlled by valves. The brine heater
having a total heating surface of 0.58 could easily be separated from the flash
square meters. The tubes were divided into tank. The method of tube installation sim
four groups, each group having a heating plified removal of tubes for inspection and
surface of 0.145 square meters. A pressure sampling of deposited scale on internal

27
surfaces of the tubes. The temperature of ing equation (ref. 5) so as to be comparable
!he heat transfer medium could be con with operations utilizing steam as a heat
trolled by the fuel feed to the furnace. transfer medium.
Liquid level in the flash tank was automati tw = tc H >H/ *H (Tc - tc) (1)
cally controlled by a solenoid valve de T»H/0H + »L/0Ll ' 1 ;
signed to govern the flow of feed water. where:
The valve responds only to a change in tc = temperature of colder fluid (brine)
liquid level of the flash tank. Any slight (°C)
variation in brine velocity, brine concentra "H — film coefficient of heat transfer for
tion, or temperature of the heat transfer warmer fluid (Kcal/hr m'°C)
medium was corrected as soon as it occurred. hL — film coefficient of heat transfer for
The operating procedures in each run colder fluid (Kcal/hr mJ°C)
were: = viscosity correction factor for
1. Fill the flash tank with sea water to warmer fluid
a fixed level; ^L = viscosity correction factor for
2. Drive the brine pump and the heat colder fluid
transfer medium pump; Tc = temperature of warmer fluid (°C)
3. Ignite the burner in the furnace;
4. Gradually raise the temperature of DETERMINATION OF DEPOSITED SCALE
the circulating heat transfer medium The brine was drained from the evapora
to a definite degree. tor after testing. Inlet and outlet side
The additive was periodically supplied headers of the brine heater were removed,
in the form of 0.4 per cent suspension to then the tubes of the heater were washed
the flash tank by a slurry pump. The ex with water. One of these tubes was taken
periments were conducted at the concentra out for complete inspection and analysis of
tion of 100, 160, and 200 mg per liter of the scale. A new tube of the same kind
feed water. was used as a replacement. To prepare the
During continuous operation, the follow tubes for the next trial, 5 per cent hydro
ing were measured once an hour: chloric acid solution was circulated in the
1. Fuel consumption (1/h) heater tube. The removed test tube was
2. Temperature of heat transfer treated for the determination of the scale
medium (°C) by the following method:
3. Brine velocity (m/s) 1. Determination of Adhered Scale. Scale
4. Feed rate of sea water (1/h) was analyzed as follows: The two 10-cm
5. Distilled water (1/h) long pieces, of which heat transfer area
6. Blow down of brine (1/h) was 0.48 dra!, were cut off from the ends of
7. Brine concentration (°B£) the tube for determination of the deposited
8. Brine temperature (°C) scale. The total weight of these cut-off
9. Brine pressure (kg/cm2) tubes was measured after cleaning the ex
10. Added amount of the additive (g/h) ternal surfaces of the tubes and drying at
11. Liquid level in the evaporator 100° to I10°C in a hot air bath. The scale
Every 3 to 6 hours, the following data was removed with 50 ml of one normal
were taken: nitric acid. Next, the tube was washed with
12. pH of brine water, dried, and weighed. The difference
13. Content of total iron ion between tube weights before and after acid
14. Brine concentration (chloride) cleaning was represented as the weight of
15. Content of the additive the scale. Thickness of the scale was calcu
lated from the density of the adhered scale,
Since thermal conductivity of chlorinated regarded as about two, and the total weight
diphenyl used as a heat transfer medium of the scale.
is low (Table III) , its coefficient is also low.
Therefore, the difference between the tem 2. Scale Analysis. The nitric acid solution
perature of the medium and the tube wall was heated to dissolve the collected scale.
is large. Temperature difference is usually The acid insoluble portion of the scale was
expressed as the difference between the filtered, washed, ignited, and weighed. The
temperature of a warmer fluid (such as filtrate was analyzed for magnesium, cal
steam) and that of a colder fluid (such as cium, chloride, and sulfate ion. Kach ion
sea water) ; in the present paper, it is was determined by the following method:
expressed as the difference between brine Mg and Ca : titration with EDTA
temperature, tc, and temperature of tube CI : Mohr's method
wall, tw, which is calculated by the follow SO, precipitation as BaSO,

28
pH TZ- Tistinn^lyZed da>^The ** ThC diStillate COn,ained 5 '° 'S mg of
P Шс dl"'»ate ranged from 5.4 to chloride ions per liter.

RESULTS AND DISCUSSION


SCALE FORMATION WITHOUT ADDITIVE TABLE V. Hours of Operation and Amount
A large amount of white glossy scale was of Scale Deposited on Heating Surface
observed on the surfaces of the brine heater
tube. A photograph of tubes after testing is Time-hours in
shown in Figure 4. Tubes from the inlet operation
side in the brine heater are shown in the 88 139 241
middle of each photograph, tubes from the Total distillate m" 2.71 4.37 7.10
outlet side at the right, and a new tube Amount of scale mit/dm- 1820 3020 5620
before test run at the left. The deposited Thickness of scale mm 0.091 0.151 0.281
scale appeared thicker on the outlet side of Scale constituent r/c
the tube than on the inlet side as shown in % %
Ms 39.2 38.Б 39.3
Figure 4. Analysis of the feed sea water (Mk(OH)j)
and the concentrated brine are shown in (94.1) (92.5) (94.3)
Ca 0.4 0.6 0.3
Table IV. Operating results are shown In CI 1.0
Table V. 1.5 1.1
SO, 3.1 2.2
Fe 0.4 0.4
Operating condition:
No addition of the additive
Brine concentration: 8eBé
Brine pressure in the heater: 0.4 кг/cm'
Brine velocity: 1.6 m/s
Temperature difference: 9.9°C
Total heat transfer area: 0.29 mJ

As seen from Table V, the scale in


creased in proportion to the lime of opera
tion. In the range of scale thickness below
0.28 mm, the amount of scale was approxi
mately proportional to the total volume of
distillate under the experimental condi
FIGURE 4. TUBES AFTER TEST tions. These results lend some support to
the hypothesis derived by McC.abe and
RUN NO. 5 ON SCALING Robinson (ref. 6), in which thickness of
POTENTIAL. adhered scale is proportional to total heal
Operating condition without addition of flux. The pH of the brine was 9.2 on the
the additive average and kept a nearly constant value
Brine velocity: 1.6 m/s during operation.
Temperature différencie: 9.9 С
Hours of operation; a: 88 b: 139 a 241 The deposited scale consisted mainly of
Brine pressure: 0.4 kg/cm* magnesium hydroxide as shown in Table
Brine concentration: 8°Bé V. It contained about 0.5 per cent of cal
cium. Small amounts of chlorides and
TABLE IV. Analysis of Sea Water and sulfates were also present in the scale.
Brine (g/I.) The fact that the scale consists pre
dominantly of magnesium hydroxide agrees
Sea Water Brine closely with results obtained by Miyogawa
CI 18.900 44.000 (ref. 7) in recovering salt from sea water.
Мя 1.265 2.850
Ca 0.395 0.940
SO. 2.500 6.010 EFFECT OF ADDITIVE
HCO* 0.136 0.030 A continuous test was made to study the
CO» 0.080 behavior of the additive as a scale-
pH 8.30 9.25
Concentration CBé) 3.4 preventing agent. The results arc shown in
7.9 Table VI. Figure 5 shows an apparent
Condition in sea water evaporation decrease of scale deposition. Figure 6 shows
Temperature difference: 9.9°C the relationship between the thickness of
Brine velocity: 1.6 m/s
No addition of the additive the scale and the operating time.

29
FIGURE 5. COMPARISON WITH
TUBES OPERATED IN ADDI
TION OF THE ADDITIVE
AND IN NO ADDITION.
Operating
Condition
Concen Tempera rao во
tration ture TIME ■ HOUM IN 0НМТЮМ
of the Hours of differ FIGURE 6. HOURS OF OPERA
Tube additives operation ence TION VS THICKNESS OF
5-b 0 ppm 139 hrs 9.9°C
4-b 200 ppm 155 hrs 9.9°C SCALE.
Brine Brine Operating Condition
Tube velocity pressure Brine velocity: 1.6 m/s
5-b 1.6 m/s 0.4 kg/cm3 Brine pressure: 0.4 kg/cms
4-b 1.6 m/s 0.4 kg/cm3 Temperature difference: 9.9°C
TABLE VI. Operating Results in Addition of the Additive

Added amount of the additive ppm


0 100 200
Hours of operation hr 88 86 168
Amount of scale ml/dm1 1,820 76 87
Adjusted to 30 days operation mg/dm- 14.900 637 397
Analysis of brine (в/1.)
„H 9.25 9.10 8.7Б
CI 14.0 4Б.0 41.0
Mg 2.85 8.04 2.71
Ca 0.94 0.96 0.87
SO, 6.01 6.26 5.Б6
HCC-3 0 030 0.040 0.026
COj 0.080 0.080 0.027
Operating condition
Brine concentration: 8°Bé
Brine velocity: 1.6 m/s
Temperature difference: 9.9°C
Temperature of chlorinated diphenyl: 170°C
Brine pressure: 0.4 kg/cm2
When 200 mg of the additive per liter per liter of feed water was added as a
of feed water was added, the pH of the seeding material to prevent scale formation.
brine was lowered from 9.25 to 8.75, and The additive was sufficient for concentra
the amount of the deposited scale was tions of 0.2 grams per liter of feed water
reduced to one-fortieth of the amount and was more effective in preventing scale
observed in tests without additive. On ad deposition than magnesium hydroxide
ding 100 mg of the additive per liter of seeding.
feed water, the pH of the brine did not Furthermore, no great change of pH in
appear to change, remaining as high as that the brine occurred with excessive amounts
in the case of no additive. The thickness of of additive. No corrosion of metal parts of
the adhered scale was considerably less the evaporator was observed. Therefore,
than that without additive. Under the test careful control was not always necessary
conditions, there was usually no accumula in the additive tests. The results indicate
tion of the additive in the system. that the additive can easily be applied in
According to Shimizu and his coworkers practice.
(ref. 8) , 20 grams of magnesium hydroxide
EFFECT OF TEST CONDITIONS perature difference and the thickness of
ON THE ADDITIVE the deposited scale,
Scale deposition usually depends on the The alkaline scale as Mg(OH) , or CaCO,
operating conditions of sea water distilla is mainly attributed to decomposition of
tion (i.e., brine velocity, temperature dif the bicarbonate ion in sea water. There
ference, pressure, etc.) . The effect of the fore, the decomposition rate depends on the
test conditions on the additive was observed temperature difference, as well as on the
to be as follows: temperature of brine. The temperature
difference had a considerable effect on scale
I. Temperature Difference. The effect of formation as shown in Figure 7. The scale
the temperature difference, tw — tc, on scale thickness was approximately proportional
deposition was investigated by the follow to this difference.
ing method: the amount of the additive is Miyauchi and Moriyama (ref. 9) reported
200 mg per liter of feed water, brine ve
locity 1.6 meters per second, temperature that the deposition rate of hard scale as
difference, tw—tc, 4.6° to 16.2°C brine calcium sulfate was governed by the degree
concentration 8°Be, and pressure in the of supersatuTation on CaSO,. The scaling
brine heater 0.4 kg per cm* gage. Figure 7 potential in the present operation was con
shows the relationship between the tem sidered in terms of the degree of super-

5.0 - A THICKNESS OF SCALE WITH 200ppm OF THE ADDITIVE


5 XIO-6
0 ADOED AMOUNT OF THE ADDITIVE /
:20oppm *
_ X "0 ADDITION OF THE ADDITIVE .

8 20| 2 XIO-6

2
10 I X I0"6 fi-i
CO
to he

CM
0L5 8X»-7 5

02 2 XIO-7
J I ' ■ ■ ■ I J l_
S 10 20 60
TEMPERATURE DIFFERENCE, ^-tg.^C)

FIGURE 7. TEMPERATURE DIFFERENCE VS AMOUNT OF SCALE


DEGREE OF SUPERSATURATION OF Mg(OH)2 IN THE BRINE.
tw: Tube wall temperature in the brine heater
tB: Brine temperature in the brine heater
Kk Solubility product constant of Mg(OH), = 10-" • at 100°C boiling (ref. 5)
Operating Condition
Brine velocity: 1.6 m/t
0.4 kg/cm1
saturation, according to their study. The
degree of supersaturation, Ds, on magne
sium hydroxide was calculated by the fol
lowing equation:
Ds = C« (C + a) - Ks (2)
where:
C = concentration of OH" in evap
orator solution (mol/1)
C a = concentration of Mg"* in evap
orator solution (mol/1)
Ks = solubility product constant of
Mg (OH), in saturated so
lution.
As shown in Figure 7, the plotted curve
of the degree of supersaturation against FIGURE 8. TUBES AFTER
the temperature difference has a similar TEST RUN NO. 4 ON BRINE
shape to the curve of the scale thickness VELOCITY.
versus temperature difference. Therefore, Operating Condition
the scale thickness is linear to the degree Concentration of the additive: 200 ppm
of supersaturation and would work as a Hours of operation: 155 hrs
driving force of the scale deposition under Temperature difference: 9.9°C
these experimental conditions. The degree Brine velocity, a: 1.2 b: 1.6 c- 2.0 m/j
of supersaturation of magnesium hydroxide Brine pressure: 0.4 kg/cm'
was observed to be higher in the operation Brine concentration: 8° Be
without the additive than with the additive.
The lowering of the degree of supersatura
tion might occur as a result of the seeding
action and the acid behavior action of the
additive.
The degree of supersaturation on calcium
carbonate calculated by the above equation
was found to be larger than that for mag
nesium hydroxide. This fact is in accord
with conclusions reported by Langelier
(ref. 2) , in which calcium carbonate does
not deposit ion, as long as it is kept in a
supersaturated state for a longer period
than magnesium hydroxide.
2. Brine Velocity. The tests were made
to determine the influence of brine velocity
on scale prevention. Results are shown in
Figures 8 and 9. It was found that scale
thickness depended to a large extent on MINE VELOCITY (nvfc)
brine velocity in the brine heater tube.
The effect of brine velocity was influenced
to a certain degree by brine temperature. FIGURE 9. BRINE VELOCITY
In the range of brine velocity, V, below 2.0 VS THICKNESS OF SCALE.
meters per second, the thickness of the Operating Condition
adhered scale was proportional to V"* 1 in Hours of operation: 130-155 hrs
the pressure above the saturation pressure Added amount of the additive: 160-200 ppm
corresponding to the wall temperature of Brine pressure: 0.4 kg/cm2
the brine heater tube, and to below Brine concentration: 8°Be
the saturation pressure. It is supposed that
this difference is due to bubble formation
in the brine heater. The operation was mainly attributed to the decomposition of
carried out at a brine velocity below 2.0 the bicarbonate ion; it is influenced by
meters per second because of economic partial pressure of carbon dioxide gas in
considerations. vapor phase. It is presumed that deposited
3. Brine Pressure in the Brine Heater scale should decrease with an increase of
Tube. Soft scale in sea water distillation is pressure in the heater tube to suppress

32
evolution of carbon dioxide gas and for
mation of vapor bubbles on the heating
surface.
The experimental results are shown in
Table VII and Figure 10. The higher the
pressure in the brine heater, the less was
the scale deposited. However, the effect of
the brine pressure was not as large in
comparison with that of temperature dif
ference and brine velocity in the experi
mental range. It is presumed that increas
ing pressure in the tubes may be more
effective in preventing scale under condi
tions where bubble formation will occur.
The most suitable tube pressure for distil
lation must be determined by the economic
factors.

TABLE VII. Influence of Brine Pressure


in Heater Tube

Brine pressure kg/cm^


0.4 0.8 1.2
Amount of scale lmy/dm3)
Inlet-side of heater tube 18 10 7
Outlet-side of heater tube 22 23 19
Average 20 17 13
FIGURE 10. TUBES AFTER
Operating condition TEST RUN NO. I ON BRINE
Temperature difference: 4.1°C
Added amount of the additive: 200 ppm PRESSURE.
Hours of operation: 137 hrs
Heat transfer area: 0.58 m* Operating Condition
Brine velocity : 1.6 m/s Concentration of the additive: 200 ppm
Total distillate: 3.75 m*
Hours of operation: 133 hrs
Temperature difference: 9.9°C
Further investigation will be required Brine concentration: 8 Ik-
for effective application of the additive as abed
a scale-preventing agent in a large-scale Brine velocity m/s: 1.6 1.6 1.6 0.8
sea water distillation unit. Brine pressure kg/cm2: 1.2 0.8 0.4 0.4

SUMMARY
Experiments were carried out in a 30 to tive. On adding 100 mg of the additive
50 liter/hr forced circulation evaporator to per liter of feed water, no change of pH
investigate the effect of the additive "Kuri- in the brine was observed. While the
verter" on scale prevention. thickness of the adhered scale was less than
The results are summarized as follows: that without the additive, it was found by
1. Without the additive, a large amount analysis of the brine that the additive-
of scale was found on the surfaces of the acted to reduce the degree of supersatura-
brine heater tube after a short run. The tion of the Mg(OH). in the brine. These
scale consisted mainly of magnesium hydro observations indicate two actions of the
xide resulting from decomposition of bi additive on scale control: the first is an
carbonate in sea water. The amount of the acid behavior action and the second a
scale was proportional to the period of seeding action.
operation.
2. When 200 mg of the additive per liter 3. The operating conditions had a re
of feed sea water was added, the pH of the markable effect on scale deposition. The
brine dropped from 9.25 to 8.75 and the thickness of the scale as well as the degree
scale was one-fortieth of the amount ob of supersaturation on Mg(OH), in the
served in the operation without the addi brine increased in proportion to tempera
ture difference, tw—tc, in the operating effect of the pressure on scale prevention
conditions. In the range of brine velocity, was not so large.
V, below 2.0 meters per second, the thick The above results prove that the additive
ness of the scale was proportional to about is effective as a scale-preventing agent in
V-*-* to V-*T. The higher pressure in the sea water distillation. In using it, care
brine heater gave a desirable result, but the must be taken in the distillation operations.

REFERENCES
1. Badger, W. L.:R & D Process, Report (Sept. 1960) .
No. 25, U.S. Department of the Interior, 6. McCabe, W. L.; Robinson, T.: Ind.
Office of Saline Water (July 1959) . Eng. Chem., no. 16 (1924) , pp. 478-9.
2. Langelier, W. F.; Caldwell, D. H.; Law 7. Miyogawa, S.: Shio (Salt) no. 8 (1955) ,
rence, W. F.: Ind. Eng. Chem. no. 42 pp. 3-5.
(1950) . pp. 126-30. 8. Shimizu, K.; Sakurai, T.; Sugita, S.:
3. Brit. Patent No. 131 (1920) . p. 279. Rept. of Central Lab., pp. 102-107.
4. Sugi, J.: SekkO-to-sekkai [Gypsum and Japan Monopoly Corp., Japan (1959) .
Lime] no. 18, (1955) p. 65-69. 9. Miyauchi, T.; Moriyama, T.: Kagaku
5. Murakami, K.; Shinagawa, J.: KOjo Kogaku (Chemical Engineering, Japan)
Sdsa, p. 20, Kagakukôgyô sha, Japan, no. 25 (1961) , pp. 531-537.

SUMMARY OF DISCUSSION
There was no discussion.

Contrôle de L'Entartrage Dans la

Distillation de L'Eau de Mer

Toshihiko Matsuda, Shinkitchi Akimoto et Yoshio Taniguchi

Japon

Les principaux ennuis rencontrés dans la l'entartrage que combine les caractéristiques
distillation de l'eau de mer sont la forma des méthodes sus-mentionnées. Avec la
tion du tartre et la corrosion. Le tartre sur nouvelle méthode, le contrôle de l'entar
les surfaces d'échange de chaleur résiste à trage peut se faire facilement par l'addition
l'échange de chaleur. Il se forme en général d'un agent de prévention de l'entartrage
trois genres de tartres dans la distillation de à l'eau de mer d'alimentation. Cet additif,
l'eau de mer: le sulfate de calcium, le car dont le nom commercial est "Kuriverter",
bonate de calcium et l'hydroxide de magné se compose principalement d'une sorte
sium. Deux méthodes ont principalement d'argile. Les particules de l'additif sont
été utilisées pour contrôler la formation du assez fines pour rester en suspension dans
tartre. La première est le traitement à l'eau. L'additif accélère le dépôt des élé
l'acide de l'eau d'alimentation pour em ments de formation du tartre sur les sur
pêcher l'élévation du pH; la seconde est faces des particules de l'additif plutôt que
une sorte de méthode physique similaire à sur les surfaces de chauffage. L'additif
l'ensemencement de cristaux dans les sys semble agir de la même manière qu'un
tèmes pour diriger le dépôt du tartre à un acide en supprimant l'élévation du pH
emplacement autre que la surface de dans la distillation de l'eau de mer. Un
chauffage. contrôle précis n'est pas critique dans
Les auteurs de cet exposé ont mis au l'utilisation de l'additif.
point une nouvelle méthode de contrôle de Cet exposé indique comment l'additif
empêche le dépôt du tartre et comment d'acide que supprime une élévation dans le
les conditions de fonctionnement (c'est-à- pH de la saumure provenant de la décom
dire la vélocité de la saumure, la pression position des ions bicarbonates; la seconde
et la différence de température entre la est une action d'ensemencement, trouvée
température de la paroi du tube de chauf dans les procédés usuels de recirculation
fage de la saumure, tw, et la température d'ensemencement, qui accélère le dépôt des
de la saumure, te) influence l'action de éléments de formation de tartre sur les par
l'additif. Un évaporateur à circulation ticules en suspens de l'additif plutôt que
forcée (capacité de distillation: 30 à 50 sur les surfaces de chauffage. On n'a pas
litres par heure) a été utilisé au cours de trouvé de changement remarquable du pH
l'étude. La concentration de la saumure au dans la saumure après une addition exces
cours des essais a été maintenue de 8 à 9 sive de l'additif. Il semble donc que l'appli
Bé (poids spécifique de 1,058 à 1,066 à cation de l'additif pour le contrôle de l'en
15°C) pour éviter la formation de tartre tartrage aille facilement en fonctionnement.
de sulfate de calcium. Du diphényl chloré S. Effets des conditions de fonctionne
utilisé comme véhicule d'échange de chaleur ment de l'additif sur l'action de prévention
dans le réchauffeur de saumure a été du tartre.
chauffé aux temperatures de 130, 170 et Le dépôt du tartre dépend généralement
200°C. La saumure a été maintenue à des conditions de fonctionnement de la
environ ÎOS'C. L'évaporateur à action distillation.
instantanée (vaporisation par détente) Premièrement, l'effet de la différence de
fonctionnait à la pression atmosphérique. température, tw-tc, sur le dépôt du tartre a
Les résultats obtenus furent les suivants: été étudié dans les conditions suivantes: le
1. Entartrage sans le nouveau additif. montant ajouté de l'additif était de 200 mg.
On a trouvé une grande quantité de tartre par litre d'eau d'alimentation, la vélocité
sur les surfaces des tubes de chauffage de de la saumure de l,6m/seconde et la diffé
la saumure après un court fonctionnement. rence de température, tw-tc, de 4,1 à
Le tartre déposé se composait principale 16,2°C. L'épaisseur du tartre adhérent ainsi
ment d'hydroxide de magnésium attribué à que le degré de super-saturation de Mg(OH)5
la décomposition du bicarbonate dans l'eau dans la saumure, augmentait en proportion
de mer. Dans la gamme d'épaisseur de avec la différence de température dans les
tartre inférieure à 0.28 mm., le montant de conditions expérimentales.
tartre était approximativement proportion Deuxièmement, des expériences furent
nel au temps de fonctionnement. effectuées sur l'effet de la vélocité de la
2. Effet de l'additif en tant qu'agent saumure dans le réchauffeur de saumure.
anti-tartre. Après l'addition de 200 mg. Il a été observé que la vélocité de la
d'additif par litre d'eau de mer d'alimenta saumure a un effet remarquable sur le
tion, le pH de la saumure est tombé de dépôt du tartre. Dans la gamme de vélocité
955 à 8,75 et le montant de tartre déposé de saumure, V, au-dessous de 2m./seconde,
était d'un quarantième du montant observé l'épaisseur du tartre adhérent était propor-
dans l'essai sans additif. En ajoutant 100 tionelle à envion V-1'7 dans les opé
mg. d'additif par litre d'eau d'alimentation, rations actuelles.
aucun changement de pH dans la saumure Enfin, la pression plus élevée de la sau
n'est apparu, le maintenant aussi élevé que mure dans le Téchauffeur de saumure a
dans le cas sans additif. L'épaisseur du tartre donné un résultat désirable, mais l'effet de
adhérent était considérablement moindre la pression sur la prévention du tartre n'a
que dans les essais sans additif. Il a été pas été aussi importante que la différence
également trouvé par l'analyse de la sau de température et la vélocité de la saumure.
mure que l'additif agissait pour réduire le Les résultats ci-dessus prouvent que l'ad
degré de super-saturation de l'élément de ditif a une action importante en tant
formation du tartre dans la saumure. qu'agent anti-tartre dans la distillation de
Les résultats indiquent deux actions de l'eau de mer. Cependant, dans l'utilisation
l'additif sur le contrôle de l'entartrage: la de l'additif il faut surveiller les conditions de
première est l'action de comportement fonctionnement du procédé de distillation.

35
Борьба с Накипью при Опреснении

Морской Воды

Тошихико Матсуда, Шинкитчи Акимото и Йошио Танигучи

Япония

Главными затруднениями при опре кипи сульфата кальция, во время опы


снении морской воды являются обра тов поддерживалась концентрация ра
зование накипи и коррозия. Накипь на створа при 8-9 градусах Бомэ/удель-
теплообменных поверхностях задержи ный вес 1,058-1,066 при 15вС). В ка
вает теплопередачу. При дистилляции честве теплоносителя в подогревателе
морской воды встречаются вообще три рассола был использован хлорирован
типа накипи: сульфат кальция, карбо ный дифенил, температура которого до
нат кальция и гидроокись магния. Для водилась в подогревателе раствора до
борьбы с накипью преимущественно 130, 170 и 200°С. Раствор имел пример
пользовались двумя методами. Первый но 105°С. Испаритель со мгновенным
состоит из обработки исходной воды вскипанием работал при атмосферном
кислотой для предотвращения повы давлении.
шения pH; второй является физическим Были получены следующие резуль
методом затравки кристаллами, чтобы таты :
отводить осаждение накипи с поверх 1. Когда реактив не употреблялся, от
ности нагрева на другое место. лагалась накипь. После короткого опы
Авторы настоящего доклада усовер та было обнаружено большое количе
шенствовали новый способ борьбы с ство накипи на поверхностях трубы
накипью, который сочетает особенно подогревателя раствора. Она преиму
сти двух вышеупомянутых. При новом щественно состояла из гидроокиси маг
методе без труда достигается предот ния, возникавшей вследствие разложе
вращение образования накипи с по ния бикарбоната в морской воде. При
мощью добавления к исходной воде толщине накипи менее 0,28 мм, ее ко
специального реактива. Он имеет тор личество было почти пропорционально
говое название «Куривертер» и глав продолжительности работы.
ным образом состоит из глинистой по 2. Воздействие добавки реактива для
роды. Частицы его настолько тонко по предотвращения образования накипи.
молоты, что остаются взвешенными в При добавлении 200 мг «Куривертера»
воде. Добавка способствует отложению на литр исходной воды, показатель pH
накипи не на поверхностях нагрева, а раствора снижался с 9,25 до 8,75, а
на поверхности частиц самого реакти количество отлагавшейся накипи со
ва. «Куривертер» видимо действует при ставляло одну сороковую часть того,
дистилляции морской воды, как кисло что замечалось при опытах без его
та, задерживающая повышение pH. добавления. При добавке 100 мг реак
При пользовании добавкой не требует тива на литр исходной воды, в раство
ся внимательного за ней наблюдения. ре не происходило изменения pH, ко
В настоящем докладе указано, как торый оставался на прежнем уровне.
добавка предотвращает отложение на Толщина сцеплявшейся накипи была
кипи, и как рабочие условия (т.е. ско значительно меньше, чем при опытах
рость потока раствора, давление, пере без реактива. При анализе раствора
пад между температурой стенки трубы было также обнаружено, что добавка
подогревателя раствора и температу уменьшала степень пресыщения со
рой самого раствора и т.п.) влияют на ставной части раствора, способствовав
действие реактива. При исследованиях шей образованию накипи.
пользовались испарителем с принуди Результаты указывают на два дей
тельной циркуляцией (дистилляционная ствия реактива: первое является ки
производительность 30-50 литров/час). слотным, которое сдерживает повыше
Для предотвращения образования на ние pH раствора, получающееся вслед
стене разложения бикарбонатного ио пень пересыщения Mg(OH)2 в раство
на; второе служит затравкой, встречаю ре увеличивались пропорционально
щейся в обычном затравочном рецир температурному перепаду, имевшему
куляционном процессе, которая способ место в условиях опыта.
ствует отложению составных частиц, Во-вторых, были произведены опыты,
образующих накипь, не на поверхно относившиеся к воздействию скорости
стях нагрева, а на самой взвеси «Кури- потока в подогревателе раствора. Бы
вертера». При чрезмерном добавлении ло обнаружено, что скорость потока
реактива не было найдено в растворе раствора оказывает заметное влияние
значительного изменения pH. Поэтому на отложение накипи. При скорости
применение добавки для борьбы с на потока раствора V < 2,0 м/сек, тол
кипью повидимому не представляет во щина сцеплявшейся накипи во время
время работы никаких трудностей. этих опытов была приблизительно про
3. Влияние рабочих условий на дей порциональна v-*,--v-*,T.
ствие добавки для предотвращения
образования накипи. Отложение наки Наконец, повышение давления раст
пи обычно зависит от рабочих условий вора в его подогревателе давало поло
перегонки. жительные результаты, но воздействие
Во-первых, было обследовано воз давления на предотвращение образо
действие перепада между температу вания накипи было менее, чем эффект,
рой стенки трубы (т.е.) подогревателя производимый температурным перепа
раствора и температурой самого раст дом и скоростью потока раствора.
вора (т.р.) на образование накипи при Вышеуказанные результаты подтвер
следующих условиях: количество до ждают, что при опреснении морской
бавляемого реактива — 200 мг на литр воды добавка играет видную роль в
исходной воды; скорость потока раст борьбе с накипью. Однако, при ее при
вора — 1,6 м/сек; температурный пе менении надо тщательно следить за
репад т.с.-т.р. — 4,1°С- 16,2°С. Толщи рабочими условиями дистилляционного
на отлагавшейся накипи, а также и сте процесса.

El Control de las Incrustaciones en

la Destilación del Agua de Mar

Toshihiko Matsuda, Shinkitchi Akimoto y Yorhio Taniguchi

Japon

La causa principal de las dificultades que sistemas para que las incrustaciones se
sobrevienen en la destilación del agua de formen en un sitio que no sea la superficie
mar son: la formación de incrustaciones y de calentamiento.
la corrosión. Las incrustaciones que se for Los autores de este trabajo han perfeccio
man en las superficies de transmisión caló nado un nuevo método en que se combinan
rica oponen resistencia a dicha transmisión. los rasgos característicos de los métodos ya
En la destilación del agua de mar se mencionados. Gracias al nuevo método, la
forman, por lo general, tres tipos de incrus prevención de las incrustaciones puede efec
taciones a saber: las de sulfato de calcio, tuarse fácilmente agregando al agua salada
carbonato de calcio e hidróxido de magne de alimentación un agente protector contra
sio. Para el control de las incrustaciones se incrustaciones. El aditivo, denominado co-
han empleado principalmente dos métodos. mercialmente "Kuriverter" por los autores,
El primero consiste en el tratamiento del consiste principalmente en una especie de
agua de alimentación con ácido para evitar arcilla. Las partículas del aditivo son lo
la elevación del pH; el segundo es una suficientemente finas para permanecer sus
especie de método fisico, tal como el espar pensas en el agua. El aditivo acelera la
cimiento de cristales de "semilla" en los precipitación de los constituyentes formado
res de incrustaciones sobre la superficie del Los resultados indican que el aditivo
aditivo y no en las de calentamiento. £1 adi ejerce dos acciones en el control de las in
tivo parece actuar como un ácido al impedir crustaciones, a saber: la primera es una
el ascenso del pH en la destilación del agua acción ácida que suspende el ascenso del pH
de mar. Cuando se emplea el aditivo no de la salmuera que resulta de la descompo
es indispensable mantener un control sición del ion bicarbonato; la segunda es
cuidadoso. una acción de sembrado de "semilla" que
Este trabajo indica cómo el aditivo evita ocurre en el procedimiento común de recir
la formación de incrustaciones y cómo las culación de "semillas" que acelera la preci
condiciones de trabajo (v.g., la velocidad de pitación de los constituyentes formadores de
la salmuera, la presión, y la diferencia entre incrustaciones en las partículas suspendidas
la temperatura de las paredes del tubo de del aditivo y no en las superficies de calen
calentamiento de la salmuera, tw, y la tem tamiento. Al agregarse una cantidad exce
peratura de la salmuera, te), influyen en la siva de aditivo no se observó un cambio
acción del aditivo. En los trabajos de inves grande de pH en la salmuera. Por lo tanto,
tigación se empleó un evaporador tie circu parece que la aplicación del aditivo para
lación forzada (capacidad de destilación: el control de las incrustaciones se lleva a
de SO a 50 litros por hora). Durante las cabo fácilmente.
pruebas, la concentración de agua salobre 3. El efecto de las condiciones de trabajo
se mantuvo entre 8 y 9 Baumé (peso espe en la acción protectora contra incrustaciones
cifico: 1.058 a 1.066 a 15° C.) para evitar la del aditivo. La formación de incrustaciones
formación de incrustaciones de sulfato de depende, por lo general, de las condiciones
calcio. El difenilo clorinado que se empleó de trabajo de la destilación.
como medio de transmisión térmica en el En primer lugar, se investigó el efecto de
califactor de salmuera, fué calentado a la diferencia de temperaturas, tw-tc, en la
temperaturas de 130, 170 y 200° C. La sal formación de incrustaciones, en las siguien
muera se mantuvo a una temperatura de tes condiciones: La cantidad adicional del
más o menos 105° C. El evaporador instan aditivo es de 200 mg. por litro de agua de
táneo trabajó a la presión atmosférica. alimentación, la velocidad de la salmuera es
Se obtuvieron los siguientes resultados: de 1,6 metros por segundo y la diferencia de
temperaturas, tw-tc, es de 4,1 a 162° C.
1. La formación de las incrustaciones sin Tanto el espesor de la incrustación adhe
el nuevo aditivo. Se encontraron muchas rida como el grado de sobresaturación de
incrustaciones en las superficies del tubo Mg(OH)2 en la salmuera, aumentaron pro-
calentador de salmuera después de un breve porcionalmente a la diferencia de tempera
período de funcionamiento. La costra depo turas en las condiciones de prueba.
sitada consistió principalmente en hidróxido
de magnesio, lo cual se atribuyó a la des En segundo lugar, se condujeron experi
composición de bicarbonato en el agua de mentos para determinar el efecto de la velo
mar. En las incrustaciones con espesor infe cidad de salmuera en el calentador de esta
rior a 0,28 mm., la cantidad de incrustacio última. Se observó que la velocidad de la
nes fué más o menos proporcional al periodo salmuera ejercía un efecto grande en la for
de funcionamiento. mación de incrustaciones. En los límites de
2. El efecto del aditivo como agente pro velocidad del agua salobre, V, inferiores a
tector contra incrustaciones. Cuando se 2,0 metros por segundo, el espesor de las
agregaron 200 mg. del aditivo por cada incrustaciones adheridas era proporcional
a entre V-*'* y V"*'T en las operaciones
litro de agua de mar de alimentación, el pH actuales.
de la salmuera bajó de 925 a 8,75 y la can
tidad de incrustaciones depositadas fué de Finalmente, la presión más alta de la
un cuadragésimo de la que se observó en la salmuera en el calentador de esta última
prueba sin el aditivo. Cuando se agregaron produjo el resultado deseado, aunque el
100 mg. del aditivo para cada litro de agua efecto de la presión en la prevención de
de alimentación, no ocurrió ningún cambio incrustaciones no fué tan notable como el
en el pH de la salmuera, manteniéndose de la diferencia de temperaturas y la veloci
tan alto como sin el aditivo. El espesor de dad del agua salobre.
la costra adherida fué considerablemente Los resultados obtenidos demuestran que
menor que en las pruebas sin el aditivo. el aditivo ejerce una acción notable como
También se comprobó por medio del aná agente de protección contra incrustaciones
lisis de la salmuera que la acción del aditivo en la destilación del agua de mar. Sin em
redujo el grado de sobresaturación en el bargo, al emplearse el aditivo debe tenerse
constituyente formador de incrustaciones en cuidado en lo que toca a las condiciones de
la salmuera. trabajo en el procedimiento de destilación.
Saline Water Distillation — Scale

Prevention by Polymer Additives

L. S. Herbert, P. F. Rolfe and U. J. Sterns

Australia

INTRODUCTION
Distillation of sea water and other natu The protective film then reformed on the
rally occurring saline waters gives rise to exposed surface and the process was re
the formation of scale deposits of low ther peated. Such a "regenerating film" mech
mal conductivity on the heat transfer sur anism is of general interest, and techniques
faces of the distillation plant. The heat based on it may find extensive practical
transfer coefficients are thereby reduced, application in saline water distillation
leading to deterioration of plant perform plants and in other plants where the prob
ance and necessitating the eventual shut lem of scale formation is encountered. The
down of the plant for cleaning. Although work reported below was carried out in an
•several methods are in use for the control attempt to establish the limits of applic
of "alkaline" scales, scaling considerations ability of the scale prevention method and
still set an upper limit on the brine boiling to elucidate the mechanism of the protec
temperature and concentration factor, and tive action by experiments with both the
hence on plant performance. experimental evaporator and small-scale
In work recently reported (réf. 1) , it was beaker tests.
found that the addition of small amounts
of certain polymeric acids of selected molec PREPARATION AND CHARACTERIZATION
ular weight range to the sea water feed of OF POLYMERS
an experimental spray evaporator had a
remarkable effect in reducing the adverse The polyacrylic acid used in the earlier
effects of scale formation on the heat trans experiments (réf. 1) was supplied by Can
fer surfaces. Of the materials tested, poly- adian Industries, Ltd., (C.I.L.) who also
acrylic acid of mean molecular weight provided details of a method of preparation
20,000, added to the extent of 3 ppm to the for low molecular weight polyacrylic acids
sea water feed, proved to be particularly (Appendix 1A) . Several batches of homo-
effective during evaporation at 240°F. Over polymer—designated Rl through R8—were
all heat transfer coefficients in excess of made by this method. Since a partially
2300 Btu/sq ft hr°F were maintained over csterified polyacrylic acid might be expected
a period of 50 hours, whereas evaporation to possess improved surface activity com
of untreated sea water resulted in a rapid de pared with the homopolymer, a 10 per cent
crease of the coefficient to about 800 Btu/sq ethyl acrylate/acrylic acid copolymer, desig
ft hr"F after only 6 hours. nated R9, was made by the method detailed
The mechanism of protective action was in Appendix IB.
not clear, but there was evidence of the In attempts to produce homopolymers of
formation of a thin film of the polyacid or differing molecular weights, the propor
a related salt on the heating surface. The tions of monomer, initiator and chain trans
scale-forming components then appeared to fer reagent given in the preparative method
deposit on the film, which stripped from the were varied.
wall, possibly as a result of stresses set up Weight average molecular weights of sev
in the film by temperature differentials. eral polymers were determined by equilib
TABLE VIII. Characterization of Polymers by Equilibrium Ultracentrifugation
Polymer Type Method No. of runs Av. m. wt.
C.I.L. Homopolynoer Long 1 19,000

K2 Homopolymer Long 2 22.000


column
R6 Homopolymer Long 1 16.000
column
R6 Homopolymer Short 3 18.000
column
R9 10% ethyl acrylate— Short 1 13.000
90% acrylic acid copolymer column

rium ultracentrifugation using a Spinco preparative method had relatively little


Model E Ultracentrifuge. using the method effect on molecular weights, which were in
outlined in Appendix 2. Typical results are the range 16,000 to 26,000. A study of molec
presented in Table VIII. ular weight distributions revealed that the
It can be seen that the effect of variation C.I.L. polymer possessed a somewhat broader
of reactant proportions in the homopolymer distribution than polymers R2 and R6.

EXPERIMENTAL
SPRAY EVAPORATION AND CLIMBING FILM this effect the apparatus was modified so
EVAPORATION TESTS that a strong polymer solution was added
continuously by a metering pump feeding
Figure 11 shows a simplified flow diagram a small mixing chamber in the preheated
for the test apparatus. It was essentially the feed water line, and positioned as near as
same as the "spray" evaporation rig de possible to the steam-water venturi mixer.
scribed in detail in a previous publication A further advantage was that longer runs
(ref. 1) . Preheated sea water was intimately could be made. As an additional modifica
mixed with steam in a venturi and the re tion, a manual throttling valve was installed
sulting two phase mixture passed upwards in the pipeline between the separator and
at high velocity through a steam jacketed the condenser to permit the use of increased
copper tube of i/s inch internal diameter pressures, and hence increased tempera
which was 2 feet long. Transfer of heat tures, within the evaporator tube.
from the higher pressure jacket steam The values of flowrates and jacket steam
caused evaporation of the sea water drop
lets. The resultant mixture of brine and temperature, e.g.. 300 lb/hr water, 96 lb/hr
steam was separated, the steam condensed, steam and 40 psig jacket steam pressure
and both product liquid streams metered. (287°F) , found to be most suitable in the
In tests with untreated sea water, the rate previous work, were used as "standard"
of scale formation was rapid and repro evaporation conditions in the present work.
ducible and, on these grounds, the method F.vaporation temperature changed along the
was selected for a detailed appraisal of tube length due to the pressure drop and
scale-prevention techniques. The rate of averaged 240°F, with a 45°F difference be
heat transfer was measured by weighing the tween heating steam and evaporating fluid
jacket condensate produced in selected time temperatures. The concentration factor ob
intervals. tained (i.e., the ratio of feed water rate to
For the work previously reported, polymer residual brine rate) was approximately 1.3.
additions were made to 240 gallon batches At the end of any test the inside tube sur
of sea water stored in a stirred tank at some face and any adhering scale could be ex
distance from the evaporator. Adsorption amined by cutting the tube in half along
of polymer on the inside tank and pipe sur its axis.
faces during runs at high polymer concen CALCULATION OF EFFECTIVENESS
tration followed by desorption into the feed
water during the succeeding low concentra OF SCALE PREVENTION
tion runs contributed to poor reproduci Instantaneous readings of pressure, tem
bility of heat transfer data. To overcome perature, and rate of condensate production
Condenser

Diati/lote

JocAet
1
Grotfuotect
Ton*

—2
Po/ymer

Feect water JocAet Com/ensote

0
Preneoter

I 5Г—^ '
1 J Steo.n/ Voter Aftxer

FIGURE 11. SIMPLIFIED FLOW DIAGRAM


FOR SPRAY EVAPORATOR.

were subject to considerable fluctuations to minor variations from test to test. Small
during any run. Consequently the heat proportional corrections were made to the
transfer coefficient at the end of a fixed weight "A" to compensate for the changes
operating time, or the rate of decrease of in the heat transfer driving force.
heat transfer at any selected time measured
from the start of the run, were unsatisfac LABORATORY BEAKER TESTS
tory criteria of effectiveness of scale preven
tion. It was decided that the quantity of A single run in the pilot plant evaporator
jacket condensate collected during the first took 61/4 hours and consumed approxi
6i/i hours of any test was a reasonable basis mately 200 gallons of sea water. Only one
for comparison of different runs. This was set of conditions could be investigated in
incorporated in an arbitrary "Improvement the period. A study was made of simple
Ratio" defined as laboratory evaporation tests with the aim
of developing a small-scale, quick method
m = ±f* x loo (i) of evaluating different polymeric compounds
for effectiveness as scale-prevention agents.
where A = weight of jacket condensate col In one such method, natural sea water
lected in ву2 hours using the samples containing various concentrations of
given polymer addition; copolymer R9 were evaporated on a hot
В — weight of jacket condensate col plate at a closely controlled boiling rate in
lected in hours with un pyrex glass beakers covered with watch
treated sea water. glasses. The evaporation was continued until
a predetermined weight of brine remained,
Due to the accumulation of deposits in corresponding to a concentration factor of
side pipelines to and from the evaporator 1.3 similar to that obtained in spray evap
tube, the pressure and consequently the oration "standard" tests. Every beaker and
temperature inside the system were subject watch glass was carefully cleaned before
each test, using a combination of hot acid washed with a measured volume of nitrate,
and alkali washes. then dried and weighed. A correction was
The residual brine was allowed to cool made for any suspended solids in the orig
overnight and any precipitates formed were inal sea water by means of a blank deter
collected on sintered glass filter crucibles, mined on untreated sea water.

EFFECT OF POLYMER CONCENTRATION R9, the ethyl acrylate/acrylic acid copoly


SPRAY EVAPORATION mer, are plotted in Figure IS. An optimum
polymer concentration at approximately 2
Data from preliminary tests are plotted ppm is indicated for sea water batches 103
in Figure 12 as Improvement Ratio versus and 107 while it appears that an optimum
polymer concentration (ppm). Several batches has not been reached at 3 ppm for batch
of sea water were used as feed with vari 106. Differences in optimum polymer con
ous concentrations of several different centration in the range 1.0-4.0 ppm have
batches of polymer additives. The polymers been observed for different batches of sea
were all polyacrylic acids, estimated to be water and may be accounted for by differ
in the molecular weight range 16,000-26,000 ences in the dissolved solids or suspended
and made by the methods described in matter content of the different batches of
Appendix 1A. An optimum polymer con sea water. Analyses of each batch showed
centration, corresponding to a maximum no gross differences in total dissolved solids
Improvement Ratio, is shown quite clearh or total alkalinity, but traces of oil con
although there is a considerable scatter of tamination or variations in the amount of
data around the optimum concentration. organic matter could lead to variable re
Data for single batches of sea water using sults with the very small quantities of poly
various concentrations of a single polymer, mer added.
O
loo r

FIGURE 12. VARIATION OF IMPROVEMENT RATIO WITH


POLYMER CONCENTRATION 7 BATCHES OF SEA WATER,
POLYMERS OTHER THAN R9, "STANDARD" CONDITIONS.
—°— Sea Voter Botch /OS
—X—
O Seo Sea
Voter
Mooter
Batch
Botch
/Otf07

2 * 6 8 W 12
Po/ymer Concentrator* -ppm
FIGURE 13. VARIATION OF IMPROVEMENT RATIO WITH
POLYMER CONCENTRATION POLYMER R9, "STANDARD"
CONDITIONS.

The optimum polymer concentration of EFFECT OF POLYMER CONCENTRATION


2 ppm of R9 was set as the additive con
centration for a 50-hour evaporation test CLIMBING FILM
on sea water batch 103. Due to operating Climbing film evaporation tests were
difficulties, the addition rate varied from made using the apparatus of Figure 11, fed
2.0 ppm at the start of the run, down to with preheated sea water feed and no en-
less than 1.5 ppm at the end of the run, trainment steam. The evaporation tempera
the average corresponding to 1.6 ppm. The ture was adjusted to approximately 240°F,
variation of overall heat transfer coefficient with an overall temperature difference be
with time is plotted in Figure 14, together tween jacket steam and evaporating fluid
with typical results obtained for spray evap of approximately 45°F.
oration of an untreated sea water for com The results for two batches of sea water-
parison. Figure 14 also shows the effect of batches 108 and 110—are plotted in Figure
a momentary interruption of the flow of 15. An optimum polymer concentration is
sea water feed after 30 hours of operation. evident in both curves, between 1 and 2
The immediate recovery of the overall heat ppm of polymer. At polymer concentrations
transfer coefficient to the "clean tube" value higher than 5 ppm, a negative Improvement
indicates that the deposit formed up to that Ratio resulted, i.e., the scale deposits formed
time was attached only loosely to the tube with excess polymer present were more dele
surface and was easily removed by the in terious to heat transfer than those resulting
terruption of water flow. from untreated sea water.

43
5.000

10 20 30 40 50 60
f/oara of operot/on
FIGURE 14. VARIATION OF OVERALL HEAT TRANSFER
COEFFICIENT WITH TIME AT "STANDARD" CONDITIONS.

— •— Sea woter botch /Og


*— Seo water batch //O

\ G 8 tO 12
\ Po/ymer Concenirotton -pp m

FIGURE 15. VARIATION OF IMPROVEMENT RATIO WITH


POLYMER CONCENTRATION POLYMER R9, CLIMBING FILM
EVAPORATION AT 240°F.

44
EFFECT OF POLYMER CONCENTRATION— cent probability that the three low precipi
LABORATORY TESTS ON tate weights at polymer concentration 3.4
NATURAL SEA WATER ppm were simply random fluctuations from
a smooth curve through the remaining
In laboratory tests on a given batch of points. In a similar series of tests with sea
sea wateT. polymer additions were made to water batch 103. minimum amounts of pre
samples of the water in several beakers to cipitate resulted at a polymer concentration
give a different polymer concentration in of 1.8 ppm (cf. optimum polymer concen
each sample, in the range 0 to 10 ppm. tration of 2.0 ppm obtained in spray evap
Beakers and contents were then subjected to oration tests—Fig. 13.
the standard test procedure outlined in a
previous section. EFFECT OF POLYMER CONCENTRATION—
Examination of the contents of the beak LABORATORY TESTS ON
ers after boiling showed that the amount SYNTHETIC SEA WATER
of visible precipitate varied with polymer
concentration. There was generally one Synthetic sea water was made up accord
beaker, corresponding to a particular poh ing to a formula of Lyman and Fleming
mer concentration (in the range 1 to 4 (ref. 3) . Special precautions taken to avoid
ppm for different batches of sea water) in contamination with surface active materials
which the amount of visible precipitate was included chemical cleaning of vessels, use of
a minimum. the purest available chemicals, and prcven-

I 2 3 4-5 6 7
Po/ymer Concentrat/on -ppm

FIGURE 16. VARIATION OF PRECIPITATE WEIGHTS WITH


POLYMER CONCENTRATION SEA WATER BATCH 104, POLY
MER R9, BEAKER TESTS.

By careful filtration and weighing it tion of ingress of airborne materials. Beaker


proved possible to determine the very small tests indicated scale deposition behavior
weights of the individual precipitates. Typi similar to that in natural sea waters, with
cal data for sea water batch 104 are plotted a minimum precipitate occurring at a polv
in Figure 16. The previous visual observa mer (R9) concentration of 0.6 ppm.
tion that a minimum amount of precipitate Modifications of the synthetic sea water
resulted from the addition of about 3.4 ppm formula were made in order to obtain mag
of polymer was confirmed by the weights nesium -deficient "sea water" (producing
of precipitate actually measured. Statistical largely calcium carbonate scale on boiling)
examination, using student's "t" tests, and calcium-deficient "sea water" Cproduc
showed that there was less than a 2 per ing largely magnesium hydroxide scale).
The variation of precipitate weights with cipitate weight at a polymer concentration
|>olymer concentration is shown in Figure of 0.4 to 0.5 ppm. Where CaCO, is being
17 from which it is seen that at small poly deposited, there is a steady decrease in
mer concentrations, the effect of polymer precipitate weight up to 3 ppm polymer
addition is most marked where Mg(OH), concentration, with no evidence of a mini
is being deposited, giving a minimum pre- mum weight.

40 r

FIGURE 17. VARIATION OF PRECIPITATE WEIGHTS WITH


POLYMER CONCENTRATION SYNTHETIC SEA WATER, POLY
MER R9, BEAKER TESTS.

FIGURE 18. EFFECT OF VARIOUS CONCENTRATIONS OF POLY-


MER R6 ON AMOUNT OF CaCO, PRECIPITATED FROM SEA
WATER.
An interesting related effect is illustrated ence was maintained at about 40°F by in
in Figure 18, which shows the results of creasing the jacket steam pressure from 40
increasing polymer additions to natural sea to about 65 psig. Operating difficulties were
water treated with excess sodium carbonate encountered using these conditions and scal
in order to give a precipitate of calcium ing behavior lacked reproducibility even on
carbonate but with no concentration by untreated sea water. The scales from un
evaporation. The amount of precipitate col treated sea water were coarse crystalline
lected at the bottom of the centrifuge tubes deposits, in contrast to the gelatinous de
is seen to decrease steadily with increased posits typical for standard conditions.
polymer concentration and the amount of Tests with polymer additions gave vari
material still dispersed is obviously greater able results with the Improvement Ratio
for the 5 and 9 ppm polymer concentrations. fluctuating between small negative and
small positive values throughout the range
EFFECT OF TEMPERATURE OF EVAPORATION of polymer concentration. Although the
—SPRAY EVAPORATION scale deposits were considerably modified
Several tests were made using increased by the higher polymer concentrations there
pressure inside the evaporator tube, corres was no evidence of significant improvement
ponding to an evaporation temperature of at any polymer concentration up to 10 ppm
about 270°F compared to 240°F at "stand or of an optimum concentration.
ard" conditions. Overall temperature differ

OBSERVATIONS ON THE NATURE OF THE DEPOSITS


Scale deposits were examined by cutting formed at the lower end of the tube, with
the heat transfer tube in half along its the self-stripping film being observed only
length at the end of a run. It was important at the upper ends of the tube. At the higher
not to allow the deposits to dry out before polymer concentrations—above about 5 ppm
cutting the tube since they dried very rapid of R9—the self-stripping plastic film was
ly in air and could be lost during the not observed anywhere in the tube. In gen
cutting operation. eral, deposits were colored light blue, indi
cating the probable presence of copper
DEPOSITS FORMED UNDER "STANDARD" polyacrylate.
EVAPORATION CONDITIONS The change of appearance of the deposit
The appearance and extent of adherence with polymer concentration was character
of deposits were observed to change mark istic and could be used as a satisfactory
edly with polymer concentration. In "stand qualitative guide as to whether polymer
ard" spray evaporation tests at a tempera concentration was above or below the opti
ture of 240°F, the use of the optimum mum for scale prevention. Quantitative
polymer concentration resulted in complete analysis was made of the deposits which
coverage of the heat transfer surface with a were approximately midway along the heat
thin film of a deposit which was transpar ed section of the tubes used in the variable
ent when wet. On immediate examination, polymer concentration series on sea water
therefore, the inside surface of the tube batch 103 reported in Figure 13. The values
appeared perfectly clean, but after a few for percentage total organic material and
seconds exposure to the air, the film became percentage MgO obtained from these analy
blue colored and began to strip from the ses are plotted against polymer concentra
copper surface to form curled "whiskers" tion in Figure 20. Stoichiometric magnesium
of a self-stripping plastic film. The drying polyacrylate would be analyzed as 22 per
and stripping action was often quite violent cent MgO, 78 per cent organic material
and resulted in parts of the dried film being (ratio 1 MgO to 3.5 polyacrylic acid) . Fig
thrown from the surface. Figure 19 shows ure 20 shows that, even at a polymer con
a series of photographs taken at given time centration of 10 ppm, there is insufficient
intervals after commencement of the first organic material for the scale to be stoichio
signs of stripping. metric magnesium polyacrylate.
At polymer concentrations lower than the DEPOSITS FORMED DURING CLIMBING FILM
optimum, the self-stripping film was con
fined to the lower parts of the tube, merg AND HIGH TEMPERATURE RUNS
ing into an increasingly adherent film of Observations for these runs are based on
crystalline appearance in the upper parts of the examination of relatively few tubes com
the tube. At polymer concentrations higher pared with those from runs at "standard"
than the optimum, an adherent deposit conditions. The self-stripping film was not
observed in any part of the tubes used for The deposits formed during the high
the climbing film tests, although the effect temperature evaporation tests did not con
of polymer addition on the appearance of form to any general pattern although lhe\
the deposits formed was quite marked. In were invariably heavier than those formed
general, at the higher polymer concentra at "standard" evaporation conditions. There
tions, a continuous, green colored film of appeared to be much less alteration in ap
glazed appearance covered all the heated pearance due to the action of the added
section: at concentrations near the optimum, polymer, even at a polymer concentration
a similar type of scale was formed, but it of 2 ppm, although there was occasional
was patchy and considerably thinner than evidence of the formation of the self-strip
at higher concentrations. ping type of plastic film.

START 40 SECS

FIGURE 19. "PLASTIC" SCALE STRIPPING FROM


HEAT TRANSFER SURFACE.

48
60г

Orçan/c moíer/о/

4Z В 8 Ю t2
Po/ymer cor/centrot/osi - pp m
FIGURE 20. VARIATION IN SCALE ANALYSIS WITH POLYMER
CONCENTRATION SEA WATER BATCH 103, POLYMER R9,
"STANDARD" CONDITIONS.

DISCUSSION
Both polyacrylic acid and a 10 per cent which may have a more deleterious effect
ethyl acrylate/acrylic acid copolymer hav on heat transfer rate than those formed
ing molecular weights of approximately from untreated sea water.
20,000 have been shown to be effective as An earlier tentative explanation (réf. 1)
scale-prevention additives in sea water dis of the scale prevention mechanism postu
tillation. Л polymer concentration of about lated the formation of a brittle magnesium
2 ppm of the weight of sea water feed gave polyacrylate film at the heat transfer sur
optimum results under standard test condi face. Thermal stresses set up in the film
tions, corresponding to a maximum Im caused it to strip from the surface, on which
provement Ratio of 70 to 80 per cent in a new film was formed which, in turn,
spray evaporation tests and of 40 to 50 per subsequently stripped. In the present work,
cent in climbing 61m evaporation tests. The the film remaining on the tube surface at
use of polymer concentrations lower or the end of a run was found to be largely
higher than the optimum gives lower values magnesium polyacrylate and it is considered
of Improvement Ratio. Varations -in the that such a "regenerating film" mechanism
value of the optimum polymer concentra has important potential in scale prevention -
tion for different batches of sea water may However, there is clear evidence of a de
be due to variations in the content of sus pendence on polymer concentration of both
pended solids and of surface active materials Improvement Ratio and the nature of the
in the sea water as collected. At polymer deposits formed. Laboratory beaker tests
concentrations considerably higher than the indicated that there was also a dependence
optimum, scale deposits can be formed on polymer concentration of the total
weight of precipitate formed during the attached portions could then participate in
evaporation of sea water and that there "bridging" interactions, leading to adher
was some agreement between the polymer ence and particle growth.
concentration required to give minimum Scale prevention during spray evaporation
precipitate weights in beaker tests and that tests at "standard" conditions may, there
required to give maximum Improvement fore, involve two different mechanisms: first,
Ratio in spray evaporation tests. the deflocculating action of the polymer
It is common practice to use surface which, in the region of optimum polymer
active materials in the treatment of super concentration, is able to prevent the growth
saturated aqueous solutions to modify or and adherence of most of the precipitate;
inhibit scale deposition (refs. 4-6). Polyac- and second, the "regenerating film" action
rylic acid and polyacrylamide additives have which removes the small amount of precipi
recently become available commercially for tate which is deposited on the heat transfer
such applications and at least one of these surface. The latter mechanism appears to
is believed to have proved effective in pre provide scale protection only when the
venting adherent scale in a sea water dis quantity of precipitate has been substanti
tillation plant (ref. 7) . ally diminished by deflocculation.
Such systems are undoubtedly extremely With this assumed mechanism, it might
complex as the surface active materials may be expected that the use of a higher molecu
modify the nucleation and growth stages of lar weight polymer would result in a lower
precipitate formation, as well as affect the effectiveness of scale prevention, since the
final state of dispersion of particles in the larger molecules are likely to be adsorbed
liquid phase. The few fundamental investi with a lower proportion of surface-attached
gations reported have generally been limited carboxyl groups and a high probability of
to studies of specific agents in simple solu the occurrence of "bridging" interactions.
tions (refs. 8,9) . Modifications of settling Preliminary experiments indicate that high
and filtration characteristics of slimes by molecular weight polymers are of little use
the flocculation/deflocculation action of for scale prevention.
polyelectrolytes are of great importance in There are many implications of the pro
metallurgical milling operations, and con posed scale-prevention mechanism which still
sequently considerably more work has been need to be tested—for example, there is no
done on the simpler systems of suspended indication of a minimum precipitate weight
solids in water used in the mineral indus when CaCO, is precipitating (Fig. 17) . In
try. In recent work (refs. 10,11) such vari order to facilitate further testing, a small
ables as polymer concentration, molecular spray evaporation test apparatus has been
weight, and pH of the liquid environment developed which uses only one-twentieth of
have been examined and physicochemical the material flow rates of the spray evapora
mechanisms suggested for the observed tor used in the present work. It will there
action of the polyelectrolytes on the sus fore be practicable to use synthetic feed
pended solids. waters as well as sea water so that, for ex
There is strong evidence from the beaker ample, the effect of polymer addition on
tests that the polymers used in the present CaSO, and CaCO, precipitation can be
work act as dispersing or, more correctly, studied.
(ref. 12) deflocculating agents. Concepts The variation of Improvement Ratio with
similar to those proposed to explain the polymer concentration for climbing film
flocculation/deflocculation action of poly evaporation (Fig. 15) can be explained by
electrolytes on mineral slimes may be rele the deflocculating action of the polymer.
vant to scale prevention. At polymer con It appears from experimental observations
centrations below optimum, it may be that the self-stripping film is not formed
assumed that polymer molecules are ad under the climbing film test conditions.
sorbed at the scale particle surface with a Spray evaporation results for higher evap
high proportion of the carboxyl groups oration temperatures indicate that the poly
attached. Higher polymer concentrations, up mers used were ineffective in scale preven
lo the optimum, lead to more complete tion at temperatures above about 260"F.
surface coverage, with increasing mutual Changes in the composition of the solid
repulsion between particles. Above the op phase deposited and an increase in the
timum polymer concentration, there would amount deposited at higher temperatures
be an increasing probability of adsorption may account for the poor results, although
of molecules with fewer carboxyl group modifications of the polymer configuration
attachments per molecule. ■ The large un may also be responsible.
CONCLUSIONS
1. Small concentrations of low molecular mer concentration. For the same batch of
weight polyacrylic acid or 10 per cent ethyl sea water, there was fair agreement between
acrylate/acrylic acid copolymer have been polymer concentration required to produce
found to be effective in preventing scale maximum deflocculation and the optimum
deposition during sea water evaporation. polymer concentration corresponding to
Significant improvements in heat transferred maximum scale prevention.
over a standard period were noted during 4. An explanation for the observed scale
tests carried out in experimental climbing prevention postulates the simultaneous op
film and "spray" evaporators, evaporating eration of two physical mechanisms. First,
sea water at 240°F. at or near the optimum polymer concen
2. The extent of scale prevention in the tration, the adherence and growth of scale
experimental evaporators was found to be particles is suppressed due to adsorption of
dependent on polymer concentration. An polymer molecules at their surface, thereby
optimum polymer concentration of about substantially reducing the amount of scale
2 ppm was observed to be most effective. deposited. Second, the small amount of
Lower and higher polymer concentrations scale deposited has a high content of mag
were less effective and, at concentrations nesium polyacrylate and, under conditions
considerably higher than optimum, scale of evaporation in the spray evaporator,
deposits in the climbing film tests proved this scale is capable of self-stripping from
to be more deleterious to heat transfer than the surface by the "regenerating film"
those from untreated sea water. mechanism.
3. Laboratory beaker distillation tests 5. The beneficial effect of the polymers
showed that polymers acted as deflocculating studied to date has been so marked that
or dispersing agents and that the extent of the phenomenon justifies further and more
deflocculating action was dependent on poly detailed investigations.

ACKNOWLEDGEMENTS
The authors wish to thank Dr. H. R. C. ander in helpful discussions on polymer
Pratt and Mr. D. F. Kelsall for continued chemistry and of Dr. B. Harrop and Dr.
support during this work. The assistance of P. Plackett in molecular weight measure
Dr. D. H. Solomon and Professor A. E. Alex ment is gratefully acknowledged.

REFERENCES
1. Herbert, L. S.: Sterns, U. J.: Saline tries (A.N.Z.), Ltd., Melbourne, Private
Water Conversion II, A.C.S. Series No. communication.
38 (1963) p. 52. 8. McCartney, E. R.; Alexander, A. E.:
2. Yphantis, D. A.: Annals New York /. Colloid Sci., no. li (Aug. 1958) p. 383.
Academy of Sciences, no. 88 (1960) p. 9. Blackadder, D. A.: Industrial Research
586. Fellow Rep. no. 3, The Chemical Engi
3. Harvey, H. W.: "The chemistry and neer, Institution of Chemical Engineers,
fertility of sea waters," Cambridge Uni CE303 (Dec. 1964) .
versity Press (1957) p. 137. 10. Linke, W. F.; Booth, R. B.: Tram.
4. Zeleny, R. A.; Vithani, K.: "Combus A.I.M.E., no. 217 (1960) p. 364.
tion" (Feb. 1963) p. 47. 11. La Mer. V. K.; Healy, T. W.: Rev. Pure
5. Badger and Associates Inc.: Ann Arbor. and Appl. Chem., no. 13 (Sept. 1963)
Michigan, "Critical review of literature p. 112.
on formation and prevention of scale," 12. Moiliet, J. L.; Collie, B.; Black, W.:
Office of Saline Water, Rep. no. 25 Surface Activity, Spon Press. (1961)
(July 1959). p. 160.
6. Ireland, G. H.: "Corrosion prevention 13. Jirgensons, B.; Straumanis, M. E.: A
and control" (Oct. 1958) p. 57. Short Textbook of Colloid Chemistry,
7. Derrick, A.: Imperial Chemical Indus Pergamon Press, Ltd. (1962).

51
APPENDIX 1A
THE METHOD OF PREPARATION OF and a cold water bath was applied. The
LOW MOLECULAR WEIGHT temperature in the flask was controlled
POLYACRYLIC ACID close to 87°C. After monomer addition was
complete, the reaction moderated and steam
Isopropanol (200 gm) was placed in a heating was used again. The stirrer was
one liter flask equipped with stirrer, ther stopped and the mixture left heating over
mometer, reflux condenser, and addition night on the steam bath. A water-white very
funnel. The stirred isopropanol was heated viscous solution of approximately 60 per
to reflux. Then a solution of benzoyl perox cent solids was obtained.
ide (6 gm) in acrylic acid (300 gm) was Some batches of polymer were made using
added dropwise during hours. After variations in the weights detailed above, in
approximately one-half hour the reaction an attempt to produce polymers having a
became exothermic, the heat was removed. range of molecular weights.

APPENDIX IB
THE METHOD OF PREPARATION OF of essentially linear polymers.
A LOW MOLECULAR WEIGHT Isopropanol (200 gm) was placed in a
10 PER CENT ETHYL ACRYLATE— one liter flask equipped with stirrer, ther
90 PER CENT ACRYLIC ACID COPOLYMER mometer, reflux condenser, and addition
funnel. The stirred isopropanol was healed
The method was similar to that given in to reflux. Then a solution of azo di-iso
Appendix 1A, except that azo di-iso butyro butyro nitrile (7.8 gm) in acrylic acid
nitrite initiator was used in preference to (270 gm) and ethyl acrylate (30 gm) was
benzoyl peroxide to insure the production added dropwise during \\/2 hours.

APPENDIX 2
EQUILIBRIUM ULTRACENTRIFUGATION hours. There was no evidence of a depend
METHOD FOR ence of results on polymer concentration
MOLECULAR WEIGHT DETERMINATION in the range 0.5 to 1.5 per cent.
To reduce the time required for deter
Determinations were made in the Spinco minations, the rapid short (1 mm) column
Model E Ultracentrifuge (réf. 13) at speeds method of Yphantis (ref. 2) was adopted.
of about 25,000 rpm. Initial determinations Sedimentation times were reduced to about
made at 20°C. using isopropanol as solvent 3 hours at speeds of about 20,000 rpm, using
in conventional long (12 mm) columns, re isopropanol as solvent at a temperature of
quired sedimentation times of about 20 20°C.

SUMMARY OF DISCUSSION
There was no discussion.

52
Distillation Des Eaux Salines —

Protection Contre L'Entartrage Par

L'Addition de Polymères

L. S. Herbert, P. F. Rolfe et U. J. Stems

Australie

Toute nouvelle amélioration du rende les tubes en fin de marche, variaient selon
ment des usines de distillation d'eau saline la concentration de polymère employée
doit attendre la mise au point de procédés dans l'essai. A la concentration optimale
efficaces et peu coûteux permettant d'em de polymère, on a observé notamment qu'il
pêcher la formation de tartre sur les sur ne se formait qu'une mince pellicule de
faces d'échange de chaleur, particulièrement matière "plastique" qui, par séchage au
lorsqu'il s'agit de saumures d'une tempé contact de l'air, se détachait rapidement de
rature et d'une concentration plus élevées la surface d'échange de chaleur. L'analyse
que celles employées actuellement. Lei a indiqué que cette pellicule était princi
travaux antérieurs ont indiqué que l'acide palement composée de polyacrylate de
polyacrylique, d'un poids moléculaire d'en magnésium.
viron 20.000, ajouté à l'eau de mer alimen Au cours de recherches parallèles en la
tant un évaporateur expérimental à pulvé boratoire, des essais d'évaporation en vase
risation, à une concentration de 3 ppm, ont été mis au point et les résultats ont
prévient très efficacement la formation de indiqué qu'une certaine concentration de
tartre pendant l'évaporation à 115°C. polymère, s'établissant entre 1 et 4 ppm
Le présent document porte sur de nou selon les différentes eaux de mer, produi
velles études de ce phénomène. Plusieurs saient une diminution marquée du préci
lots d'acides polyacryliques de faible poids pité formé au cours de l'évaporation. Avec
moléculaire et un lot d'un copolymère, le même lot d'eau de mer, on a constaté
composé de 10% d'acrylate d'éthyle et de qu'il existait une certaine correspondance
90% d'acide acrylique, ont été préparés et entre la concentration de polymère donnant
mis à l'essai comme additifs contre l'entar la précipitation la plus faible dans les
trage. Le copolymère a été choisi pour les essais en vase et la concentration optimale
études plus poussées au moyen d'essais d'é- de polymère donnant la meilleure protec
vaporation par pulvérisation et par la tion contre l'entartrage dans les essais
méthode à longs tubes verticaux à écoule d'évaporation par pulvérisation.
ment laminaire ascendant. Pour tenter d'expliquer le mécanisme de
Les auteurs ont constaté que la protec protection des polymères contre l'entartrage,
tion la plus efficace contre l'entartrage se les auteurs offrent des théories analogues à
manifestait à une concentration optimale celles qui ont été avancées pour expliquer
de polymère se situant entre 1 et 4 ppm l'effet de floculation et de défloculation des
pour différents lots d'eau de mer. Les con polyélectrolytes sur les boues minérales.
centrations plus faibles ou plus fortes Deux mécanismes simultanés sont énoncés.
étaient moins efficaces et, aux concentra A la concentration optimale de polymère,
tions beaucoup plus élevées que la concen l'effet de dispersion ou de défloculation du
tration optimale, on a constaté que les polymère empêche le dépôt d'une partie
dépôts de tartre formés dans les essais importante des éléments d'entartrage; l'accu
d'évaporation à écoulement laminaire as mulation de la partie restante est prévenue
cendant s'opposaient plus fortement aux par la formation, à la surface d'échange
échanges de chaleur que ceux de l'eau de de chaleur, d'une mince pellicule, composée
mer non traitée. On a constaté que les principalement de polyacrylate de magné
caractéristiques physiques et la composition sium, qui est capable de se dépouiller et
chimique des dépôts formés sur les surfaces de se reconstituer spontanément et à
d'échange de chaleur, examinées en fendant maintes reprises au cours de l'évaporation.
Дистилляция Соленой Воды —

Предотвращение Образования Накипи

Посредством Добавки Полимеров

Л. С Герберт, П. Ф. Ролфе и Ю. Дж. Стерне

Австралия

Для дальнейшего повышения произ ческие характеристики и химический


водительности установок, опресняю состав отложений, образовавшихся на
щих соленую воду, требуется развитие теплообменных поверхностях, которые
дешевых и эффективных методов для по окончании опыта были обследованы
предотвращения образования накипи с помощью разрезания трубы, оказа
на теплопередаточных поверхностях, лись неоднородными и зависящими от
особенно при высоких температурах концентрации полимера, примененного
соленого концентрата и при более вы во время испытания. Следует отметить,
соких коэффициентах концентрации, что при оптимальной концентрации по
чем те, которые применяются в насто лимера была обнаружена только тон
ящее время. Прежние исследования по кая пленка из «пластичного» материала,
казали, что добавление полиакриловой которая по высыхании на воздухе бы
кислоты с молекулярным весом около стро отделялась от теплопередаточной
20.000 (при концентрации 3 мг/л.) к поверхности. Анализ показал, что она
морской исходной воде, было весьма главным образом состояла из поли-
эффективным в смысле предотвращения акрилата магния.
образования накипи на эксперименталь При параллельных исследованиях в
ном испарителе с распылением при лабораторном масштабе был проведен
температуре выпаривания 240°F. ряд выпарочных испытаний в химиче
Настоящий доклад связан с дальней ской посуде, результаты которых по
шим исследованием этого явления. Бы казали, что имеется концентрация по
ло произведено несколько загрузок по лимера, колеблющаяся в пределах от
лиакриловой кислоты с низким молеку 1 до 4 мг/л для различной морской
лярным весом и одна загрузка сополи воды, которая явно уменьшает коли
мера 10% этилакрилата — 90% акри чество осадка, образуемого во время
ловой кислоты, которые испытывались, процесса испарения. При одинаковом
как добавка для предотвращения обра составе морской воды было обнаруже
зования накипи. Сополимер был выбран но известное соответствие между кон
для более широкого обследования вы центрацией полимера, дающей мини
парки «с разбрызгиванием) и испыта мальный осадок при испытаниях в хи
ния испарения с ползучей пленкой. мической посуде, и оптимальной кон
Максимальная эффективность в смы центрацией полимера, максимально пре
сле предотвращения образования на дотвращающей образование накипи при
кипи имела место при оптимальной по испытании выпарки «с разбрызгива
лимерной концентрации, которая ко нием».
лебалась в пределах от 1 до 4 мг/л В настоящем докладе, пытающемся
для отдельных загрузок морской воды. объяснить противодействие полимеров
Более низкие и более высокие концен образованию накипи, были использова
трации оказались менее эффективны ны идеи подобные тем, которые были
ми, а при концентрациях значительно предложены для объяснения флокку
превышавших оптимальные, отложение лирования — дефлоккулирования, про
накипи при испытаниях на выпарку с изводимых полиэлектролитами на ми
ползучей пленкой оказалось более неральный шламм. Считается, что од
вредным для теплопередачи, чем от новременно существуют два механиз
необработанной морской воды. Физи ма. Благодаря диспергирующему или
дефлоккулирующему действию полиме стигается образованием на теплообмен-
ра при его оптимальной концентрации ной поверхности тонкой пленки, пре
предотвращается отложение значитель имущественно состоящей из полиакри-
ного количества составных частей на лата магния, которая сама собой пери
кипи. С другой стороны, предотвраще одически отваливается и регенерирует
ние накопления остальной накипи до во время процесса выпариавния.

Destilación del Agua Salina —

Evitación de la Formación de

Incrustaciones Mediante la Adición

de Polimeros

L. S. Herbert, P. F. Rolfe у U. J. Sterns

Australia

La ulterior mejora del rendimiento de las concentraciones considerablemente mayores


plantas de destilación de agua salina depen que la óptima, las incrustaciones deposita
derá del establecimiento de métodos econó das en las pruebas de evaporación por capa
micos y eficaces para evitar la formación ascendente resultaron ser más perjudiciales
de incrustaciones en las superficies transmi con respecto a la transmisión térmica que
soras de calor, especialmente cuando las las procedentes de agua de mar no sometida
temperaturas de la salmuera son más ele a tratamiento. Las características físicas y
vadas y los factores de concentración mayo composición química de los sedimentos for
res que los utilizados en la actualidad. En mados en las superficies de transmisión
investigaciones anteriores se había demos térmica, examinados después de abrir el
trado que el ácido poliacrflico de peso tubo al final del curso de cada prueba,
molecular aproximado a 20.000, añadido en resultó que variaban según la concentración
concentración de 3 ppm al agua de mar de polímero utilizada en la prueba. En
con que se alimentaba un evaporador expe particular, a concentraciones óptimas de
rimental por rociamiento, resultaba muy polímero, se observó tan sólo una película
eficaz para evitar la formación de incrusta delgada de una materia "plástica" que, al
ciones durante la evaporación a 240°F. secarse al aire, se desprendía rápidamente
El presente trabajo trata de las investiga de la superficie de transmisión térmica. El
ciones ulteriores relativas a este fenómeno. oportuno análisis indicó que se trataba prin
Varias partidas de ácidos poüacrflicos de cipalmente de poliacrilato de magnesio.
peso molecular bajo y una partida de un En una investigación de laboratorio simi
determinado copollmero, compuesto de 10% lar a la anterior, se llevaron a cabo pruebas
de acrilato de etilo y 90% de ácido acrilico, de evaporación en vaso de precipitados y
fueron preparadas y sometidas a prueba los resultados indicaron la existencia de una
como substancias aditivas evitadores de in determinada concentración de polímeros,
crustaciones. El copolfmetro fue seleccio que variaba de 1 a 4 ppm según las dis
nado para una investigación más extensa en tintas aguas de mar, lo cual producía una
las pruebas de evaporación por "rociamien notable reducción en la cantidad de preci
to" y por capa ascendente (LTV) . pitado formado durante la evaporación. Con
La máxima eficacia en la evitación de respecto a la misma partida de agua marina
incrustaciones se produjo a una concentra se observó cierta armonía entre la concen
ción óptima de polímero, la cual varió de 1 tración de polímero que produda un míni
a 4 ppm para las distintas partidas de mo de precipitado en las pruebas efectuadas
agua de mar. Las concentraciones inferiores en vaso de precipitados y la concentración
y superiores resultaron menos eficaces y, a óptima de polímero con la que se obtenía
el grado máximo de evitación de incrusta óptima de polímero se evita la sedimenta
ciones en las pruebas de vaporación por ción de una parte importante de los ele
rociamiento. mentos constituyentes de las incrustaciones
En el trabajo que nos ocupa, se aplican mediante la acción dispersante o desflocu
conceptos similares a los expuestos para lante del polímero, y se impide la acumula
explicar la actividad de floculación-desflocu- ción del resto por medio de la formación,
lación de los polielectrólitos en los fangos en la superficie de transmisión térmica, de
de origen mineral, en una aclaración tenta una capa delgada constituida principal
tiva de la eficacia de los polímeros para mente por poliacrilato de magnesio, la cual
evitar la formación de incrustaciones. Se da es capaz de desprenderse y reaparecer, es
por supuesta la existencia de dos meca pontánea y repetidamente, en el curso de
nismos simultáneos. Con la concentración la evaporación.

56
Heat and Mass Transfer in Flash

Distillation Without Metallic

Interfaces

Abraham Kogan

Israel

Methods of sea water desalination based and the amounts of vapor flashed off in
on distillation are today practically the each stage are condensed by direct contact
only ones that have reached an industrial with the surface of a converted water
production scale application. On the basis stream. This stream flows through the
of the considerable amount of theoretical stages in a countercurrent direction and
and experimental work that went into the emerges from the hottest stage at an in
development of these desalination systems, creased rate of flow and temperature. It is
it is possible to estimate with fair accuracy passed through a liquid-liquid-liquid heat
the minimum cost of water which they can exchanger, where it surrenders heat to the
achieve. makeup sea water stream. A product stream
Such estimates (ref. 1) have shown that is diverted from the plant and the remain
for optimized plants of one mgd capacity, ing stream of cold converted water is
the energy cost of desalination is still larger recirculated through the flashing stages.
by an order of magnitude than the theoret The performance of the multiple-flash
ical minimum energy necessary for the evaporator can be evaluated by setting up
removal of salts from solution. These large material and heat balance equations for
thermodynamic losses are explained by the each stage and solving them successively
need to maintain considerable temperature with the aid of an automatic computer.
differences across metal heat exchanger An alternative analytic solution would be
surfaces which would otherwise become more advantageous for design and optimi
exceedingly large. zation studies, since it would exhibit explic
A distillation process which avoids the itly the influence of the various parameters
use of metallic interfaces (ref. 2) for heat upon performance of the system. It is the
transfer holds promise for a real break purpose of this paper to develop such an
through in desalination technology. In such analytic approach to calculation of the
a process a stream of heated sea water is performance of a multiple-flash evaporator
cascaded through a series of flash stages without metallic interfaces.

RATE OF PRODUCTION
Figure 21 is a schematic representation widely different values for the two water
of temperature distribution in the distilla stream rates passing through the stage,
tion system. since a great difference in heat capacity
GB1 and GCi represent the rates of saline rate of the two streams would be incom
water and converted water, respectively, patible with small terminal temperature
leaving stage i and Xi —the rate of transfer differences at both ends of the cascade. It
of vapor from saline water stream to con is, therefore, reasonable to consider the
verted water stream in this stage. case in which the rate of sea water entering
It is obviously impractical to allow the hottest stage is equal to the rate of
converted water leaving it: in conjunction with Equation (1) , we
G.W = Ge. (1) obtain:
Using recursively the material balance G„U1 = GCl = G„ (i = 1,2.3 ...,..) (3)
equation for stage i An energy balance between rate of en
"i 1 GHui — CiH, = GC| thalpy loss by saline water stream passing
-С (2) through stage i and rate of enthalpy

z
о
"H
H
S3
03
5
h

M
S
■H

58
investment into production of stream gives Observe that since (Ih,.! — tH|) is of the
(Get) Blrt - (Get) h, = X, (hUV4 + ctBl) order of 1°F. ai is of the order of 0.001.
(4) Terms of second order in ai may, there
where fore, be neglected for engineering purposes.
, = i/2 (h, + hul) (5) Equation (10) gives, to a second order of
is a mean value of latent heat of saline approximation,
water in the system at temperature tH) and
G. i=i i=i hUii (П)
We shall define a relative production rate Approximating the variation of heat of
a, as the ratio of the rate of converted vaporization with temperature over the tem
water production in stage i to the rate of perature range of interest by a straight line.
converted water outflow from stage i. As h=a(l— bt) (12)
suming a constant value с for specific heat we can write
and writing
GHl = GH|<1 — X, (6) ¿-=| {l + b(.„m -.„,)}
in Equation (4) , we obtain neglecting terms of order (bt) '.
X, _c(tH|,1_ t,„) Equation (11) becomes:
<7) X с , - tHl)V + —
G, be (t',.tI - fHl)
g-= -(tHn.I
Equation (7) for the n stages of the cas
cade forms a linear system in X,. Indeed, = К (t^,. tHl) (IS)
substituting Thus the total production rate of the
G i =; G„ — 2 XK cascade is, to a high degree of approxima
we obtain tion, independent of the detailed tempera
ture distribution in the intermediary stages.
2 XK-a,G„,(i = 12.3, . -n) It is determined by the terminal tempera
(8) tures of the saline water stream only.
with the solution Figure 2 represents the variation of heat
X| — G„ ai nil - aK) (9) of vaporization h with temperature. Substi
tuting in Equation (12)
The total production rate X is obtained a = 1090 Btu/lb, b = 0.54Я . 10"* ("F) -1
by summation: the values of h differ from the linear ap
proximation by less than 0.3 per cent in the
X
Л Ы
2 ] (10) range
П (1 - ok)
G. G„ 32°F < t < 280°F

EXACT CURVE

60 IM 200
100 260 300
t CF)
FIGURE 22. VARIATION OF HEAT OF VAPORIZATION WITH
TEMPERATURE.

59
Based on these values of a and b, the t„, as a parameter. The relative production
variation of relative production X/G„ has is roughly proportional to the difference
been calculated and plotted in Figure 23 between inlet and outlet temperatures of
as a function of hot sea water inlet tempera saline water stream.
ture tH„.,, with brine outlet temperature

150 200 250 300


Wl <°F)
FIGURE 23. VARIATION OF RELATIVE PRODUCTION WITH
BRINE INLET TEMPERATURE.

Heat consumption analysis of heat consumption in the cascade


The rate of heat input necessary to com proper.
pensate for the thermodynamic irreversibili Define a stage heat transfer efficiency 1,:
ties of the cascade is given by I tc' — ten
H = G.c(tHM-tO (14) ' _ tHl - ten <15>
It should be emphasized that Equation In a completely inefficient cascade there
(14) does not represent the entire heat con would be no temperature rise in the con
sumption of the process. Heat recovery from verted water stream, i.e.. I , = 0. Conversely,
converted water leaving the hottest stage to in an ideally efficient cascade the converted
sea water entering it must be accomplished water would leave the stage at the tempera
by some kind of heat exchanger. Part of the ture of saline water in the stage, tc, =tH,,
total heat consumption is due to the irre i.e., I, — 1. This ideal condition can, of
versibilities in the heat exchanger. But we course, only be approached in a very large
shall limit ourselves in this discussion to the and completely deaerated stage, carrying
two water streams of equal salt concentra ditions and stage efficiencies, the relative
tion. The actual value of 1, is determined production rates n in Equation (22) must
by stage geometry, by flow characteristics of be evaluated in terms of I , , (i — 1 2fi, . . . , n) .
the two water streams and, to a great ex The relationships between aK and I, are
tent, by the degree of water deaeration. An defined implicitly by the nonlinear system
upper limit to 1 1, is set by the boiling of Equations (15), (16), and (17). Neg
point elevation of brine. For given geom lecting second order terms, it is possible to
etry, flow pattern, deaeration conditions, eliminate the temperatures from these equa
and salt concentration, it may be consid tions. Indeed, by Equations (15) and (16) ,
ered as a constant parameter that may be tHU1 — tH, = (tH,„ — tCl) +
determined by experiment.
(tc, - tc,.,) - (t„, - tc, J =
A second relationship between tempera (I, - a,) (t„, - tc,_,)
tures in stage i is given by an energy balance
between the two water streams: Hence, by Equations (7) and (16) ,
Gbu, tH,., — GH, tH, = Gc, tc, — GCl., tc,_, a, + i = -rh, + ^ • I, +; i — a, ♦ i • 0 — a,).
or, making use of Equations (3) , (6) , and at n, t щ i, — a,
(7). (23)
lHlrt - tCl = (1 - c) (tHl - t0l.,) (16) Again, neglecting second order terms,
Then, by recursion, £LLi = ÍLti.(l_ei) (24)
ai t.
'■«i — tc. = (t*,- te*)' П (1-a,)
(17) Equation (24) gives bj multiplication
Similarly, by Equations (15) and (16) П (1 - o») = a,/m„ (i = 23 n)
lc, - tcu, = (Ih, + tc.) • I, • П (1 - o«) (25)
(18) or, to a second approximation,
and, hence i-i
1 — 2aK : : a,/m,,(i = 2,S n)
tc. - tCo = 2 (tc, - tCUl) = K=l (26)
with
(tHl-tc„) -2 1|П (1 -аж)
1=1 *=* (19) m,= * I,
Ii
Inserting the Equations (17) and (19) This is a linear system of (n — 1) equa
into the relationship tions defining ai, a» • • • , a. in terms of a,
'я»»! — tH, — (tH„„ — tc„) -+- and the stage efficiencies I„ I I„. Its
(tc„ - tc) - (tHl - tc.) solution is given by
and eliminating (t„, — tc.) between the re i-i
o, = (1 — ai) m, П (I — Oi) ■
sulting equation and Equation (17) , we
obtain by Equation (14) (1 = 2А.".1.п) (27)
П (1 _«,,)• О (t„„ The value of «, can now be determined
H tBl) by substituting Equation (27) into the total
production expression, Equations (11) and
2 1, П (1 _aK) -I- II (1 _ai) _ 1 (13) . We obtain
1=1 K=l 1=1
(20) К = 2 a,
Also 1:1 n 1-1
X _ X/G. = oi + (1 — ai) 2 m, П (1 — m»)
H — H/G„ 1 = 3 к=з
(1 - a,)} {2 I, П (1 _aK) = ai+ (l-o.) {l-П (1-m,)
1=1 Izl K=l i=а
+ i=_i
П (1-a,) -1} =i-)rî (i
1=1 h
П (1 -a,) -C • <t„„,t — tBl) (21) = ^-21,
•i , = i +0 (a,")
1= i
or, neglecting second order terms in aK and Thus, to the second order of approxima
in bt, tion.
—={2 I. П (l_a,)-K}. 2 I,
Ii. i=i
H , .1 к l
К 1 Ol К (28)
1_ K -C(tHo>1-tHl) í22) To complete the calculation of steam
In order to obtain the cascade steam economy, we don't have to substitute ex
economy in terms of end temperature con plicitly for all values of aK in Equation
(22) . Making use of Equation (25) , we tion in the cascade by
obtain
(32)
2» I. П (1 - oK) = —I, 2» «■ = К • -i-
I,
i^i K=i at isi a, Equation (31) may then be put into the
(29) form of a steam economy expression:
hX 2 I, - К
and Equation (22) takes on the simple form i= i
_x_/_L__i) _í! i H 1-K <">
The dependence of steam economy on
H a, * 1 - К * С (tB.„ - t„,) saline water temperature drop in the cas
(30) cade and on stage efficiencies is exhibited
separately by this formula. Observing that
The last stage production rate en may
finally be eliminated from Equation (30) by 2n 1 1 is much larger than K, it is seen that
Equation (28) : 1=1
an increase in temperature range, i.e., an
— -ill П K 1 increase in relative production K, also has
a beneficent effect upon steam economy.
(31) For constant terminal temperatures, steam
economy increases linearly with the sum of
Define a mean value for heat of vaporiza all the stage efficiencies.

OPTIMUM NUMBER OF STAGES


The optimum number of stages of a de in that equation and a mean value î for g,
salination plant is determined by capital in Equation (35) , we obtain after some
investment in equipment and specific heat algebraic calculations:
consumption. The capital investment per 2 1 1 = n —A n2 (38)
stage will depend much upon the charac i=i
teristics of stage design. It will increase with with
stage efficiency. But it seems that there arc A —. . L (39)
no conclusive results concerning this param 1 — К tH„, — tHl
eter at present. It will have to be determined Equation (38) shows that even from the
by experiment. point of view of heat consumption alone
Interesting conclusions can be drawn, there is no advantage in increasing the
however, from Equation (33) by assuming number of stages indefinitely. The number
numerical values for the minimum tem of stages which gives maximum steam
perature difference. economy is expressed by
a, = t„, _ tci (34) n.„ = - =' -K . - '"' (40)
is attained in each stage. Expressed in terms 2A 21 Í
of Si the stage efficiency becomes and the corresponding value of steam
I, = 1 *! economy is
Ih, — tcUl
(35)
Using Equations (15) and (16) , the dif- (41)
erence tH, — tci _ , may be put into the
form 4I*
tH, — t C|-l — Figure 24 is a diagram of steam economy
as a function of a number of stages, with К
П (1 - ok) • (Ih«, - tHl) and i/ (t„nil — tH,) as parameters. The
(36) straight lines through the origin connecting
2 I, ПО -aK) + П (1 _„,) _ 1 all optimal points for К = 0.15 and К —
1=1 K=l 1=1
In order to obtain an insight into the 0.20 (i.e., approximately for tHluI — tH, =
■ 150°F and 200°F, respectively) do not vary
dependence of 2 I| upon the number of much in inclination. But the optimal
1= 1 points corresponding to the same value of J
stages n, we shall consider the particular lie quite far away. The great advantage of
case where
ai = as — ■ . . — an = a (37) a high temperature drop of saline water
through the cascade and of a small mean
Making this assumption in Equation (36) minimum temperature difference S is quite
and also substituting a mean value I for I, evident.
X«leF

FIGURE 24. VARIATION OF STEAM ECONOMY WITH NUMBER


OF STAGES.

REFERENCES
1. Fluor Corp.: U. S. Office of Saline Water landris, G. C.: Chem. Eng. Prog. vol.
Rcpt. no. 34 (1959) . 57 (1961), p. 47.
2. Othmer. D. F.; Benenati, R. F.; Gou

SUMMARY OF DISCUSSION
There was no discussion.

63
Transfert de Masse et de Chaleur

Dans la Distillation Spontanée Sans

Interfaces Métalliques

Abraham Kogan

Israel

Les trois méthodes de distillation pour tournée du système en tant que produit
le dessalement de l'eau de mer qui sont de la distillation, tandis que la plus grande
en utilisation sur une grande échelle—la partie circule à nouveau à travers les étages
distillation à effets multiples à faible ten de vaporisation spontanée.
sion de vapeur, la distillation spontanée à Comme la condensation par contact
étages multiples et la thermocompression— direct avec l'eau convertie peut se faire
ont toutes une caractéristique commune: avec des coefficients de transfert beaucoup
elles utilisent toutes des échangeurs de plus élevés que ceux obtenus dans la con
chaleur métalliques pour le transfert de la densation pelliculaire normale, cette mé
chaleur de la vapeur de condensation à thode semble offrir des possibilités pour
l'eau saline. Dans la conception de ces arriver à une réduction importante des
installations, une diminution des dimen frais de dessalement.
sions de l'équipement de transfert de Ce document porte sur le traitement
chaleur a pour résultat une augmentation analytique du système à vaporisation spon
dans la différence de température à travers tanée à étages multiples par contact direct.
les parois de l'échangeur de chaleur pour On peut décrire la performance de trans
une capacité donnée de l'installation. Les fert de chaleur et de masse entre les deux
conceptions optimums, dans lesquelles on courants d'eau, d'un seul étage d'un tel
effectue un compromis entre le coût de la système, par un paramètre d'efficacité
vapeur et l'amortissement de l'investisse d'étage:
ment en biens d'équipement, pour arriver I, = (t., - t,ul)/(tHI - UUJ
à un coût minimum de l'eau convertie,
ont pour résultat une consommation rela donnant l'élévation de température du
tivement élevée de chaleur spécifique. courant froid en tant que pourcentage de
la différence maximum de température
Une méthode alternative de distillation dans cet étage. I, dépend de la géométrie
a été proposée par Othmer dans laquelle de l'étage, des caractéristiques de débit, de
on évite complètement la condensation sur la concentration en sel et du degré de
des surfaces métalliques. Dans cette mé désaération de l'eau. On peut le déterminer
thode, un courant d'eau saline et un de façon empirique.
courant d'eau convertie passent à contre- En supposant des taux égaux d'entrée
courant à travers une série d'étages à vapo d'eau saline et de sortie d'eau convertie
risation spontanée. Dans chaque étage, une dans un étage, l'équilibre énergétique de
certaine quantité de vapeur est dégagée l'étage devient:
spontanément du courant d'eau saline et '■M — l«l = (' — ('hi —
condensée par contact direct avec le courant
d'eau convertie qui est un peu plus froid. où tH| et t,., sont respectivement les tem
La saumure concentrée est déchargée de pératures des courants chauds (H) et froids
l'étage à la plus faible température en (c) quittant l'étage i, tandis que «, est le
tant que résidu, tandis que le courant taux de production relatif de l'étage:
d'eau convertie émergeant de l'étage le plus ai = X,/G, = c (t„ui — tH1)/h, 4. i/2
chaud abandonne sa chaleur au courant Les trois équations ci-dessus forment un
d'entrée de l'eau de mer dans un échangeur système non linéaire en tHul, tCl et ai.
de chaleur liquide-liquide-liquide. Une En observant que ai est de l'ordre de
partie de l'eau convertie refroidie est dé 0.001 et que la variation de la chaleur de
vaporisation avec la température peut très moyenne donnée entre les deux courants
bien s'exprimer en approximation par une d'eau dans un étage I, on obtient l'écono
ligne droite ce système se simplifie en négli mie de vapeur la plus élevée lorsque:
geant les terms de second ordre. On obtient nOI>t = {(1-K) / 21}. {(tBlwl _ t„,)/a}
alors les résultats significatifs suivants: L'économie maximum de vapeur corres
1. Le taux relatif de production d'en pondante est donnée par:
semble ne dépend pas des efficacités des
étages séparés. Il est déterminé par les (hX/H),1I = (l„„-g/4Ie
températures terminales du courant d'eau En contraste avec les méthodes normales
saline: de distillation, dans lesquelles l'entartrage
X/Gn = K(tHlul_tHl) = (c/a) limite fortement la température la plus
[(tiw - tHl) +b(tH.%, - t„',)] élevée de l'eau de mer, on peut, dans la
2. Considérant seulement la consomma méthode à distillation par contact direct,
tion de chaleur provoquée par les irréver tolérer des températures d'eau de mer
sibilités dans la cascade des étages de vapo beaucoup plus élevées, ce qui a pour résul
risation spontanée, l'économie de vapeur tat à la fois une plus grande économie de
dépend du taux de production et de la vapeur et une augmentation du taux de
somme de toutes les efficacités de chaque production.
étage: La dernière équation montre également
l'importance d'une faible valeur de la
hX/H = ^| I,-K^/(l-K) différence de température terminale d'étage
i. Dans la méthode à distillation par con
3- La consommation de chaleur spéci tact direct, on devrait pouvoir obtenir des
fique ne diminue pas indéfiniment avec valeurs très faibles de J, ayant pour résultat
l'augmentation du nombre des étages. Pour une plus grande économie de vapeur.
une différence de température minimum

Перенос Тепла и Массы при Дистилляции

со Вскипанием без Металлических

Поверхностей Раздела

Абрахам Коган

Израиль

Три метода дистилляции для опрес компромисс с амортизацией капитало


нения морской воды, достигших широ вложения, чтобы снизить до минимума
кого применения — 1) Многоступен стоимость опресненной воды, получа
чатая дистилляция с длиннотрубным ется относительно высокое потребле
вертикальным испарителем; 2) Много ние удельной теплоты.
ступенчатая дистилляция со вскипани бттмер предложил альтернативный
ем; и 3) Со сжатием пара — имеют метод дистилляции, при котором совер
одну общую черту: они все применяют шенно не применяется конденсация на
металлические теплообменники для пе металлических поверхностях. При этом
реноса тепла от конденсируемого пара методе поток соленой воды и поток
к соленой воде. В проектах таких уста опресненной воды движутся во взаим
новок заданной производительности, но-противоположных направлениях че
уменьшение размеров теплообменного рез ряд ступеней вскипания. В каждой
оборудования сопровождается увели ступени мгновенно отводится из потока
чением перепада температур у стен соленой воды некоторое количество
теплообменников. В оптимизированных пара, который конденсируется при со
проектах, где стоимость пара идет на прикосновении с несколько более хо
лодным потоком опресненной воды. ние, что ai является величиной поряд
Концентрированный раствор сбрасыва ка 0,001, и что колебания тепла паро
ется в виде продувки из ступени с са образования в зависимости от темпера
мой низкой температурой, в то время туры близко приближаются к прямой
как поток опресненной воды, выходя линии, эта система может быть упро
щий из самой горячей ступени, отдает щена, отбросив члены второго поряд
в жидкостно-жидкостно-жидкостном те ка. Тогда получатся следующие суще
плообменнике свое тепло исходному ственные результаты:
потоку морской воды. Часть охлажден 1. Общая относительная скорость
ной опресненной воды отводится из продукции не зависит от эффективно
системы в качестве конечного продук сти отдельных ступеней. Она опреде
та, в то время как ее большая часть ляется конечными температурами со
рециркулируется обратно через ступе леного потока
ни вскипания.
Так как при конденсации путем пря А = - { (Ч,., -tHl) + 0(t,M _ tHl)}
мого контакта с опресненной водой 1 a =K(tHM:tHl)
коэффициенты теплопередачи гораздо
выше, чем при обычной пленочной кон 2. Принимая во внимание только по
денсации, то с помощью этого метода требление тепла, вызываемое необра-
видимо удастся значительно снизить тимостями в каскаде ступеней вскипа
стоимость опреснения. ния, экономия пара зависит от скоро
Этот доклад аналитически разбирает сти продукции и от суммы эффектив-
многоступенчатую прямо-контактную ностей всех отдельных ступеней:
систему вскипания. в
fix £ !|-к
Производительность одной ступени
такой системы, при переносе тепла и н - 1 _к
массы между двумя потоками воды, 3. Потребление удельной теплоты не
может быть изображена параметром ограниченно не уменьшается с увели
эффективности ступени чением числа ступеней. При заданном
I, — tC| ~ tc'-i среднем минимальном температурном
'и, - te,., перепаде § между двумя потоками во
где повышение температуры холодно ды в ступени, максимальная экономия
го потока выражено в процентах мак пара получается, когда
симального температурного перепада _ 1 — К >н„., — tHi
ступени. Ii — эффективность теплопе -~2Г~' i
редачи ступени зависит от геометриче
ской формы ступени, характеристик Соответственная максимальная эко
потока, концентрации соли и степени номия пара выражается в виде
деаэрации воды. Она может быть опре
делена эмпирически. (ш\ _ t«.ti - tu,
Считая, что в одной ступени вток \Н/"
N BU 41«
соленой воды и истечение опресненной
воды имеют одинаковую скорость, В противовес обычным методам ди
энергетический баланс ступени выра стилляции, при которых отложение на
зится в виде кипи сильно ограничивает температуры
морской воды, метод прямо-контактной
'"1*1 — tci = 0 — «i) ('и, — te,.,) дистилляции допускает применение го
aïïj tB, и te, являются температурами раздо более высоких температур мор
горячего и холодного потока, соответ ской воды, благодаря чему снижается
ственно выходящих из ступени, в то потребление пара и возрастает ско
время как а, представляет собой отно рость производства.
сительную скорость продукции ступени Последнее уравнение указывает так
X, C(t„ul-t„) же на важность иметь в ступени малый
конечный температурный перепад §.
0,1 - G, - h, + v4 : При прямо-контактной дистилляции
Вышеуказанные три уравнения пред можно получить весьма низкие значе
ставляют собой не-линейную систему ния §, что улучшает паровое хозяй
в tHl.,, te, и m- Принимая во внима ство.

G6
La Trasmisión Térmica y de Masas

en la Destilación Instantánea Sin

Interfaces Metálicas

Abraham Kogan

brad

Los tres métodos de destilación usados como producto, si bien la mayor parte del
para la desalinización de agua de mar que agua vuelve a circular a través de las etapas
han llegado a aplicarse en gran escala— de evaporación instantánea.
destilación con evaporadores verticales de Como la condensación por contacto di
tubos largos (VTL) de efecto múltiple, recto con el agua transformada puede lo
destilación instantánea en etapa múltiple y grarse con coeficientes de transmisión tér
compresión de vapor—tienen una caracter mica mucho más altos que los obtenidos en
ística en común: la utilización de intercam la condensación convencional por formación
biadores térmicos metálicos para trasmitir, de película, el método que nos ocupa ofrece,
al agua salina, el calor procedente de la al parecer, la posibilidad de reducciones
condensación del vapor. En el diseño de importantes en el costo de la desalinización.
tales instalaciones, la reducción de las di En el presente trabajo, se expone el trata
mensiones del equipo trasmisor de calor miento analítico del sistema de destilación
resulta en un aumento de la diferencia de instantánea en etapa múltiple por contacto
temperatura a través de las paredes del directo.
intercambiador térmico, para una capaci El rendimiento de una etapa de tal
dad determinada de la planta. En los di sistema, en cuanto a la trasmisión de calor
seños calculados para un rendimiento y masa entre ambas corrientes de agua,
óptimo, en los que se establece un equili puede determinarse mediante un parámetro
brio entre el costo de la producción de de la eficiencia de etapa.
vapor y la amortización del capital inver
tido, a fin de conseguir un costo mínimo I, = (tc.-tc,.,) /(t,, - tc.J
de agua transformada, se obtiene como re considerando el aumento de temperatura
sultado un consumo específico de calor de la corriente fría como porcentaje de la
relativamente elevado. máxima diferencia de temperatura habida
Como método alternativo de destilación en la etapa. El valor I, depende de la
Othmer ha propuesto uno mediante el cual estructura geométrica de la etapa, caracter
se evita por entero la condensación sobre ística de la corriente, concentración de sal
superficies metálicas. En este método, una y grado de desaireación del agua. Puede
corriente de agua salada y otra de agua determinarse empíricamente.
transformada fluyen en contracorriente a Dando por supuesta la igualdad del flujo
través de una serie de etapas de evaporación de entrada de agua salada y de salida de
instantánea. En cada etapa de la corriente agua transformada, en una etapa, el equili
de agua salada se evapora instantáneamente brio de energía de la etapa es
una cantidad de vapor, que se condensa por
contacto directo en la corriente, algo más t„m - t,., = (1 - ct) (tw, - te, - 1)
Ma, de agua transformada. La salmuera donde tHl y tc, son. respectivamente, Ы
concentrada es eliminada como descarga de temperaturas de las corrientes caliente y
la etapa de menor temperatura, mientras fría que salen de la etapa i, mientras que
que la corriente de agua transformada que ai es un índice relativo de la producción
surge de la etapa más caliente entrega de la etapa
calor a la corriente de entrada de agua de a, = X,/G, = c (tw, + 1 - tw,)/h, + i/2
mar, en un intercambiador térmico líquido-
líquido-líquido. Parte del agua transforma Las tres ecuaciones anteriores constitu
da, ya fría, es desviada fuera del sistema, yen un sistema no lineal en tWui, tr¡ y ai
Teniendo en cuenta ai es del orden de número de etapas. Para un determinado
0,001 y que la variación del calor de vapo promedio de diferencia mínima de tempera
rización con la temperatura puede repre tura entre ambas corrientes de agua en la
sentarse aproximadamente por una recta etapa, la mayor economía de calor se logra
este sistema se simplifica despreciando los cuando
términos de segundo orden. De esta forma, n„pt = { (1 - R) /21} - { (t.M - tWl) ¡i }
se obtienen los resultados significativos
siguientes: La correspondiente economía maxima de
1. £1 índice relativo total de producción vapor se calcula mediante
no depende de la eficiencia de cada una de (ïïx/H) = (tw..t _ tWl) /4ia
las etapas. Se determina mediante las tem
peraturas finales de la corriente de agua En contraste con los métodos de destila
salada ción convencionales, en los que la forma
ción de costra limita considerablemente la
X/Gr = К (t.M = (ca) { (tw>il _ twi) temperatura máxima del agua del mar, en
+ b (tfj-tw,1) } el método de destilación por contacto di
2. Considerando únicamente el consumo recto pueden admitirse temperaturas de
de calor ocasionado por las irreversibili- agua de mar mucho más elevadas, lo cual
dades existentes en la catarata de etapas in da por resultado una economía de vapor
stantáneas, la economía de vapor depende mejorada y un índice de producción mayor.
del Indice de producción y de la suma de La última ecuación indica asimismo la
todos los valores de la eficiencia de cada importancia de un valor pequeño de la
una de las etapas: diferencia mínima de temperatura de la
■ etapa. En el método de destilación por con
EX/H = (S I, - K)/(l - K) tacto directo es posible obtener valores de
muy reducidos, lo cual da origen al mejora
3. El consumo específico de calor no dis miento de la economía del vapor.
minuye indefinidamente con el aumento del
A New Ion -Exchange Desalination

Technique

Robert Kunin

United States of America

INTRODUCTION
The various programs throughout the some practical problems that require re
world, geared to the development of brack agents for amelioration. Whereas these
ish and sea waters as well as sewage efflu problems may not appear to be funda
ents as sources of water for domestic, mental to these processes, they are, for all
agricultural, and industrial uses, have re practical purposes, fundamental when one
sulted in studies of new techniques for the considers operation of the processes under
desalination of such supplies. These tech field conditions. Too often, cost estimates
niques include various evaporative, freezing, are made for processes operating on a
membrane, ion-exchange, and extraction sparkling clear solution of NaCl instead
processes. Although ion-exchange has been of a turbid saline water containing such
widely used for many years in various water troublesome constituents as CaSO,, organic
treatment practices, including softening, de- acids (humic and fulvic acids) , iron, and
ionization, and dealkalization, the principle manganese. For example, all evaporative
has been ignored as a desalination tech processes operating on saline waters require
nique to a considerable degree in recent chemicals to prevent scaling, foaming, and
years. Ion-exchange processes have been corrosion. Electrodialysis cannot be effec
limited primarily to concentrations below tively accomplished without extensive water
1,000 ppm; however, in some instances, 500 pretreatment. If the water is not effectively
ppm has been an upper limit. Although pretreated, the membranes will foul with
some ion-exchange deionization plants are organic matter and scale rapidly on many
built for operation above this concentration raw waters. The same action may be antici
level, the number is quite small and re pated for other osmotic membrane proc
stricted to unusual conditions. esses. The "shutdowns" created by these
One of the problems associated with the scaling and fouling problems are quite
use of ion-exchange resins for the desalina costly and have been grossly underesti
tion of water is the fact that a minimum mated in many evaluations. Their severity,
of equivalents of a base and an acid must however, must be considered when the
be used for each equivalent of salt re processes are compared with ion-exchange.
moved. Although this fact has limited the The limitations of ion-exchange in treat
use of ion-exchange heretofore to salini ing waters of high concentrations are based
ties below 500 ppm, it is most important upon two factors: the ion-exchange resin
to reassess the virtues of ion -exchange in regeneration costs and the rinse require
terms of the technology that has been de ment. The first factor is quite obvious and
veloped in recent years. In comparison with has already been discussed. The relation
other desalination techniques, ion-exchange ship between the second factor and influent
is often neglected in many desalination concentration, however, is not usually real
programs because of this obvious salinity- ized by investigators. When the feed con
cost relationship. However, the other tech centration is low, the rinse requirement is
niques such as distillation, membrane proc not a serious problem since there is usually
esses, freezing, etc., although fundamentally ample deionized product available for rin
less sensitive to salinity, are plagued with sing, or raw water can be used for rinse
without appreciably exhausting the resins. salinity such as brackish water is the de
At high concentrations, the problem be velopment of ion-exchange resins of high
comes quite serious since sufficient product capacity and high regeneration efficiency
is not available and the use of raw water using régénérants of low cost, and the de
for rinse exhausts an appreciable fraction velopment of techniques for employing
of the capacity of the exchangers. such resins in a desalination process. This
The simplicity and flexibility of ion- is not a novel thought; the literature is
exchange as a unit operation has resulted replete with the description of such efforts.
in the worldwide acceptance of ion-exchange In previous publications, the author and
techniques for normal water treatment prac his associates (refs. I. 2) have described the
tices. Of considerable significance in this nature and properties of such ion-exchange
respect are the high flow rates that one resins and their use in deionization systems.
can achieve with small units and the ease It becomes quite obvious that for efficient
with which one can operate such equip regeneration with either acid or base, the
ment continuously and intermittently with ion-exchange resin must essentially be a
but minimum degrees of difficulty. Recent weak electrolyte, i.e., a carboxylic acid
developments in ion-exchange engineering, cation-exchange resin (R-COOH) or an
resulting in practical means for conducting amine-based anion-exchange resin (R-NH,) .
ion-exchange in continuous, countercurrent These structures are in contrast to the
fashion coupled with the development of strong electrolyte ion-exchange resins such
new ion-exchange resins of high capacity as the sulfonic acid cation-exchange resin
and regeneration efficiency, have extended (R-SO,H) and the quaternary ammonium
the limits of ion-exchange methods to in anion-echange resin,
clude the desalination of waters of higher CH,
salinity than before. R-N CH^OH"
The key to extension of ion-exchange CH,
deionization techniques to waters of higher

CONVENTIONAL ION-EXCHANGE
Before considering the extension of ion- RSO.H + R-OH + NaCI -»
exchange to brackish waters, some aspects RSOjNa + R-Cl + НгО (3)
of the deionization of water with a conven In most conventional deionization systems,
tional ion-exchange resin system must be the water is first passed through the cation-
considered. exchange resin to remove cations in ex
In conventional deionization the water change for hydrogen ions. The efficiency of
may first be passed through a column of this operation depends upon the selectivity
a strong acid cation-exchange resin in the of the cation-exchange resin for the various
hydrogen cycle in order to remove the cations to be removed as compared with
cations in exchange for hydrogen ions, the hydrogen ions in the regenerated form
RSO.H + NaCl ï± RSO.Na + HCl (la) of the cation-exchange resin, normally a
The effluent from this operation must then sulfonic acid exchanger. It is quite obvious
be passed through a column of anion- that, if the exchanger is not very selective
exchange resin in the hydroxide form to for a particular cation, leakage of this
remove the acid formed in the first step, cation will readily occur, resulting in poor
ROH + HCl -> R-Cl + H.O (lb) effluent quality. Table IX summarizes the
In contrast to the above procedure, the selectivities of the various cations normally
water may first be passed through a strong encountered in the deionization of water.
base anion-exchange resin in order to re It is readily evident from these data that
move the anions in exchange for hydroxide leakage problems in the hydrogen cycle
ions, operation will depend upon the amount
of monovalent ions (Li, Na, and K) pres
R OH + NaCl ;± R-Cl + NaOH (2a) ent in the influent.
The effluent from this step must then be It is also quite obvious that the divalent
passed through the column of the hydrogen (Ca, Mg) or hardness-contributing ions do
form of the cation-exchange resin, not pose leakage problems. It is quite in
RSO.H + NaOH -> RSO.Na + H.O (2b) teresting to note that most natural waters
Л third technique is to pass the water used for domestic and industrial purposes
through a single bed containing an inti are low in monovalent ions as compared to
mate mixture (Monobed) of the above divalent ions. This fact has contributed
anion- and cation-exchange resins. significantly to the success of ion-exchange

70
as a deionizacion technique. If the salts in monly found in water supplies with those
most waters now being treated by ion- of the hydroxide ion. It is evident from
exchange were primarily sodium chloride, these data that the leakage would be consid
deionization by means of ion-exchange erably less if this procedure were followed.
would not be as popular as it now is. There are, however, practical problems that
discourage the use of this technique. These
TABLE IX. Selectivity of Cations in the include the precipitation of CaCO, and
Hydrogen Cycle of a Sulfonic Acid Mg(OH) , in the anion-exchange column
Cation-Exchange Resin and the extra expense of removing CO,
and НСО,- by ion-exchange rather than by
mechanical means.

W 0.8 TABLE X. Selectivity of Anions in the


H«« 2.0 Hydroxide Cycle of a Quaternary Anion-
K* S.0 Exchange Resin
NH<* S.0
Mr" 20 Selectivity coefficient
Ca» 42 Anion vs hydroxide Ion
Leakage of monovalent ions during the HCOi- 4
hydrogen cycle can best be understood by ГЛ- 11
NOr 40
tracing the course of the resin using the 80.= 60
sodium ion (Na*) as the model. In most
waters encountered, the sodium is present The economics and the effluent quality
as the sulfate, chloride, bicarbonate, or which can be achieved with any of the
carbonate salt. The possible exchange re above techniques depend to a large degree
actions involved are: upon the choice of both the ion-exchange
RSO,H + NaCl ^ RSO.Na + HCl (1) resins and the technique as well as the
2 RSO.H + Na,SO, -> 2 RSO.Na + H.O (4) regeneration levels. In the multiple bed
RSO.H + NaHCO, ;± techniques, the economics and quality that
RSO,Na -f. CO, + H,0 (5) can be achieved usually depend upon the
2 RSO.H + Na,CO. — leading column of ion-exchange resin. The
2 RSO,Na + CO, +H.O (6) leakage characteristics of an NaCl water
and the excess regeneration requirements
In the case of NaCl and Na,SO„ the of the leading column in each of the above
hydrogen ions liberated during the ex two methods are summarized in Tables XI
change process are present as hydrochloric and XII. These data depict the excessive
or sulfuric acid (reactions 1 and 4) . This quantities of régénérants required if NaCl
acidity limits the extent to which the re salinity is present and if good quality of
actions can proceed. In the case of NaHCO, water is required. Countercurrent operation
and Na,CO„ the products of the exchange reduces the leakage and improves the eco
reaction are CO, and H,0 and, therefore, nomics of the regeneration.
the reactions (5 and 6) proceed to com There are, however, various ion-exchange
pletion. Even though the selectivity coeffi techniques, developed over the last several
cient for the sodium ion is low, efficient years, which have improved the economics
removal (low leakage) can be achieved if of ion-exchange as a deionization tech
the sodium ion is present as alkalinity nique. Some of these, although rather
(NaHCO,, Na,CO„ and NaOH) . Leakage obvious, have been ignored in various de
of sodium ions is, therefore, only encoun salination programs. None of these tech
tered in waters high in chlorides and sul niques is of any great importance by itself,
fates. but they become significant when used as
It is quite interesting to note that if one a group. For example, one would not gen
reversed the order of the two ion-exchange erally employ a strong base resin following
resins and passed the water first through the sulfonic acid exchanger in the conven
the hydroxide form of the anion-exchange tional deionization technique. Unless one
resin (strong base, quaternary ammonium wished to remove CO, and SiO„ a weak
anion-exchange resin) and then through base anion-exchange resin would be used
the hydrogen form of the sulfonic acid since it usually exhibits a much higher
cation-exchange resin, the leakage would capacity than the strong base anion-ex
be determined by the anion-exchange selcc- change resins and since it can be regener
tivities. Table X compares the anion- ated with base at high efficiency. It is,
exchange selectivities of those ions com however, possible to regenerate such resins
TABLE XI. Leakage and Regenerant Efficiency of a Sulfonic Acid Cation-Exchanger
Operated in the Hydrogen Cycle on an NaCl Water

Pounds HtSOt (66° Be) True capacity, Leakage Excess acid


per cu ft kgr per cu ft percent reQuired, per cent
tJt 10.4 68 58
6.0 17.0 45 95
7.5 24.5 80 104
10.0 27.8 22 148
15.0 32.1 10 210
20.0 S4.0 6 290
25.0 84.9 8 875

TABLE XII. Leakage and Regenerant Efficiency of a Quaternary Ammonium Anion-


Exchange Resin Operated in the Hydroxide Cycle on an NaCl Water

Pounds. NaOH per True capacity. Leakage Excess caustic


cu ft kg-r per cu ft per cent required, per cent
1 6.0 12 74
1 6.1 8 186
1 8.8 6.5 215
4 9.7 8.7 260
( 11.8 1.5 818
8 18.8 0.7 595

with lime slurries or with NH, using lime cut the cost of regeneration significantly.
to recover the ammonia from the waste If these approaches were coupled with the
regenerant. The same is true for the com use of countercurrent and continuous mov
bined use of strong and weak acid cation- ing bed techniques, ion-exchange could be
exchange resins. This approach has not re even more useful as a desalination process.
ceived proper attention although it would

WEAK ELECTROLYTE ION-EXCHANGE RESIN SYSTEMS


The quest for an ion-exchange process, resins in deionization systems is not new.
based solely upon weak electrolyte ion- In fact, both carboxylic acid cation-exchange
exchange resins, is predicated upon the as resins and weak base anion-exchange resins
sumption that the ion-exchange desalina have been used to increase the efficiency of
tion process involves the overall removal deionization systems; however, in these cases
of electrolyte from water by exchanging the the weak electrolyte ion-exchange resins
anions and cations for hydrogen and hy were always used in conjunction with strong
droxide ions and that an acid and a base electrolyte ion-exchange resins. It is impor
are required for regeneration. Thus, the tant to note, however, that when such resins
author has rejected all techniques which were used in deionization systems, they were
employ ion-exchange resins for removing regenerated at approximately 100 per cent
electrolytes with water, electrical energy, efficiency with inexpensive regenerants.
or steam as a regenerant. Experience has When used without strong electrolyte ion-
shown that such techniques are ineffective, exchange resins, the nature of the equili
resulting in poor utilization of the ion- bria involved limited their use to a mixed
exchanger's capacity. An ideal ion-exchange bed or Monobed system, i.e., an intimate
system is one in which the exchangers can mixture of the two weak electrolyte ion-
be regenerated by an equivalent of cheap exchange resins. Several years ago, the au
acid and base for each equivalent of salt thor and his associates (ref. 1, 2) investi
removed. In addition, the exchangers must gated the properties of a weak electrolyte
be capable of effectively removing salt from mixed bed for dionizing brackish waters
water at high degrees of utilization of the using the ion-exchangers then available and
ultimate capacity of the ion-exchange resins. concluded that the system was poor from
Unless these requirements are met, ion- a kinetic point of view, requiring finely
exchange cannot be used economically for divided material. A comparison of the de
the desalination of brackish or saline waters. ionization efficiency of Monobeds of normal
The use of weak electrolyte ion-exchange particle size and of finely divided material
70

ELECTROLYTE TREATED, Equiv /Liter


FIGURE 25. PERFORMANCE OF A WEAK ELECTROLYTE
ION-EXCHANGE MONOBED.

is given in Figure 25. The author and his generation was ineffective, particularly if
associates found such mixed beds to be divalent ions were present in the feed. A
difficult to handle in cyclic processes since system (ref. 3) has been developed for
the two ion-exchange resin components regenerating such exhausted mixed beds
were difficult to separate for the purpose without separation of the ion-exchange
of regeneration. resin components, using ammonia followed
The authors also investigated the use of by water saturated with CO,. The method
finely divided exchangers employing super has not been sufficiently economic to be
heated water as a regenerant. Although useful for treating brackish waters, although
some success was achieved, the quality of it does hold promise in chemical processing.
the water was poor and the method of re

A NEW ION-EXCHANGE DESALINATION TECHNIQUE


Quite recently, the author (ref. 4) and a reverse deionization system (anion-ex-
his associates (ref. 5) developed a new ion- changer followed by cation-exchanger)
exchange desalination technique for em based upon the following reactions:
ploying weak electrolyte ion-exchange resins [R-N] + H,0 + CO,-»
without the use of the mixed bed principle. [R-NH] HCO,
This technique is based upon the discovery (carbonation) (1)
that certain anion-exchange structures of a [R-NH] HCO, + NaCl ->
weakly basic nature can form the bicarbon [R-NH] CI + NaHCO,
ate salt with solutions of carbon dioxide (alkalization) (2)
and that the chloride-bicarbonate selectivity R-COOH + NaHCO, -»
coefficient, CI" , is favorable. This dis- R-COONa + CO, + HsO
KHCOa- (dealkalization) (3)
covery suggested the possibility of employ [R-NH] CI + NH.OH-*
[R-N] + NH.C1 + HsO
ing weak electrolyte ion-exchange resins in (anion-exchanger regeneration) (4)
or TABLE Xin. K hco^ Selectivities of
2 [R-NH] CI + CaO-»
[R-N] + CaCl, +H.O (4a) Anion-Exchange Resins
2 RCOONa + H.SO. -»
2 RCOOH + Na^O. Amberlite K Cl« Degree of chloride
(cation-exchanger regeneration) (5) resin HCO» saturation, per cent
Since (he equilibria for these ion-exchange IRA 68 60 26
reactions were favorable, the basic aspects IRA-68 20 60
of these reactions and the deionization sys IR-45 1 9
tem were studied in detail both in the IRA-9S 4 28
laboratory and in the field. IRA-400* 2 40
■ Measured at 0.02N concentration.
LABORATORY STUDIES b A strong base anion-exchange resin.

The key factors in the new process are alkalinity. However, since the alkalinity
the unusual characteristics of the weak base would normally be present as sodium al
anion-exchange resin, Amberlite IRA-68. kalinity, not all weak acid cation-exchange
This weak exchange resin is not onh resins are useful and Amberlite IRC-84 is
capable of absorbing CO, to form the bicar unique in this application. The properties
bonate salt, but also the bicarbonate- of these two resins as compared with other
mineral acidity selectivity is such that the weak electrolyte ion-exchange resins are
salts present in brackish water and even summarized in Table XIV. By selecting the
sea water can be converted to alkalinity proper weak electrolyte ion-exchange resins,
with negligible leakage. The unusual it is possible to employ them in a de
Khcoj- of Amberlite IRA-68, as compared salination technique at high regeneration
with other anion-exchangc resins, is illus efficiencies at capacities corresponding to a
trated in Table XIII. high degree of utilization of the ion-ex
Because of this, one may select a weak acid change resins' theoretical capacities.
cation-exchange resin for removing the The new cyclic deionization process in-

TABLE XIV. Properties of Weak Electrolyte Ion Exchange Resins

Ion-exchange resin Moisture Capacity pK"


per cent Meq/g Meq/ml or "pKb
Cation-exchangers :
Amberlite IRC -60 60 10.1 S.6 6.1
Amberlite IRC-84 66 11.5 8.6 5.8
Anion-exchangers :
Amberlite IRA-68 60 6.6 1.6 8.6
Amberlite IR-45 46 6.0 2.0 9.2
Amberlite IRA 93 67 6.2 1.4 9.0
Note: "Apparent pK« ( cation-exchange resins ) and pKh (anion-exchange resins) values measured by
Henderson-Hasselbach equation.

volves a series of three columns: Amberlite erated with base to convert the resin to the
IRA-68 (HCOa) -* Amberlite IRC-84 (hy free base and the second column is already
drogen form) -» Amberlite IRA-68 (free in the bicarbonate form. The deionization
base) . Saline water passing through the is now accomplished by passage of the
first column undergoes the alkalization re saline water in the opposite direction i.e.,
action in which the anions are exchanged through the third column first. In other
for bicarbonate ions, e.g., NaCl is converted words, the first and third column contain
to NaHCCv Passage of the NaHCO, through ing the Amberlite IRA-68 alternate with
the second column results in the exchange each other as the alkalization or the car
of Na* for H* (dealkalization) , with the bonation (CO, recovery) column. To start
effluent containing merely CO, and H,0. the operation, the leading column is first
The effluent from the second column is conditioned with CO,-saturated water. Since
passed through the third column with the the CO, is recovered by the third column,
resultant recovery of the CO, forming the CO, is only employed to make up for losses
bicarbonate salt of the Amberlite IRA-68 due to leakage. A flow sheet is shown in
(carbonation) . The first column is regen Figure 26.
NoCI

A A A
M M M
B B B
E E E
R R R
L L L
I I I
T T T
E E E

IRA -68 IRC-84 IRA-68

I ;
ALKALIZATION DEALKALIZATION CARBONATION
(COg RECOVERY)
« * *
NaHC03 H2O+ C02 H2O
FIGURE 26. NEW DEIONIZATION FLOW SHEET.

The regeneration efficiency is excellent ous methods of regeneration studied, it has


for a system of this type, since weak elec become apparent that regeneration costs
trolyte ion-exchange resins are employed, can be reduced to approximately the use
permitting regeneration with cheap acids of one equivalent each of H.SO, and CaO
and bases at regeneration levels approach per equivalent of NaCl removed.
ing 100 per cent efficiency. The regenera The effectiveness of the new desalination
tion of resins described in this study, in technique is described in Figures 27. 28. and
cluding the recovery of the ammonia from 29 using a synthetic water containing 1,000
the waste regenerant using lime, has al ppm. It is quite obvious that the new tech
ready been discussed in detail. A study em nique yields excellent quality water and
ploying a lime slurry directly as a regenerant excellent capacities.
was of considerable success. From the vari

75
eOr

l_

tu
о Со' 1000 рря
и ■ 2 gal /ftVmln
< h • 24"

10

10 2030 40 50 60 70 80 90
BED VOLUMES, THROUGHPUT
FIGURE 27. EFFECT OF THE TEMPERATURE ON THE PER
FORMANCE OF AMBERLITE IRA-68 IN THE NEW DEIONIZA-
TION PROCESS.

60i—

0 10 20 30 40 50 60 70 80 90
BED VOLUMES, THROUGHPUT

FIGURE 28. EFFECT OF REGENERANT AND RINSE WATER


QUALITY ON NEW DEIONIZATION TECHNIQUE.
50,

Со ■ 1000 ppm
(9 и » 2 gal / ft5/ min
4 h » 24"
at го!
< T » RT*

10

10 20 30 40 50 60 90
MEQ THROUGHPUT
FIGURE 29. EFFECT OF C02 RECOVERY ON NEW DEIONIZA
TION TECHNIQUE.

PILOT PLANT TESTS Sturla (ref. 6) , of Direzione Construzioni


Termiche E Nucleari (ENEL) , Rome, Italy,
In view of the encouraging laboratory at the Laboratorio Centrale in Piazenca,
results, it was deemed advisable to study Italy, using a brackish water of approxi
the new desalination process on a pilot mately 2,300 ppm in salinity and having
plant scale in the field. This study was the composition described in Table XV.
conducted in cooperation with Dr. Piero

TABLE XV. Typical Analysis of the Brackish Water

Calcium — 230 ppm pH — 7.8


Magnesium — 490 ppm Chlorides — 1,823 ppm
Sodium — 1.574 ppm Sulphates — 180 ppm
Total solids — 2.294 ppm Nitrates — 21 ppm
Organice — 8.5 ppm as KMnOi Bicarbonates — 270 ppm
Note:—The above amounts are expressed as ppm of CaCOa.

Conventional ion-exchange equipment also the same, i.e., Amberlite IRA-68 -»


was employed, and was slightly modified to Amberlite IRC-84 -» Amberlite IRA-68.
accommodate the use of CO, to saturate Each column, 30.7 cm in diameter and 190
water for replacing CO, losses from the cm high, contained 60 liters of ion-exchange
system. The ion-exchange resins used were resin at a depth of approximately 80 cm.
the same as those used in the laboratory Figure 30 describes the pilot plant in detail.
study; the arrangement of columns was
SO.
TRIALS.
FIGURE
BPILOT
FOR
SKETCH
WATER
PLANT
RACKISH

00
The pilot plant was operated for approxi and regenerant efficiency were achieved.
mately one year during which period 105 Table XVI summarizes the operating data
cycles were completed. During the course including effluent quality, regenerant con
of this study, consistent effluent quality sumption, and exchange capacity.

TABLE XVI. Summary of Operating Data


Flow rate:
Exhaustion — 1-2 gal/cu ft/mln
Regeneration — 0.5 gal/cu ft/mln
Regeneration levele:
Amberlite IRA-68 — 110% theory (4% NHi or CaO slurry)
Amberlite IRC-84 — 110% theory (4% HC1 or HsSOt)
Capacity:
Amberlite IRC-84 — 20 Kgr/cu ft
Amberlite IRC-68 — 18 Kgr/cu ft
Effluent quality: — 10-20 micromhoa

At the conclusion of the study, samples cu ft of ion-exchange resins in each of the


of each ion-exchange resin were removed three units. This involves a capital cost for
and evaluated in the laboratory to deter the ion-exchange equipment installed of
mine if any changes in the properties of approximately $300,000 and an operating
the exchangers had occurred during the cost of 11 to 22 cents per 1,000 gallons,
course of the study. A comparison of the depending on the availability and cost of
properties of the ion-exchange resins before the regenerant chemicals. It is quite evident
and after the pilot plant study is sum that the installation and operating costs
marized in Table XVII. This illustrates the compare favorably with other desalination
fact that both the exchangers changed only techniques.
slightly and appear quite stable in this
application. Included in the pilot plant was TABLE XVII. Properties of Ion-Exchange
a series of runs in which the anion-exchange Resins Before and After Use.
resin, Amberlite IRA-68, was successfully
regenerated, using a slurry of lime in place Amberlite IRA-68: Used Fresh
of the ammonia. According to the results
of this field study, the cost for treating the Moisture (%) 62.8 61.6
water in question was significantly less than Total anion-exchange capacity
(meq/gm) 5.68 S.70
that of evaporative processes at concentra Carboxyl capacity
tions less than 3,000 ppm. A modest-sized (meq/gm) 0.62 0.48
plant based upon the described process is Net adsorbed organic matter
(meq/gm) 0.82
now being erected for treating brackish Whole bead content ( % ) 98.0 98.0
wateT to be used by a power utility.
Using the data of Peak (ref. 7) , an esti Amberlite IKC-li:
Moisture (%) 49.6 49.8
mate has been made of the cost of a large Cation-exchange capacity
installation based upon the new process. (meq/gm) 10.68 10.62
To treat 1,000.000 gallons of brackish water Whole bead content (%) 98.0 98.0
(1,100 ppm) per day would require 400

CONCLUSIONS
As a result of the laboratory and pilot economically so as to extend the range of
plant studies, it is quite apparent that weak ion-exchange to brackish waters. One may
electrolyte ion-exchange resins can be used speculate in terms of future developments.
efficiently to deionize brackish waters, em For example, further economies may be
ploying regenerants such as lime and possible if it becomes possibe to adapt the
HjSO, at efficiencies close to 100 per cent. newer moving bed, countercurrent engineer
In addition, the new technique utilizes the ing designs to the above-described desal
capacities of the ion-exchange resins most ination process. In addition to the use
efficiently when employed with conventional of lime as a regenerant for the anion-
equipment. exchange resin, the possibility of using C02
It is apparent from these studies that as a regenerant for the carboxylic cation -
ion-exchange resins can now be employed exchanger.
RCOONa + CO, ^ RCOOH + NaHCO,
berlite IRA-68, possessing a high K
and the resulting NaHCO, as the regen- HCO,"
erant for the anion-exchange resin, as sug selectivity coefficient and the carboxylic
gested in a previous paper (ref. 5) , has cation-exchange resin, Amberlite IRC-84,
potential merit in certain situations. In with improved kinetic and equilibrium be
practice, the less acidic cation-exchanger, havior when employed with the new de-
Amberlite IRC-50, would be required lo ionization technique, extend the economic
achieve efficient use of the CO, and obtain utility of ion-exchange resins to the range
a high concentration of NaHCO,. A pre of many brackish waters (at least to 2,000
liminary study has revealed that the utility or 3,000 ppm) . Some of the advantages of
of this system would be limited to situ the new process over the older ion-exchange
ations permitting modest amounts of leak methods are:
age. In addition, about one-half to 1. High regeneration efficiency, ap
three-fourths of the required base necessary proaching 100 per cent utilization of
for regeneration could be recovered in this regenerants, can be achieved.
manner. 2. Low cost regenerants can be used.
The direct use of lime as a regenerant
for the anion-exchange resins is most at 3. Raw water can be used for rinse
tractive and has been used with success in and regeneration without notable losses
the pilot plant studies. The economic gains in capacity and quality.
are most encouraging if one considers that 4. Very low leakages are noted at effici
a pound equivalent of CaO costs only $0.11 ent regenerant levels.
as compared with NH, at $0.74 and NaOH 5. The system can be readily integrated
at SI.20. with other ion-exchange resin deioniza-
The weak base anion-exchange resin, Am tion systems.

REFERENCES
1. Kunin, R.; Barry, R. E.: Ind. and Eng. 5. Kunin, R.; Vassiliou, B.: Ind. and Eng.
Chem., no. 41 (1949) p. 1269. Chem. Prod. Res. Develop., no. 2
2. Kunin, R.; McGarvey, F. X.: Ind. and (1963) p. 1.
Eng. Chept., no. 43 (1951) p. 734. 6. Sturla, P.: 25th Meeting Int. Water
3. Kunin, R.: U.S. Patent 3,111,485 (Nov. Conf. Eng. Soc, Western Pennsylvania
11. 1963). (Sept. 30. 1964) .
4. Kunin, R.: U.S. Patent 3,156,644 (Nov. 7. Peak, R. F.: Univ. of Washington,
10, 1964). Ph.D. Dissertation (1955).

SUMMARY OF DISCUSSIONS
Further comment was requested concern the resin bed is exhausted and that normal
ing the technique of backwash flow rate. backwash is employed. Actual backwash
The reply stated that backwashing the resin rates were not given.
bed is the conventional procedure when
Nouvelle Technique de Dessalement

Par Echange DTons

Robert Kunin

Etats-Unis D'Amérique

D'une manière générale, la désionisation 2 RCOONa + HjSO, -» (5)


économique de l'eau par des résines échan 2 RCOOH + Na,SO,
geuses d'ions s'est limitée aux eaux con (régénération de
tenant moins de 500 ppm de solides dissous. l'échangeur
En général, la désionisation des eaux sau- cationique)
mâtres par les techniques normales à ré Le nouveau procédé de désionisation
sines échangeuses d'ions ne peut pas con cyclique comporte une série de trois co
currencer les procédés par distillation et lonnes: Amberlite IRA-68 (HCO,) —Am-
par membranes, principalement à cause berlite IRC-84 (hydrogène) — Amberlite
des frais de régénérateurs et la nécessité IRA-68 (base à l'état libre) . Les deux
d'utiliser de l'eau désionisée pour l'opéra résines échangeuses d'ions, Amberlite IRA-
tion de rinçage. Pour les eaux à faibles 68 (résine échangeuse anionique à base
teneurs en solides, ces facteurs sont faible) et Amberlite IRC-84 (résine
d'une importance secondaire; à une con échangeuse cationique à acide faible) , sont
centration supérieure à 500 ppm, ils de des résines échangeuses d'ions faiblement
viennent d'une importance primordiale. On électrolytiques et conviennent particulière
a étudié une nouvelle technique de désio ment bien pour ce procédé. L'eau saline
nisation par des résines échangeuses d'ions passant à travers la première colonne subit
faiblement électrolytiques dans lesquelles la réaction d'alcalinisation, dans laquelle
l'échangeur anionique à base faible est les anions sont échangés pour des ions bi
utilisé dans le cycle du bicarbonate pour carbonate—par exemple NaCl est trans
convertir l'acidité minérale de l'eau en formé en NaHCO,. Le passage de NaHCO,
alcalinité et la résine à acide faible dans le à travers la seconde colonne a pour résultat
cycle d'hydrogène pour éliminer l'alcalinité. l'échange de Na* pour H* (désalcalinisa
Grâce à ce système on peut désioniser des tion) , avec l'cffluent contenant seulement
eaux saumâtres avec très peu de pertes et CO, et HsO. L'effluent de la deuxième co
à une haute efficacité de régénération. Le lonne passe à travers la troisième colonne
nouveau procédé de dessalement peut se avec pour résultat la récupération du CO,
résumer par les réactions suivantes: formant le sel bicarbonate de l'Amberlite
[R-N] + HsO-f CO,-> (1) IRA-68 (carbonatation) . La première co
[R-NH] HCO, lonne est régénérée avec NH, (NH,OH) ou
(carbonatation) bouillie de chaux pour transformer la
[R-NH] HCO, + NaCl -> (2) résine à l'état de base libre, et la seconde
[R-NH] Cl + NaHCO, colonne avec HrSO, pour transformer la
(alcalinisation) résine à la forme acide. La troisième co
lonne est déjà sous forme bicarbonate. La
R-COOH + NaHCO, -> (S) désionisation se fait alors par le passage de
R-COONa -f CO, + H20 l'eau saline dans la direction opposée, c'est-
(désalcalinisation) à-dire à travers la troisième colonne en
[R-NH] Cl + NH.OH -» (4) premier. En d'autres termes, les première et
[R-N] + NH.C1 + H,0 troisième colonnes, contenant l'Amberlite
(régénération de IRA-68, alternent l'une avec l'autre en tant
l'échangeur que colonne d'alcalinisation ou de carbona
anionique) tation (récupération de CO,) .
ou L'efficacité de régénération est excellente
2 [R-NH] Cl + CaO -> (4a) pour un système de ce genre, car on utilise
[R-N] + CaCl, -I- H,0 des résines échangeuses d'ions faiblement
électrolytiques permettant de les régénérer été réalisée avec un certain succès dans des
avec des acides on des bases bon marché études d'installations pilotes. Les gains éco
(HjSO, et chaux ou ammoniac) à des nomiques sont des plus encourageants si
faibles niveaux de régénération. l'on considère que l'équivalent d'une livre
Lorsqu'on utilise des résines échangeuses (452 g) de CaO ne coûte que $0,11, com
d'ions pour la désionisation de l'eau dans paré avec le NH, à $0,74 et le NaOH à
la gamme de 500 à 3.000 ppm, les régénéra $1,20.
teurs, même les meilleur marché, utilisés à Le procédé a fait l'objet d'essais pra
leur efficacité théorique, représentent la tiques satisfaisants dans une installation
proportion la plus importante du prix de pilote de grande échelle, avec de l'eau
revient du système de désionisation. L'utili saumâtre d'une salinité de 2.000 ppm. Le
sation d'ammoniac, en tant que régénérateur coût des produits chimiques pour l'exploi
pour la résine échangeuse anionique, as tation de l'installation pilote a été de 22
sociée avec sa récupération en utilisant de cents par mille gallons (environ $0,058 par
la chaux m') , en se servant de chaux pour l'un des
2 NH.C1 + CaO -> 2 NH, + CaCl, + H.O régénérateurs, et la qualité de l'eau était
peut constituer une importante réduction en moyenne de 10 à 20 micromhos.
du prix de revient. L'ammoniac est récu Une installation de dimension modeste,
péré de cette manière dans les industries basée sur le procédé décrit, est actuellement
du sucre et de la soude. en cours de construction pour le traitement
L'utilisation directe de la chaux en tant d'une eau saumâtre destinée à être utilisée
que régénérateur pour les résines échan par une centrale électrique.
geuses anioniques est très attrayante et a

Новый Метод Ионообменной Техники

Обессоливания

Роберт Кунин

Соединенные Штаты Америки

Экономичная деионизация воды по кислотной смолой пользуются в водо


средством ионообменных смол обычно родном цикле для удаления щелочно
ограничивалась водами, которые со сти. Эта система позволяет деионизи-
держали менее 500 ч/миллион раство ровать солоноватые воды с лишь не
ренных твердых частиц. Деионизация большой утечкой и с высокой эффек
солоноватых вод путем обыкновенного тивностью регенерации. Новый про
применения ионообменных смол, вооб цесс обессоливания может быть пред
ще не может конкурировать с мембран ставлен схематически в следующих ре
ным и перегонным методом, главным акциях:
образом вследствие высокой стоимо
сти регенераторов и потребности в де- /R-N/ + Н,0 + СОг —
ионизированной воде для промывания. /R-NH/HCO,
Эти факторы менее важны для вод с (карбонизация) (1)
низким содержанием твердых веществ; /R-NH/НСО, + NaCl
но они имеют очень большое значение /R-NH/C1 -I- NaHCO,
при концентрациях свыше 500 ч/мил (алкализация) (2)
лион. Теперь выработана новая техника
деионизации, которая основана на ио R-COOH + NaHCO, —
нообменных смолах для слабых элек R-COONa -f С02 + Н30
тролитов, причем слабоосновной ани- (деалкализация) (3)
онит применяется в бикарбонатном цик /R-NH/C1 + NH,OH —
ле, чтобы превратить минеральную ки /R-N/ + NH.Cl + Н20
слотность воды в щелочность, а слабо (регенерация анионита) (4)
или Эффективность регенерации в системе
2/R-NH/Cl + CaO — этого типа превосходна, так как ионо
/R-N/ + CaCl, -(- H,0 (4a) обменные смолы для слабых электроли
2 RCOONa + H,SO. — тов поддаются регенерации на низких
2 RCOOH + Na^O, уровнях дешевыми кислотами и щело
(регенерация катионита) (5) чами (H2S04 и известь или аммиак).
Применяя ионообменные смолы для
В новом циклическом процессе деио- деионизации воды в диапазоне 500 до
низации пользуются серией трех коло 3000 ч/миллион даже самые дешевые
нок: Amberlite IRA-68 (НС03) — Ат- восстановители при полной их теоре
berlite IRC-84 (водородная форма), тической эффективности, представляют
Amberlite IRA-68 (свободное основа самую значительную статью в себесто
ние). Две ионообменные смолы, Am имости деионизационной системы. При
berlite IRA-68 (слабо-основной ани- менение аммиака в качестве регенера
онит) и Amberlite IRC-84 (слабо-ки тора для анионита, связанное с его из
слотный катионит) представляют собой влечением посредством извести
ионообменные смолы для слабых элек
тролитов и особенно подходят для про 2 NH.C1 + CaO -> 2NH, + CaCl, + Н,0
цесса. Соленая вода, проходящая че
рез первую колонну подвергается ще может значительно уменьшить себе
лочной реакции, при которой анионы стоимость. Аммиак таким образом ре
заменяются бикарбонатными ионами, куперируется в сахарной и содовой
например NaCl превращается в промышленности.
NaHCOg. Прохождение NaHCOs через Непосредственное использование из
вторую колонну приводит к замене вести в качестве регенератора весьма
Na+ на Н+ (расщелачивание), причем выгодно, и оно удачно применялось при
вытекающий раствор содержит лишь исследованиях на опытных установках.
С02 и Н20. Раствор, вытекающий из Экономические выгоды очень привле
второй колонны, проходит через тре кательны если принять во внимание,
тью, где С02 извлекается, образуя дву что фунт СаО стоит только 11 центов,
углекислую соль Amberlite IRA-68 по сравнению с 74 центами для NH, и
(карбонизация). Первая колонна реге 120 центами для NaOH.
нерируется посредством NH3(NH4OH) Процесс был успешно испытан на
или известковым шламмом для того, практике в большом масштабе на опыт
чтобы дать смоле свободное осно ной установке, перерабатывавшей со
вание, а вторая колонна регенерирует лоноватую воду с соленостью в 2.000
ся посредством H2S04 чтобы превра ч/миллион. Стоимость химических ве
тить смолу в ее кислотную форму. ществ при работе опытного завода до
Третья колонна уже принадлежит к стигала приблизительно 22 цента за
двууглекислой форме. Деионизация до 1.000 галлонов, причем в качестве од
стигается прохождением соленой воды ного из регенераторов употреблялась
в противоположном направлении — т.е. известь, а качество воды достигало в
сначала через третью колонну. Иными среднем 10-20 микроомов.
словами, первая и третья колонны, со Небольшой завод, основанный на
держащие Амберлит IRA-68 действуют вышеописанном процессе, строится в
поочередно как подщелачивающая или настоящее время для обработки соло
карбонизирующая (извлечение С02) новатой воды, употребляемой для пи
колонка. тания энергетической установки.
Una Nueva Técnica de Desaliniza-

cion por Intercambio Iónico

Robert Kunin

Estados Unidos de Norteamérica

La desionización de agua mediante resi 2 RCOONa + H.SO. -»


nas de intercambio iónico, en forma eco 2 RCOOH -f Na,SO,
nómica, ha estado generalmente limitada (regeneración del permutador (5)
a aguas que contienen menos de 500 ppm catiónico)
de total de sólidos disueltos. En general, El nuevo proceso cíclico de desionización
la desionización de aguas salobres mediante emplea una serie de tres columnas. Amber-
técnicas convencionales por medio de resinas lite IRA-68 (HCO,) — Amberlite IRC-84
de intercambio iónico, no puede competir (forma de hidrógeno) — Amberlite IRA-68
con los métodos por medio de membranas (base libre). Las dos resinas de intercambio
y por destilación debido principalmente al iónico, Amberlite IRA-68 (resina de inter
costo de los regenerantes y a la necesidad cambio aniónico base débil) y Amberlite
de emplear agua ionizada para la opera IRC-84 (resina de intercambio catiónico
ción de enjuague. En el caso de aguas de ácido débil), son resinas de intercambio
bajo contenido de sólidos, estos factores son iónico débilmente electrolíticas que se adap
de menor importancia; por sobre una con tan singularmente para el proceso. El agua
centración de 500 ppm, éstos pasan a ser salada que pasa a través de la primera
de mayor importancia. Se ha desarrollado columna es sometida a la reacción de alca
una nueva técnica de desionización me linización en la cual los aniones son inter
diante el empleo de resinas de intercambio cambiados por iones bicarbonato — por
iónico débilmente electrolíticas en que el ejemplo, el NaCI es convertido a NaHCO,.
permutador aniónico de base débil es em El pasaje del NaHCO, a través de la se
pleado en el ciclo del bicarbonato para gunda columna resulta en el intercambio
convertir la acidez mineral del agua a alca de Na + por H -\- (desalcalinización), con
linidad, y la resina de ácido débil es em teniendo el liquido que sale simplemente
pleada en el ciclo del hidrógeno para CO, y H,0. El liquido proveniente de la
extraer la alcalinidad. Este sistema permite segunda columna pasa a través de la tercera
desionizar aguas salobres con poca pérdida columna recuperándose, como resultado, el
y a una alta eficiencia en la regeneración. CO, el cual forma la sal bicarbonatada de
El nuevo proceso de desalinización se puede la resina Amberlite IRA-68 (carbonatación).
resumir mediante las siguientes reacciones: La primera columna es regenerada con NH,
[R-N]+ H.O + CO,-> [R-NH] HCO, (NH,OH) o suspensión de cal para conver
(carbonatación) (1) tir la resina a la base libre mientras que
la segunda columna es regenerada con
[R-NH] HCO, + NaCl -> H,S04 para convertir la resina a la forma
[R-NH] Cl + NaHCO, ácida. La tercera columna ya se encuentra
(alcalinización) (2) en la forma bicarbonatada. La desionización
R-COOH + NaHCO, -> se logra ahora mediante el pasaje del agua
R-COONa + CO, H.O salada en sentido contrario—es decir, co
(desalcalinización) (3) menzando por la tercera columna. En otras
palabras, la primera y la tercera columnas
[R-NH] C1 + NH.OH-» conteniendo Amberlite IRA-68 se turnan
[R-N] + NH4C1 + H20 entre sí en la función de columna de alcali
(regeneración del permutador (4) nización o carbonatación (recuperación del
aniónico) CO,).
La eficiencia en la regeneración es ex
° 2 [R-NH] Cl + CaO -> celente para un sistema de este tipo, dado
[R-N] + CaCl, + H,0 (4a) que se emplean resinas de intercambio
iónico débilmente electrolíticas permitiendo aniónico es sumamente atractivo y ha sido
las regeneraciones con ácidos y bases bara ensayado con cierto éxito en los estudios de
tos (H,SC), y cal o amoniaco) a bajos niveles planta piloto. Las ganancias económicas
de regeneración. son sumamente alentadoras si se considera
Cuando se emplean resinas de intercam que una libra equivalente de CaO cuesta
bio iónico para la desionización de aguas sólo $0.11 comparado con amoniaco a $0.74
con contenido de sólidos entre 500 y 3000 y NaOH a $1.20.
ppm, aún los regenerantes más baratos, El proceso ha sido probado con éxito, en
usados a eficiencia teórica, representan la forma práctica, en planta piloto en gran
contribución principal al costo del sistema escala, con un agua salobre con un con
de desionización. El empleo de amoniaco tenido salino de más de 2000 ppm. El costo
como regenerante de la resina de inter de productos químicos para el funciona
cambio aniónico, junto con su recuperación miento de la planta piloto fue de aproxi
por medio de cal madamente 22 centavos de dólar por mil
2 NH«C1 + CaO -> 2 NH, -f CaCl, + H20 galones, empleando cal como uno de los
regenerantes y la calidad del agua promedió
puede disminuir el costo en forma significa entre 10 y 20 micromhos.
tiva. El amoniaco es recuperado de esta Actualmente se está construyendo una
manera en las industrias del azúcar y de la planta de modesta envergadura, basada en
soda Solvay. en proceso descrito, para el tratamiento de
El empleo directo de cal como regene agua salobre destinada a ser utilizada por
rante para las resinas de intercambio una planta de energía eléctrica.
Survey of Water Desalination in

Israel

I. Vilentchuk

GENERAL INFORMATION
The State of Israel lies between the lati Rainfall decreases from north to south.
tudes of 29°30' and S3" 15' north, its total In the north it is about 20 inches on the
area being 21,000 sq km (about 8,000 sq Mediterranean coast, increasing to 24 to 30
miles). Its total border is 1,215 km (770 inches in the mountainous region to the
miles) long, 190 km (120 miles) of which east; further south, the rainfall diminishes
is formed by the Mediterranean. Israel's to about 8 inches in Beersheba, which lies
total population was, at the end of 1963, at the northern border of the Negev, and
2.430,000. (In 1948, the year in which Israel declines to li/£ to 2 inches in the southern
became a sovereign state, the total popu
lation was 915,000. Almost 75 per cent of Arava and Eilat. Rainfall occurs only dur
the population is concentrated along the ing the winter months (November to Feb
Mediterranean coastal plain where the ruary) , and the variations between dry and
largest towns are located. The citrus planta wet years are considerable. The relative
tions, as well as the country's main indus geographical distribution of water resources
trial plants, are also situated in this area. and water demand is extremely unfavor
The climate in the northern part of the able; whereas about two-thirds of the avail
country is characteristic of the eastern able water resources are to be found in the
Mediterranean region, whereas the southern north, the greater part of the irrigated and
part—comprising the area known as the irrigable land, as well as a considerable
Negev and the Arava—is for the most part part of the industrial and municipal con
an arid desert region. This represents over sumption, lies in the central part of the
half the total area of the country and country. The additional agricultural devel
tapers off at its southern extremity to an
11 -km (7 -mile) point at the Gulf of Akaba. opment of land in the nothern Negev
The Red Sea port town of Eilat is located planned for the future will further aggra
here. vate the situation.

WATER SUPPLY
The total fresh water resources of Israel sources is still in its beginnings.
are estimated at about 1,500 million eu m During the period 1963-64, the total
(330 billion gals) per year. It is expected water consumption in Israel was 1,290
that these resources will be fully developed million eu m, which represents 85 per cent
by the early 'seventies. About 55 per cent of the total fresh water resources. As the
of these resources is groundwater (wells national water carrier (diversion of Jordan
and springs) , 31 per cent Jordan River River) with its proposed 320 million eu m
basin, 5 per cent intermittent floods (irreg per year supply was not then in operation,
ular flow during a few winter rainstorms) , the deficits created by water demand dur
and 9 per cent reclaimed sewage effluent. ing 1963-64, as well as during preceding
Development of the last two of these years, were covered by temporary over
pumping from wells, primarily in the gradually discontinued before 1970.
coastal area. To prevent lowering of the The increase in water consumption dur
water table beyond the planned safe levels, ing the years 1948-63 may be seen from
the temporary overdraft will have to be the following table.

TABLE XVIII. Increase in Water Consumption from 1948 to 1963


(Million eu m per year)
1954-56» 1966-57 1958-69 1960-61 1962-68 1963-64
Agriculture 760 830 990 1,150 1,160 1,040
Municipal and
industrial 200 280 240 250 280 260
Total 960 1,060 1,280 1,400 1,430 1,290
* In the present report, wherever a year is designated by two figures, e.g., 1964-55, it denotes the
fiscal year beginning April 1st and ending March 31st of the following year. This division coincides
closely with the agricultural year.
Administrative measures, including the age reservoir in lieu of the originally pro
adoption of an appropriate pricing policy, posed diversion of the upper Jordan. The
have been taken to arrest the growing con salinity of Lake Tiberias is relatively high
sumption of water because of several con (1,000 ppm tds of which chloride ions
secutive years of severe drought. These account for about 365 ppm) , owing to the
measures have been supplemented by an discharge of a number of saline springs
educational campaign through press and rising along the shores and at the bottom
radio. of the lake. A number of remedial works
It is difficult to forecast the water con are under construction or have been pro
sumption of agriculture since this depends posed for early execution; these are de
on the quality and the cost of water. Tak signed to gradually reduce the salinity of
ing into account the municipal and indus the lake's water.
trial demand for water for the rapidly It is proposed that most of the projects
growing population and the agricultural for the reclamation of sewage—regarded as
water demand primarily for the existing part of the national water resources (9
citrus and other plantations, the anticipated per cent) —should operate on the principle
rise in general water demand in Israel will of discharging the treated effluent into the
be as follows: aquifer and subsequently withdrawing it
from the underground storage by means of
TABLE XIX. Anticipated Water shallow wells. The sewage effluents have a
Consumption tds about 200 ppm higher than that of the
incoming water; consequently, this form of
Million eu m sewage utilization will gradually raise the
Fiscal year per year Population salinity of the underground resources in
the coastal plain.
1963-64 1,290 2.480,000 The country's most important source of
••1970-71 1,415 8,020,000
••1976-76 1.670 water—the aquifer in the coastal plain—is
••1980-81 1,900 undergoing a process of constant increase
of its mineral content as a result of the
•• Forecast. gradual accumulation of salts accruing from
industrial, municipal, and agricultural use.
A comparison of these figures with the This process of mineralization is further
estimated total safe yield of the total intensified by the diminishing discharge of
natural water resources after their full de water fand salts) into the sea by the aqui
velopment indicates the significant role that fer as a result of its excessive utilization.
desalination must assume in Israel. Almost all the salinity problems reviewed
The anticipated shortage of water from occur in the central and southern parts of
natural resources, especially for agricultural the coastal plain where, out of the total
use, is further aggravated by the excessive supply of 800 million eu m anticipated for
salinity of this water. The chief salinity 1975, about 280 million eu m, which will
problem derives principally from the na be used mainly for agriculture, will contain
tional water carrier project and is due to about 300 ppm of chloride ions. A figure
the selection of Lake Tiberias as the stor of 170 ppm of chloride ions has been pro
visionally adopted as the ceiling for such ion content of irrigation water to the de
salt-sensitive crops as citrus. sired level of 170 ppm. Incidentally, this
In the early "seventies, salinity problems quantity will also be adequate to meet the
will become acute and an improvement of water deficit as indicated above. This quan
the mineral quality of the irrigation water tity of desalted water required to meet both
will be necessary to prevent a possibly sig the shortage and excess salinity is con
nificant drop in crop yields of the citrus tingent on the cost of conversion.
plantations. It should be noted that citrus There is also about 150 million cu m
represents the main export item of the per year of brackish water containing be
country. tween 500 to 1,200 ppm of chloride ions,
About 125 to 150 million cu m per year one-half of which could be utilized for
(100 to 125 mgd) of extremely high quality- agriculture, if economic methods of desalt
converted sea water will thus be required ing were found.
at that time in order to reduce the chloride

POWER DEVELOPMENT
At present, dual-purpose (power genera extrapolation in accordance with the gen
tion with flash evaporation conversion) eral trend observed up to 1970-71. The
plants would seem to offer the most eco annual electric generation will, by the end
nomical solution. Hence, a brief review of of this period, reach over 9,000 million
the power development situation in Israel kwh per year. The maximum demand
is given below. (MD) will increase from 560 Mw in
The Israel Electric Corporation, Ltd. 1963-64 to 1,110 Mw in 1971-72 and to
(I.E.C.) , is the only power utility in the about 1,650 Mw by 1975-76. The system
country, supplying virtually its entire elec load factor will remain high—over 65 per
tric energy. Steam turbine power plants are cent.
situated in Haifa (Northern District) , Tel Since the dual-purpose plants can oper
Aviv (Central District) , and Ashdod ate most economically at base load, it is
(Southern District) . The total nominal important to note that the base load of
rating capacity of the system, including two the power system was 27 per cent of MD
125 Mw units now under construction in in 1963 and is expected to reach about
Haifa, is 965 Mw. Of these, 840 Mw were 35 per cent in 1971; it will gradually de
installed after March 31, 1954. All the crease to 31 per cent by 1975 and stay at
power plants are situated on the seashore 30 per cent during the following years. The
and use sea water for their condensers. The base load in 1971 would be approximately
supply system consists of an interconnected 20 Mw and would increase by 35 Mw each
grid covering the whole country except, year during the following period (1971-80) .
temporarily, the Eilat region. The main The largest power unit now under con
transmission lines operate at 110 kv, gradu struction is of 125 Mw nominal rating
ally being changed to 150 kv. capacity. For future extension of the sys
According to the forecast of the I.E.C.', tem up to the year 1975, units of 175 to
the total annual electric sales will increase 200 Mw will be used. Units of 6 Mw to
from 2,700 million kwh in 1963-64 to 5,600 30 Mw capacity installed before 1953-54
million kwh in 1970-71 —a total increase, will be used for peak hours and as standby.
of 110 per cent. The sales are about 85 Some of them may be subsequently inte
per cent of generation. For the period 197 1— grated with sea water conversion.
72 to 1975-76 the forecast is based on an

THE SEA WATER CONVERSION COMMISSION


In 1959 the Government of Israel ap of the country's absorptive capacity and the
pointed the Sea Water Conversion Com strengthening of its economy by the aug
mission whose principal function is advising mentation of known water resources through
the Government on the possible expansion the conversion of sea water. The Commis
sion was also instructed to advise the
* The I.E.C. prepares an annual sales and de Government on efficient methods for achiev
mand forecast for five to six years based on a ing the above objective, either independ
detailed analysis of the expected consumption
pattern of the main consumer groups. ently or in conjunction with electric power.
"* Maximum demand as measured at power The water situation in the country is
plants, including powerhouses' own use.
periodically reviewed by the Commission tion as a demonstration plant in connection
on the basis of reports presented by govern with future plans for large-scale water con
ment and public agencies. It also keeps version in Israel. It was upon this recom
abreast of the technological development of mendation that the Government allocated
saline water conversion in Israel and else the funds for the clectrodialysis demonstra
where. The Commission reports periodically tion plant at the settlement of T'zeelim.
to the Government on related questions The Commission has systematically dis
and submits its recommendations. seminated information on sea and brackish
In the course of its activities, the Com water conversion development among in
mission advised the Government to erect terested circles in Israel. It has also accu
a dual-purpose plant in Eilat which, while mulated an extensive library.
serving the needs of the town, would func

U.S.-ISRAEL JOINT SEA WATER DESALTING PROJECT


A project at present under consideration heat source—fossil or nuclear fuel—will be
is a 175 to 200 Mw salable electric power one of many problems to be studied by the
unit integrated with a conversion plant Consulting Engineer whose report is ex
(most probably using multistage flash type pected to be submitted by December 1965.
evaporators) of 375,000 to 475,000 cu m In an interim report to be ready by July
per day (about 100 to 125 mgd) capacity 1965, the Consulting Engineer will make
to be put into operation by 1971-72. his recommendations with regard to the
This scheme has been studied by a Joint development program which will precede
U.S.- Israel Desalting and Power Team. A the actual design of the conversion plant.
preliminary report was submitted in Octo According to the preliminary schedule
ber 1964. Two alternative sources of heat adopted by the Joint Board, the plant
had been examined: (1) a boiler fired by should be operating at full capacity by
fossil fuel and (2) a nuclear reactor. The April 1972. This timetable provides for a
plant would be designed for base load certain lag of intensive technological devel
operation of water and power and would opment of the conversion plant with regard
use a back pressure steam turbine. A pre to unit sizes, temperatures, materials, scal
liminary analysis indicates that a nuclear ing control, and constructional details,
heat source would produce the quantities which will be undertaken upon the recom
of water considered in this project at lower mendation of the Consulting Engineer.
cost than a fossil -fired heat source. How This development work will be conducted
ever, the cost of water converted by heat in coordination with the Office of Saline
from a nuclear reactor has now shown a Water, U.S. Department of the Interior.
striking difference and depends on the A paper on this subject is being pre
capital charges. The cost of generated sented to this Symposium.
power has been taken at 5.3 (dollar) mills Taking into account that only relatively
—which, according to the Israel Electric small conversion units (up to 1.7 mgd)
Corporation, will equal the cost of the have hitherto been built elsewhere, the
large power units to be erected by the Israel Sea Water Conversion Commission
I.E.C. in the early 'seventies. considers the construction of an intermedi
The reactor considered by the joint team ate size prototype unit extremely important.
would be rated at 1200 to 1,300 Mw ther All the converted water will be used in
mal, which is larger than any power reactor the coastal plain and consequently the
now operating in the United States but of cross-country water delivery will be rela
a type and size now being constructed by tively inexpensive. The existing country
electric utilities. wide water supply system forms, to all
A multistage flash type conversion plant intents and purposes, an interconnected
of the proposed capacities would, however, water grid. The latter, together with the
be many times larger than any plant in countrywide power grid, considerably sim
operation elsewhere and the risk factors— plifies the selection of the sites for the
reliability, cost, and performance—appear integrated power and water conversion
to be high. plants. The base load of the power system,
A Consulting Engineer appointed by a which is and will remain a considerable
Joint Board (the latter nominated by both part of the maximum demand, creates fa
governments) is now preparing a feasibility vorable operating conditions for integrated
study of the project. The question of the plants.
CONVERSION OF SEA WATER—WATER SUPPLY FOR TOWN OF EILAT
The town of Eilat is situated in the the town until 1968. As a result of the
southernmost part of the country on the admixing, the chloride ion and Fluor con
Gulf of Akaba (Red Sea) . In the summer tents will be reduced to a lower ratio than
the maximum temperature is higher than those stipulated by the Ministry of Health.
40°C (104°F) , and the lowest mean relative The sulfate content, however, will remain
humidity is about 25 per cent. Water con higher during a considerable part of the
sumption is relatively high, mainly because year.
of the widespread use of desert coolers.
The maximum daily consumption in 1964, EILAT CONVERSION PLANTS
for a population of over 11,000, was about 1. Dual-Purpose Plant. This plant was
9.000 cu m. The estimated maximum con started in April 1965 and is now under
sumption for 1967—68 is 14,500 cu m. going the acceptance tests.
At present, the town's water comes from Data on the Flash Type Evaporation Unit
wells situated about 45 km (28 miles) to
the north. The water is of inferior quality, Net capacity 3,800 cu m per
containing more than 2,300 ppm tds. An day (1 mgd)
excessive amount of water is used to con No. of stages 30
trol scale in the coolers. According to a Performance ratio
1960 study, demineralization of the water (cu m of water per
would cut the amount used in the coolers ton of steam) 8
by half. Top operating
The Israeli health authorities have estab temperature 93°C (200°F)
lished the following stipulatons for Eilat's
drinking water: Concentration factor 1.7*
(1) The chloride ion content must not Guaranteed quality of
exceed 500 ppm (desirable limit) . distillate 25 ppm tds
(2) The yearly average Fluor (F) con Chemicals for scale 2 to 5 ppm of
tent must not exceed 0.8 ppm. control (additional "Hagevap"
(3) The sulfate (SO,) content must not arrangements for
exceed 250 ppm (desirable limit) . periodic acid treat
In 1959, a 40 cu m per day ion-exchange ment)
plant was built. It is now close to its Manufacturers Baldwin-Lima-
maximum capacity; increased water con Hamilton, U.S.A.
sumption would necessitate additional in
vestment (mostly in mains and pumps) . The power plant consists of one 6,000 kw
The quality of the water would not be capacity back pressure steam turbine inte
changed. grated with the conversion plant and three
Eilat has two conversion plants. One is a portable 1,200 kw capacity diesels as a
dual-purpose plant with a flash type evap standby. The latter supplied the power
orator of 3,800 cu m per day capacity (1 until the turbine generator was built.
mgd) ; the other is a vacuum freezing plant Data on the Back Pressure Power Turbine
of 1 ,000 cu m per day (250,000 gpd) . Two boilers at 30 metric tons of steam
The Mekorot Water Company, Ltd., per hour**
which supplies the town's water, has recom Throttle steam pressure 43.2 abs (614 psia)
mended ordering a second flash type evap
oration unit, with approximately the same Back pressure turbine 15 stages; 3,000 rpm
capacity as the first, to be put in operation Exhaust steam to sea water heater 1.02 abs
in the spring of 1968. The recommendation (14.5 psia)
has been endorsed by the Sea Water Con Net salable power:
version Commission. The construction of a First construction stage \ _ .
second conversion unit is included in the 2,170 kw / °Pt,mum
original design of the dual-purpose plant. Second construction stage ( "sage
It is estimated that the increased amount 5,230 kw ) °fsteam
of converted water available from these Manufacturer: International General Elec
two plants will meet the requirements of tric. U.S.A.
• The sea water at Eilat baa 41.500 tds. For flow chart and heat balance diagram
" The third boiler of about the same capacity of the integrated plant, see Appendix A.
will be erected together with the second conversion The conversion plant is jointly owned by
unit. One of the three boilers will serve as a
the Israel Electric Corporation, Ltd. and
the Mekorot Water Company, Ltd. (The possible without impairing safe operation
major part of their equity is owned by the to test advances in distillation technology
government.) The water company will be which may be beneficial in implementing
responsible for the converted water. The the larger Joint Israeli-United States De
fixed charges and operating costs of con salting Project now under study.
verting water will be calculated on the 2. Vacuum Freezing Plant (Zarchin
basis of marginal expenses as compared Process). The desalination plant at Eilat,
with those of an independent power plant employing the vacuum freezing vapor com
of similar capacity with a full condensing pression process, was commissioned at the
turbine. The costs will be determined in beginning of 1964. This was the first field
the near future. The plant includes ar plant of its kind to be erected anywhere in
rangements for taking steam from the the world. A prototype test unit has been
boiler through a pressure reducing valve in operation at Beloit, Wisconsin, since
for conversion in case of an outage of the 1962.
turbine and for using one of the two sea Various improvements and modifications
water heaters as a dump condenser in case have been made in the operation of these
of an outage of the distillation unit. units to improve efficiency, production, and
A general view of the plant and the sea stability of operation.
water conversion unit will be found in The Eilat plant consists of four desalina
Appendix B. tion modules, each nominally rated at 250
The plant will not only improve the eu m per day (65,000 gpd) . Power con-
water supply of the town but also serve as sumplion for the nominal production rate
a demonstration plant for the current study was initially 22 kwh per eu m (85 kwh/
of large flash type conversion plants and 1 ,000 gals) .
help train personnel. A research program The Eilat plant, as well as the Beloit
for the plant has been worked out. Last unit, was developed and is owned and
year, the owners delegated three men to operated by Desalination Plants (Developers
visit several conversion plants on islands in of Zarchin Process) , Ltd., of Tel Aviv, a
the Caribbean and gather information on joint venture of the Government of Israel
the operation and maintenance of flash and Colt Industries (formerly Fairbanks
type evaporators. Whitney Corp.) .
It has also been considered advisable to A paper on this plant is being sub
use the second conversion unit as much as milted to this Symposium.

CONVERSION OF BRACKIS WATER—T'ZEELIM PLANT


A well containing brackish water at the for the stacks came from various makers
agricultural settlement of T'zeelim in the and were, in part, manufactured at the
Negev yields about 80 eu m per hour laboratory.
(350 gpm) , the water level being 120 A full report on the T'zeelim plant is
meters. The water is highly mineralized, given in a special paper presented to this
containing about 2,400 ppm tds. An electro- Symposium.
dialysis plant of 500 eu m per dav (125.000 The Beersheba Laboratory is at present
gpd) capacity is at present being erected cooperating with the Mekorot Water Com
and will be commissioned during June pany on the design of a plant of 4,800 eu m
1965. The plant was designed and the per day (1.25 mgd) for another Negev
stacks constructed by the F.lectrodialvsis settlement, Mashabei Sadeh, whose brackish
Research Laboratory of the Negev Institute water contains about 2,500 ppm tds. This
for Arid Zone Research at Beersheba. is to be reduced to about 500 ppm. The
The product water will contain about decision with regard to the erection of the
500 ppm tds. The reject water will contain Mashabei Sadeh plant has been deferred
about 10,000 ppm and amounts to 20 per pending the results of the operation of the
cent of the feed; it will be discharged for T'zeelim plant.
evaporation into an open, shallow earth It is believed that within the next decade
reservoir covering an area of about 10 Israel's industry will prove capable of
dunams (2.5 acres) . undertaking the construction of electro-
The plant consists of three desalination dialysis plants for the demineralization of
stages in series in a single closing frame, some 75 million eu m per year (about
with the possibility of adding a fourth 60 mgd) of brackish water, a quantity
stage. Each stage contains 100 membrane which is considered worthwhile for desalting.
pairs of 1.0 m by 0.6 m. The membranes
RESEARCH IN SALINE WATER CONVERSION
The upsurge of interest in the problems brane characteristics and the development
of saline water conversion in Israel has led of suitable membranes. This research was
to the intensification of research and devel suggested by Mr. Г.. Forgash, a member of
opment work. This research is being con the laboratory staff. A paper dealing with
ducted at the Negev Institute for Arid Zone this research is being submitted to this
Research in Beersheba, at the Technion Symposium.
(Israel Institute of Technology) in Haifa,
at the laboratories of Desalination Plants HEAT AND MASS TRANSFER PROBLEMS
(Developers of Zarchin Process) , Ltd. at The research workers of the Department
Tel Baruch (in the vicinity of Tel Aviv) , of Chemical Engineering of the Technion
at the Weizmann Institute of Science in have paid considerable attention to heat
Rehovot, at the Hebrew University in transfer problems and scaling in the distil
Jerusalem, and at the Petach-Tikvah pilot lation and freezing processes.
plant iOsdor's process) . Measures have 1. The object of the research conducted
recently been taken toward closer coordina by Dr. S. Sideman and his associates was
tion in research among all these institu to study the basic phenomena associated
tions. Part of the research work deals with with the problem of direct contact heat
specific problems that have arisen in the transfer between two immiscible fluids.
course of the construction of conversion Heat transfer coefficients, as well as other
units (freezing method and electrodialysis) . data, have been determined for conditions
The remainder represents general research both with and without change of phase.
in various fields of saline water conversion. The study was inspired by the freezing
A brief description of some of the re process. Theoretical and empirical corre
search work being carried out in the above- lations have been suggested, broadening the
mentioned institutions follows. scope of the study for any temperature
ELECTRODIALYSIS level.
Studies of a single organic drop (such as
Research work in electrodialysis is being butane and pentane) evaporating in sea
carried out at the Electrodialysis Research water showed the heat transfer coefficient
Laboratory of the Negev Institute for Arid to be larger by at least one order of mag
Zone Research. nitude than that for noncvaporating drops.
1. Work has been proceeding on polari Studies of condensing vapors indicated simi
zation phenomena and the electrical resist larity to the mechanism of transfer to the
ance components associated with them. evaporating drops.
This has necessitated some fundamental The behavior of populations of drops
research on the construction and function evaporating in a spray column in counter-
of the membrane. Research is being done current flow was found to be different from
on microstructure of permselective mem that of a single drop. The temperature
branes by electron micrography and X-ray driving force between the two fluids and
diffraction in order to gain an insight into the volatile phase flow rate were found to
the microporous structure of permselective be the controlling factors.
membranes. Preliminary experiments have In another study, the effect of mechanical
shown that, under certain conditions, it is mixing on the transfer characteristics of a
possible to introduce a silver deposit into volatile liquid evaporating in contact with
the porous structure of membranes and in another immiscible liquid was investigated.
this way obtain a better picture of its A general correlation relating to power
internal structure. This research was sug input, temperature driving force between
gested by Dr. F. de Korosy, a member of the two fluids, and heat flow rates was
the laboratory staff. The Office of Saline derived. Experimental data with a pentane-
Water has awarded a $15,500 contract for water system confirmed the validity of this
this research. correlation. Data from a pilot plant oper
2. The preliminary work carried out ated by Desalination Plants (Developers of
during 1963 showed that a considerable Zarchin Process), Ltd. also confirmed the
saving in power can be achieved when the correlation.
process is carried out at a temperature 2. The work of Dr. E. Kehat and Mrs. R.
above 80°C. The Office of Saline Water Letan indicated the uniqueness of mechan
has awarded the Negev Institute a $37,000 ism of heal transfer in a spray column
contract for this research. The work is operated as a heat exchanger between two
directed toward the determination of mem immiscible liquids, such as kerosene and
water. These features are important for a result of accumulated scale at the
proper scale-up. interface.
Two modes of operation of a spray A temperature jump observed at the
column are possible: (I) dense packing water inlet for dispersed packing prevents
and (2) dispersed packing. Dense packing close approach of the temperatures of the
is broken up when the coalescence rate is two liquids at the top of the column
increased at the kerosene-water interface as (Fig. 31) .

Kerosene
Inlet

Water
Outlet
Kerosene
Outlet

Water
Inlet

Bottom Top
Length of Spray Column

FIGURE 31. TEMPERATURE PROFILES IN A SPRAY COLUMN


HEAT EXCHANGER (DISPERSED PACKING).

The use of overall heat transfer coeffi carried out, with the assumption that the
cients will, therefore, lead to poor scale-up system is free of air contamination. The
of laboratory data, particularly for dis validity of these analyses has been con
persed packing. It is preferable to operate firmed by experimental data, under condi
the column with dense packing, and drain tions of airfree steam and water.
age of the interface will be required. Experimental results show that, under
The optimum ratio of the flow rates of normal water supply conditions, i.e. tap
kerosene to those of water required for water containing about 100 cm* free air
the establishment of full dense packing in per liter of water but without air in the
the column may not be the desired ratio steam, the local Nu (Nusselt Number) and,
of flow rates for heat balance. Additional consequently, the heat transfer coefficient,
work is required to study the conditions are half of the theoretical value calculated
for optimum operation and scale-up of above.
heat exchange spray columns. A correlation was obtained on the reduc
3. Heat transfer in the direct contact tion in the heat transfer coefficient with
condensation of steam on a water jet has increasing air content of steam with normal
been studied by Dr. D. Hasson and his tap water. This was measured at steam
associates. This method of condensation is pressures 133 Hg and 850 Hg, which pro
particularly important for the "vapor re duced very similar results. The correlation
heat flash process", which is based entirely Nu, — 4.8e-°•«•
on the principle of direct contact heat c = % vol. air in steam,
transfer between water vapor and water jets. so by 1 per cent of air the Nu. will de
Theoretical analyses of steam condensa crease by 2.
tion on various types of jets have been 4. Dr. D. Hasson and Dr. W. Resnik
01
95
96
have studied the mechanism of scale dep of the Hebrew University in Jerusalem are
osition on heat transfer surfaces. studying the ion transport in Dead Sea
The object of this research is to elucidate bacteria as a possible means of biological
basic scaling mechanisms and determine desalination. This study is being carried
quantitative relationships for predicting out under a contract with the Office of
rates of scale deposition. So far, work has Saline Water. A paper on this subject is
been restricted to nonboiling conditions being submitted to this Symposium.
under which CaCO, scale is deposited. 2. A study sponsored by the Interna
A practical method has been developed tional Atomic Energy Agency (Vienna) on
for correlating the variations of thermal "The Feasibility of Nuclear Reactors for Sea
resistance with time in steam heat Water Distillation in Israel" is being con
exchangers. ducted by Dr. S. Yiftah and Dr. F. S.
A fundamental analysis of processes tak Aschner and associates of the Department
ing part in scale deposition has been of Nuclear Science of the Haifa Technion.
proposed and the rates of some of these 3. A pilot desalination plant for opera
processes have been determined. tion in the vicinity of the critical point of
A noteworthy achievement is the devel water is at present being erected in the
opment of a constant heat flux electrical town of Petach Tikvah. The process has
exchanger for scale investigations. been suggested by an Israeli engineer, A.
5. Within the Department of Aeronau Osdor, and its development is privately
tical Engineering of the Haifa Technion, financed. The incoming sea water is heated
Professor A. Kogan is experimenting with and compressed by means of direct contact
a single-stage direct contact evaporation- heat exchangers and pressure exchangers
condensation unit. The influence of stage
geometry and inert gas content upon per respectively. Hydrocarbon and nitrogen gas
formance is being investigated. A paper on are used as heat transfer agents. After
this subject has been submitted to this separation at the critical point, the product
Symposium. steam is further compressed. Consequently,
the raising of the temperature proceeds at
OTHER RESEARCH WORK a lower specific heat; the cooling cycle is
1. Professor A. Katchalsky of the Weiz- effected at a higher pressure than the heat
mann Institute of Science and Dr. Margaret ing cycle, securing a 10°C temperature dif
Wickson Ginzburg and Dr. B. Z. Ginzburg ference between the fluids.

COORDINATION OF RESEARCH ACTIVITY


Following the recommendations of the industrial enterprises equipped for the
Joint U.S.-Israel Desalting and Power Team production of such items as large heat
on coordination between the development exchangers, large pumps, boilers, etc., it is
programs of the Governments of the United expected that research work in the future
States and Israel, the Israel National will perforce be primarily devoted to more
Council for Research and Development is basic aspects, such as scale deposition, cor
actively engaged in the preparation of a rosion, membrane structure and function.
comprehensive coordinated research pro At Israel's present stage of development,
gram. It is estimated that about fifty sci her scientists can contribute in the fields
entists in the institutions of higher learning of heat and mass transfer and membrane
and research institutions of Israel are pre processes. Work in these fields is being
pared to work in the field of saline water carried out at the Technion, the Negev
conversion. Such a group of research Institute for Arid Zone Research, and the
workers will require a yearly expenditure Weizmann Institute. In time, other institu
of SI,000,000, as compared with the $150,000 tions, such as the universities in Jerusalem
being spent on conversion research during and Tel Aviv, may become active in this
the current year. work.
In view of the fact that Israel still lacks

SUMMARY OF DISCUSSION
In response to questions concerning the the problem of wind stirring the water and
solar ponds being worked on at Beersheba dirt settling in, it was stated that the
and the progress being made in solving answer would be given by representatives
bom the Negev Institute. of the water when put to bénéficiai use.
The question of which process is of in The speaker stated further that if the
terest to serve irrigation water purposes water could be obtained for 7 cents per
was raised. In answer, it was stated that eu m (equivalent to about 30 cents per
rate of interest on money and years of thousand gallons) , and if the water were of
writeoff on capita! and operating costs high quality and blended with brackish
determine the cost of desalinated water, water to improve the quality of the mix
and that the price of this water, in turn, ture for agricultural purposes, this would
is related to these costs and to the value be acceptable for agricultural use in Israel.

Aperçu Sur le Dessalement de L'Eau

en Israel

I. Vilentchuk

La consommation de l'eau en Israël ap Une seconde installation d'une capacité


proche de 85% de la totalité des ressources similaire est envisagée pour le début de
naturelles en eau du pays, si bien qu'après 1968.
1970 le pays souffrira d'une pénurie aiguë Une installation de congélation sous vide
d'eau. Une proportion appréciable de ces de 1.000 m*/jour a également été construite
ressources sont minéralisées, les rendant à Eilat. Une installation d'électrodialyse est
impropres à l'agriculture, à moins d'être en cours de construction dans un kibboutz
mélangées à de l'eau de qualité très élevée. du sud et, selon les résultats de son fonc
Vers 1970, il faudra un appoint d'environ tionnement, une installation de 4.800 m'/
475.000 m3 par jour d'eau de mer convertie. jour est à l'étude pour une autre commu
Une installation à double usage, produisant nauté agricole dans la même région aride.
200.000 kW d'énergie et 380.000 m'/jour Des travaux de recherche sur les diffé
d'eau de mer convertie, est actuellement à rents aspects du dessalement sont effectués
l'étude de la part d'une équipe conjointe dans les hautes écoles et dans des labora
Etats-Unis/Israël, se spécialisant dans la toires spéciaux en Israël. Il convient de
déminéralisation. noter tout particulièrement les travaux de
Une installation à double usage, de 6.000 recherche portant sur les problèmes de
kW d'énergie, intégrée avec un ensemble transfert de chaleur et de masse dans les
de conversion du type à évaporâtion instan procédés de distillation et de congélation
tanée de 3.800 m'/jour, a récemment été au Technion (Institut de Technologie d'Is
construite dans la ville d'Eilat, dans la raël à Haifa) , et sur l'électrodialyse à
partie la plus méridionale d'Israël, ce qui l'Institut du Neguev pour les recherches sur
augmentera les approvisionnements exis la zone aride, à Beersheba. Des mesures
tants en eau saumâtre. Cette installation sont prises en vue d'assurer une coordina
est considérée comme une installation de tion plus étroite de la recherche effectuée
démonstration dans le cadre de l'important par toutes ces institutions.
projet de conversion mentionné ci-dessus.

90
Обзор Опреснения Воды в Израиле

И. Виленчук

Израиль

Потребление воды в Израиле прибли начале 1968 года предполагается по


жается к 85% суммы всех естественных строить второй агрегат такой же про
водных ресурсов страны, так что в на изводительности.
чале семидесятых годов наступит В Эйлате была также построена ва
острый недостаток воды. Значительная куумная холодильная установка на
часть этих ресурсов содержит в себе 250.000 галлонов в сутки. Агрегат на
минералы, делая их непригодными для 125.000 галлонов в сутки строится в
земледелия без смешения с водой одном южном поселке, а по выяснении
очень высокого качества. В начале се его эксплуатационных качеств намеча
мидесятых годов потребуется выраба ется постройка завода на 1,25 миллиона
тывать 125 миллионов талонов опре галлонов в день для другого земледель
сненной морской воды в день. Сейчас ческого поселка в том же пустынном
объединенная американо-израильская районе.
группа по опреснению изучает вопрос В высших учебных заведениях и спе
постройки завода двойного назначения, циальных лабораториях Израиля иссле
производящего 200 мегаватт электри дуются различные вопросы, касающие
ческой энергии и 100 миллионов галло ся опреснения. Заслуживает особого
нов опресненной морской воды в сутки. внимания исследование проблем пере
Установка двойного назначения на носа тепла и вещества при процессах
6.000 киловатт электроэнергии с сов дистилляции и замораживания, которое
местным опреснительным агрегатом, ведется в Технионе — Израильском
типа мгновенного испарения, на 1 мил Технологическом институте в Хайфе, и
лион галлонов воды в сутки была не электродиализа — в Негевском инсти
давно построена в городе Эйлате, в туте по исследованию пустынной зоны
самой южной части Израиля, что уве в Беершебе. Принимаются меры для
личит существующее снабжение соло большего координирования исследова
новатой водой. Этот завод считается тельской работы всех этих учрежде
показательным в связи с вышеупомя ний.
нутой крупной схемой опреснения. В

100
Estudio Sobre la Desalinizacion del

Agua en Israel

I. Vilentchuk

Israel

El consumo de agua en Israel está aproxi mente. Se contempla una segunda unidad
mándose al 85% de los recursos totales de una capacidad casi igual para principios
de agua en el pais, de tal modo que para de 1968.
los primeros años de la década de 1970 se También se ha construido en Eilat una
experimentará una gran escasez de agua. planta congeladora al vacío de 250.000 ga
Una proporción considerable de estos re lones diarios. Está en construcción en una
cursos contienen minerales, lo que los hace colonia en al sur una planta de electro-
no aptos para la agricultura, a menos que diálisis de 125.000 galones diarios y, pen
se mezclan con agua de buena calidad. Una diente de los resultados de su operación,
cantidad aproximada de 125 millones de se está contemplando la construcción de
galones por día de agua de mar desalini- una planta de 1.250.000 galones diarios
zada será necesaria para los primeros años para otra colonia agrícola ubicada en la
de la década de 1970. Una planta de doble misma región árida.
fin, con capacidad de 200 megavatios de Se están llevando a cabo trabajos de
energía y 1O0 millones de galones diarios investigación sobre los diferentes aspectos
de agua de mar desalinizada, está en la de la desalinización en las instituciones de
actualidad bajo la consideración de un enseñanza superior y en laboratorios espe
grupo de trabajo conjunto de Israel y ciales de Israel. De especial importancia
Estados Unidos sobre desalinización. son los trabajos de investigación sobre los
Una planta de doble fin de 6.00kw de problemas de la transferencia del calor y
energía integrada con una unidad de con de la masa en los procesos de destilación
versión de tipo instantáneo de 1 millón de y congelación en el Instituto Tecnológico
galones por día fue construida reciente Technion-Israel de Haifa, y sobre electro-
mente en la ciudad de Eilat en la región diálisis en el Instituto Negev de Investiga
más meridional de Israel que aumentará ciones para Regiones Aridas en Beershcba.
el suministro existente de aguas salobres. Se están tomando medidas para una co
Esta planta se considera como una planta ordinación más estrecha de las actividades
de demostración en relación con el proyecto de investigación entre todas estas institu
extenso de conversión mencionado anterior ciones.

101
The "Siro therm" Demineralization

Process — An Ion-Exchange Process

With Thermal Regeneration

D. E. Weiss, B. A. Boko, R. McNeill, A. S. M acpherson,


R. Siudak, E. A. Swinton, and D. Willis

Australia

INTRODUCTION
Although the technology of water de- ture long-term needs undoubtedly influence
mineralization is the subject of research the selection of the sea as an immediate
effort today, there is little evidence that source of water, the fact that removal of
much thought has been given to the inte 35.000 ppm of salinity by distillation can
gration of municipal demineralization be considered to compete with the removal
processes with other sources of water sup of 250 ppm of salts by alternative methods,
ply to achieve minimum overall costs. We highlights the deficiencies of the latter, and
have suggested elsewhere (ref. 1) that effi the lack of attention that the problem of
cient integration of surface and under maintaining a salinity balance in water
ground water supplies, coupled with the supply schemes has hitherto received.
use of a demineralization plant to provide With processes such as ion-exchange and
a salt bleed from the supply system, pro electrodialysis, it is possible to remove
vides a realistic approach to preventing small amounts of salinity more cheaply
the accumulation of salinity within water than large amounts, but the removal of
supply systems considered on a regional, small amounts of salinity is currently re
rather than on a local basis. ceiving comparatively little attention com
The need for a salt bleed in arid regions pared with sea water conversion. Priority
when complete utilization of water supplies should be given to the development of
is in sight is well illustrated in a recent cheap methods for preventing excessive
report on the water supply situation in pollution of existing water supplies by in
Israel (ref. 2) . An almost completely closed organic salts. Such methods are more likely
cycle of water use will occur in Israel by to achieve a treatment cost of about ten
1975 and means will then have to be found cents per thousand gallons, and are more
for removing salt from the supply system urgently needed than the conversion of
economically. As a result of accumulating heavily polluted resources such as sea
salinity, there will be available by 1970 a water. This paper presents a new approach
daily flow of 200 million gallons of water to the problem of salinity control and
with an average salinity of 500 ppm (as demonstrates the feasibility, in the labora
NaCl) , which will have to be reduced to tory, of using ion-exchange resins for de
250 ppm to maintain the quality required mineralization by the "Sirotherm" process*,
for growing high value export crops. An in which regeneration of the spent resins
investigation is now being made of the is performed with heat rather than chemi
feasibility of using sea water desalination cals. The work to date has been confined
to provide distilled water for dilution of mainly to equilibrium studies.
the flow to the desired value by 1972.
Although political considerations and fu * Patent applications have been submitted in the
United States of America and in other countries.

103
A SYSTEM OF WATER MANAGEMENT FOR CONTROLLING THE SALINITY
OF MUNICIPAL SUPPLIES ON A REGIONAL BASIS
Since incremental municipal water sup phenomena (ref. 1) . Regional salinity con
plies become increasingly expensive and trol requires the segregation of irrigation
quality deteriorates owing to extensive re drainage waters from the river, and a cheap
use, there arc four logical, successive stages demineralization process for taking out the
of water management for reducing costs: salinity which accumulates with each mu
1. Improvement of conservation methods; nicipal or industrial use cycle from supplies
2. Reclamation of effluents for reuse; derived from the river. If demineralization
3. Demineralization of waters of mar were applied to nearby underground waters,
ginal quality which are too saline for as shown in Figure 32, space would be
general use; created which could be recharged with
4. Once water is efficiently utilized, use surplus waters of good quality in wet
must be made of expensive supplies periods, and the demineralization load
from long-distance pipelines or from would be thereby reduced (ref. 1) .
desalination of the sea or highly The use of demineralization for salinity
brackish waters. control warrants widespread attention, as
Inorganic salts accumulate when river it would make possible complete utilization
water is reused extensively in an arid of existing river supplies. Fundamental
climate. Consideration of the factors con considerations suggest that the cheapest
tributing to the salinity* of rivers shows process for this purpose would use ion-
that the contributions from man's use of exchange resins regenerated with heat
the water, particularly for irrigation, is of rather than chemicals (ref. 1) . Our investi
ten much greater than those from natural gation of this approach is presented below.

THE "SIROTHERM" PROCESS


The purpose of the "Sirotherm" project resin pair and the optimum conditions of
is to develop a demineralization process in pH and resin ratio, but this problem is
which regeneration of ion-exchange resins of unusual complexity, and is not suitable
is accomplished by the use of low grade for direct empirical experimentation owing
heat rather than by chemicals. The process to the large number of resin pairs and
depends on the marked influence of temper variables requiring study. A rapid scanning
ature on the equilibrium between a solu procedure was therefore devised to select
tion of sodium chloride and a mixed bed the systems for detailed study.
of weak base (Rb) and weak acid (RaH) It will be shown that the titration
ion-exchange resins: curves of weak-acid and weak-base resins
R.H + Rb + NaCl ;± R.Na + R„HC1 (1) provide a means of independent charac
Heating promotes hydrolysis of the resin terization which enables us to predict the
salts and thereby reduces the adsorption equilibrium behavior of a mixture of the
of salt. resins under many different conditions. As
The equilibrium depends on many varia a prelude to the scanning program, it was
bles besides temperature, such as the basicity necessary to synthesize a large number of
and acidity of the resins, pH value and ion-exchange resins, as the structure of
ionic strength of the solution, resin affin commercial resins is not usually disclosed
ities for different ions, and the ratio of by the manufacturers, and to study the
equivalents of acid to base resin (resin titration curves of the experimental and
ratio) . The basicity and acidity of the commercial resins in detail. Detailed exam
resins can be varied widely by changes in ination of a pair of commercial resins,
polymer structure. selected on the basis of this information,
The first problem in the "Sirotherm" shows that the equilibrium changes on
project was the selection of the optimum heating are of a magnitude sufficient for
performing useful demineralization oper
* In this paper, salinity refers to the total ations.
amount of dissolved inorganic solids in a water.

104
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105
PROPERTIES OF WEAK-BASE RESINS
Our experimental study of the properties curves of a number of resins are presented
of weak-base resins, which will be presented in Figures 33 and 34 and show two types
elsewhere (ref. 3) , shows that satisfactory of behavior. Two resins, "De-Acidite G"
commercial resins* are available for use in and "Amberlite IRA-93", have titration
the "Sirotherm" project. Therefore this curves with a pronounced plateau region
paper will be concerned mainly with the of almost constant pH value, whereas the
commercial resins. curves for the other resins slope steeply,
(1) Homofunctional Resins: Titration but to different extents. The plateau be
havior occurs only with resins containing
* The following registered trademarks are used functional groups having predominantly
by ion-exchange resin manufacturers: "Amber- the same basicity (ref. 3) . The latter resins
lite", the Rohm and Haas Company, U.S.A.;
"Dowex", the Dow Chemical Company, U.S.A.: will be termed "homofunctional" whereas
"Duolite", the Western Division of Diamond resins with sites of different basicity will
Alkali, U.S.A.; "Zeo-Karb" and "De-Acidite",
the Permutit Company, Ltd., London; "Lewatit", be termed "heterofunctional".
the Farbenfabriken Bayer, A.G., West Germany.

pH

0 Acid Fraction 1

FIGURE 33. TITRATION CURVES OF AMINE RESINS IN


29,300 PPM SALINE AT ABOUT 20°C.
1. "De-Acidite J" S. "De-Acidite G"
2. "De-Acidite M" 4. "De-Acidite H"

106
о I
Acid Fraction
FIGURE 34. TITRATION CURVES OF AMINE RESINS IN
29,300 PPM SALINE AT ABOUT 20°C.
1. Dowex 3" 5. "Ambcrlite IRA-9S"
2. "Dowex 4" 6. "Duolite A-30T"
3. "Amberlite IRA-45" 7. "Lewatit MP-60"
4. "Amberlite IRА 6И"

The commercial weak-base homofunc shown in Figures 33 and 34, the pH values
tional resins contain mainly tertiary amino recorded being those of the supernatant
groups but the presence of some quater solutions, which were removed from the
nary ammonium groups is unavoidable. resins while hot and cooled to about 20T.
The titration curve of a special sample of before measurement. The data on hot titra
"De-Acidite C" containing 26 per cent of tion curves at acid fractions of 0.25, 0.50,
its functional groups as quaternary am and 0.75 are shown in Table XX as the
monium centers given in Figure 35 shows difference- in pH value between the titra
the resin to be heterofunctional. Heating tion curves at about 20°C and S0°C. The
the resin with alkali dealkylates the quater data show that heating reduces the basicin
nary structures and yields a tertiary amine of the resins and that homofunctional resins
resin with homofunctional properties (Fig. exhibit greater temperature effects over the
35). widest range of acid fraction. This is also
(2) Effect of Temperature: Titration illustrated by the data in Figure 35.
curves were prepared at 80°C for the resins

107
0 Acid Fraction 1
FIGURE 35. TITRATION CURVES OF AMINE RESINS IN
1,760 PPM SALINE AT ABOUT 20° AND 80°C.
1. "De-Acidite G," containing 26 per cent quaternary ammonium groups. The titration
curve was determined at about 20° C
2. Same at 80°C.
3. The above resin was treated with boiling 2N alkali for 48 hrs. to yield a resin
containing 5.5 per cent quaternary ammonium groups. The titration curve was
obtained at about 20°C.
4. Same at 80°C.
TABLE XX. Difference in pH Valves for (3) Effect of Resin Structure and Ionic
the Titration Curves of Various Com Strength: A study of experimental homo-
mercial Resins in a 29,000 ppm Solution functional tertiary resins prepared from
of Sodium Chloride at about 20°C and crosslinked polystyrene beads showed that
Mr*C the pH value of the plateau may be varied
by three pH units by changing the alkyl
pH differe substituents on the amino nitrogen atoms.
Add fnotion The basicity and also the total exchange
Rata capacity of the resins increase with decreas
0.25 0.60 0.75 ing chain length of the alkyl substituents
so that the basic resins requiring further
Homofunctional resins: study may be limited to dimethyl, diethyl,
"De-Acidite G" 1.1 1.2 1.0 or monoethyl derivatives (ref. S) . The
"Amberlite IRA-98" 0.9 1.0 1.2 titration curve of an experimental dimethyl
Hcterofunctional resins: resin is very similar to that of "Amberlite
"De-Acidite M" O.S 0.5 0.7 IRA-93", and a diethyl tertiary amine resin
"De-Acidite J" 0.4 0.4 1.0 is available as "De-Acidite G".
"De-Acidite H" 0.7 0.7 0.6 Crosslinking does not have a great influ
"Amberlite IRA-46" 0.8 0.6 0.0 ence on the basicity of the resins (ref. 3) .
••Amberlite IRA-68" 0.1 -0.1 -0.2
"Dowel S" 0.5 0.8 0.2 Increasing the ionic strength of the solu
"Dowex 4" 0.8 1.0 0.8 tion in equilibrium with the resins has a
"Duolite A-SOT" 0.1 0.8 0.4 pronounced base-strengthening effect but
"Lewatit MP-60" 0.5 0.2 -0.4 does not greatly change the shape of the
titration curves (ref. S) .

PROPERTIES OF CARBOXYLIC RESINS


Available carboxylic resins with satis decreases with temperature, the thermal
factory thermal stabilities are limited to variation is not as marked as for the amine
polymers or copolymers of acrylic or meth- resins. Calcium and magnesium ions exert
acrylic acids. As shown in Figure 36, the a much greater acid-strengthening effect on
hot and cold titration curves of the poly the titration curve than do sodium ions,
(methacrylic acid) resin, "Amberlite IRC- probably because of chelation with the
50", differ by about one pH unit from carboxyl groups (ref. 4) .
those of the poly (acrylic acid) resin, "Zeo- We iave prepared copolymers containing
Karb 226"*. A change in acidity of com carboxyl groups which possess flatter titra
parable magnitude can also be made by tion curves, but so far these resins are too
changing the crosslinking of the resin (refs. weakly acidic and have too small an ex
4, 5) , but in practice resins with low cross- change capacity to be of practical interest
linking must be used to obtain satisfactory (ref. 4) . We have also enhanced the ther
exchange rates. As shown in Figure 36, the mal effect by preparing snake cage polymers
titration curves of the carboxylic resins do from crosslinked poly (acrylic acid) cages
not show a pronounced plateau, even and linear polymeric snakes containing
though the acidity of the resins is due ether and hydroxyl groups, but the lower
solely to carboxyl groups; while the acidity capacity and increased cost of these resins
• The titration curve of "Amberlite XE 282" ia do not warrant their use in place of exist
very similar to that of "Zeo-Karb 226". ing poly (acrylic acid) resins (ref. 4) .

SELECTION OF OPTIMUM RESIN PAIR


A detailed study of the procedure for de positions derived by the two methods for
termining the titration curves (ref. 6) the hot curve of "De-Acidite G". As a first
shows that for the hot and cold curves of approximation, it is therefore permissible
"Zeo-Karb 226", and the cold curve of to use the titration curve data for easily
"De-Acidite G", the resin composition cal determining resin compositions as a func
culated from the amount of acid added tion of pH. This information, approximate
(acid fraction) agrees with that obtained as it is at 80°C, can be used in screening
by direct analysis of the resin over the pH tests to predict comparative equilibrium
range 4 to 9. There is a significant differ data for various resin combinations under
ence of up to 8 per cent in the resin com different conditions of pH and ionic

109
BASE FRACTION
FIGURE 36. TITRATION CURVES OF CARBOXLYIC ACID
RESINS IN 1,760 PPM SALINE.
1. "Amberlite IRC-50" at 80°C 3. "Zeo-Karb 226" at 80°C
2. "Amberlite IRO50" at about 20°C 4. "Zeo-Karb 226" at about 20°C

strength. From this data it is possible to value; (3) resin ratios other than unity
select a pair o[ resins for more detailed may be used and the final equilibrium pH
study and to see the relative importance of value may be adjusted to any desired value
the different factors influencing the equilib- by the addition of acid or alkali.
riinn conditions of difference combinations (1) Resin Ratio of Unity Without pH
of resins. Adjustment: This situation can be con
Three alternative procedures may be used sidered as in Figures 37 to 40 by super
to study the adsorption of salt by a pair of imposing the titration curves of the acid
acid and base resins in a salt solution: (1) and base resins at the specified temperature
equimolar mixtures of the resins in the un- and equilibrium salt concentration, so that
dissociatcd form may be added to the salt the scales of the resin composition cor
solution without any adjustment being respond. The equilibrium resin composition
made to the final equilibrium pH value and pH value of the solution are shown by
of the solution; (2) equimolar mixtures of the point of intersection of the titration
the resin can be added to the solution to curves, since this represents the individual
gether with acid or alkali to adjust the resin compositions which correspond to the
final equilibrium pH value to any desired same pH value. Since at about pH 4 to 10

110
the hydrogen ion concentration in the solu sociated acid and base resins at about 20°C
tion is negligible compared with that of and 80°C ("effective capacity") have been
the ions of a 0.03 molar salt solution, there measured by direct experiment for a large
will be one sodium ion adsorbed by the number of resin combinations. They show
acid resin for every chloride ion adsorbed trends similar to those indicated by the
by the amine resin. Both resin composi intercepts in Figures 37 to 40 (ref. 6) .
tions will change to the same extent after A comparison of Figures 37 and 38 shows
adsorption, since the resin compositions that the bigger effective capacity with a
were the same before adsorption. The dif poly (acrylic acid) resin, rather than a
ference between the projections onto the poly (methacrylic acid) resin in combina
resin composition axis of the points of tion with "De-Acidite G", is due to greater

pH

3 h

IONIZATION FRACTION 1

FIGURE 37. MATCHING OF TITRATION CURVES IN


1,760 PPM SALINE (RESIN RATIO UNITY).
1. "Amberlite IRC-50" 2. "De-Acidite G"

intersection of the hot and cold titration overlapping of the basic resin curves by
curves shows the change in resin composi the titration curves of the more acidic poly
tion which occurs on heating the resin (acrylic acid) resin. A comparison of
mixture in the salt solution. Figures 37 and 40 reveals that the effective
The differences in the amount of salt capacity for a combination of "De-Acidite
adsorbed by equimolar mixtures of undis- G" with "Amberlite IRC-50" is consider-

Ill
g

7 П

pH

5 h
io'c !

IONIZATION FRACTION
FIGURE 38. MATCHING OF TITRATION CURVES IN
1,760 PPM SALINE (RESIN RATIO UNITY).
1. 2.5 per cent cross-linked poly (acrylic acid) 2. "De-Addite G"

ably greater in a 29,300 than in a 1,760 therefore, one in which both resins have
ppm salt solution, since the effect of salt homofunctional titration curves which over
concentration on the titration curves is such lap to the maximum extent. For maximum
as to favor better matching at the higher performance it is also desirable that the
concentration. Figures 39 and 40 show that position of the titration curves of both
salt concentration has less influence on the resins with respect to the pH axis should
adsorptive behavior of heterofunctional shift as little as possible with changes in
than of homofunctional amine resins, ionic strength.
since changes in the positions of the (2) Resin Ratio of Unity with pH Ad
hot and cold intercepts on the sloping justment: If the resin ratio is unity but
titration curves of heterofunctional resins the pH value at equilibrium is altered by
do not greatly change the distance between the addition of acid or alkali, the situation
the intercepts, in contrast to homofunc is described by superimposed titration
tional resins. cunes as before, but shifted with respect
These examples show that the effective to each other along the resin composition
capacity increases as the overlapping of axis so that the point of intersection of the
the hot and cold acid and base titration cold curves is at the prescribed pH value.
curves extends. The ideal resin combina Such an analysis shows that the pH value
tion at a specified salt concentration is, has a large influence on the amount of salt

112
IONIZATION FRACTION
FIGURE 39. MATCHING OF TITRATION CURVES IN
29,300 PPM SALINE (RESIN RATIO UNITY).
1. "Amberlite IRC-50" 2. "De-Addite M"

adsorbed by the mixed resins, particularly change in composition of the acid resin on
when a homofunctional base resin is used the ionization fraction scale will be only
in which a large composition change can one-third that of the base resin. The rela
occur with very little change in pH. tive position of the curves can be moved,
(3) Resin Ratios Other than Unity with as in the preceding examples, so that the
pH Adjustment: When the resin ratio is intercept of the titration curves occurs at
no longer unity and the equilibrium pH any desired pH value.
value after adsorption has been adjusted Figure 41 also shows the hot and cold
to any desired value by the addition of titration curves of the same resins drawn
acid or alkali, the situation can be de on composition axes of the same length
picted, as in Figure 41 for an acid to base and superimposed so that the point of
resin ratio of 3, by superimposing the titra intersection corresponds with that of the
tion curve of the acid resin over that of previous example. The diagram thus illus
the base resin drawn on a composition trates the behavior of resin mixtures, with
axis only one-third the length of that of resin ratios of 1 and 3 respectively, and equi
the acid resin. Since one sodium ion must librated to the same pH value. It shows that
be adsorbed by the acid resin for every increasing the resin ratio increases the over
chloride ion adsorbed by the anion resin to lapping of the two titration curves so that
maintain electrical neutrality, and there are the salt uptake is considerably greater than
three equivalents of acid to base resin, the for the equimolar mixture. The effect of
9 h

7 h

PH

IONIZATION FRACTION
FIGURE 40. MATCHING OF TITRATION CURVES IN
29,300 PPM SALINE (RESIN RATIO UNITY).
1. "Amberlite IRC-50" 2. "De-Addite G"

increasing the resin ratio is therefore optimum resin ratio at each pH level. Con
equivalent to using an acid resin with a sequently, it is necessary to evaluate effec
flatter titration curve, and this approach tive capacities at various pH values and
represents a practical method of improving resin ratios when selecting the optimum
the matching characteristics of a pair of resin pair from the many resins available.
resins, since homofunctional acid resins Figures 42 and 43 show the effective
are not available. capacities at the optimum resin ratio for
(4) Optimum Resin Ratio and pH: It a variety of amine resins in combination
can be shown from an analysis of the titra with '"Zeo-Karb 226" plotted against pH:
tion curve data that for each pH value the optimum resin ratios of the maximum
there is an optimum resin ratio for maxi effective capacities are given in parentheses
mum effective capacity (ref. 6) . Figure 41 is the figure legend. The curves show that
shows that there will be greater overlap resins differ widely in their performance.
ping of the titration curves as the resin The effective capacity is critically depend
ratio increases. However, increasing the ent on pH when the amine resin is homo-
resin ratio also increases the weight of the functional; the dependence is less critical
resins per unit of base resin capacity, so for the heterofunctional resin "De-Acidite
that the effective capacity passes through M". The pH values corresponding to maxi
a maximum when expressed on a unit of mum effective capacities are shifted slightly
weight basis, and there will be a different by a change in salt concentration.

114
1,760
FOR
SALINE
UNITY
OF
RATIOS
RESIN
WITH
IN
BEDS
MIXED
AND
EPPM
3 QUILI
TG"
OF
"CURVES
AND
MFIGURE
226"
41.
DZIAET-ORAC-HKTIDAINROTBGE

3)
(resin
"IoZfor
F226
of
nratio
erioaz-catKiornb

00
06
05
2
3
01
00
074t
"Zefor
IoF-rnKaizcratb2io6n*
(Tft
0^2
<M
08

I)
of
(resin
ratio

AT
BRATED
20°C.
ABOUT
5.8
pH

1'—1i
11
1-4,

i 1 i i 1
4-6 50 60 70
pH AT OPTIMUM RESIN RATIO
FIGURE 42. PREDICTED EFFECTIVE CAPACITY (20° TO 80°C)
VS pH AT OPTIMUM RESIN RATIO FOR MIXED BEDS OF
VARIOUS AMINE RESINS WITH "ZEO-KARB 226" IN 1,760 PPM
SALINE. THE OPTIMUM RESIN RATIO AT MAXIMUM EFFEC
TIVE CAPACITY IS SHOWN IN PARENTHESES.
1. 3 to 5 per cent cross-linked polyvinylbenzylethylamine (1.9)
2. "De-Aadite G" containing 2.6 per cent quaternary ammonium groups (2.5)
3. 7 to 9 per cent cross-linked polyvinylbemyldimethylamine (1.9)
4. "Amberlite IRA-9S" (2.5)
5. As in 2, but with "Amberlite IRC-50" as the acid resin (4.0)
6. 7 to 9 per cent cross-linked polyvinylbenzyldipropylamine (4.0)
7. "De-Acidite G" containing 26 per cent quaternary ammonium groups (1.5)
8. "De-Acidite M" (1.0)
116
5 0 60
pH AT OPTIMUM RESIN RATIO
FIGURE 43. PREDICTED EFFECTIVE CAPACITY (20° TO 80°C)
VS pH AT OPTIMUM RESIN RATIO FOR MIXED BEDS OF
VARIOUS AMINE RESINS WITH "ZEO-KARB 226" IN 500 PPM
SALINE. THE OPTIMUM RESIN RATIO AT MAXIMUM EFFEC
TIVE CAPACITY IS SHOWN IN PARENTHESES.
1. "De-Atidite G" containing 2.6 per cent quaternary (S.3)
2. "Amberlite IRA-9S" (2.5)
3. "De-Acidite M" (1.0)

The results show clearly that "De-Acidite A similar analysis is given in Figure 44
C" and "Amberlite IRA-93" are the best for the titration curves of "Zeo-Karb 226"
commercial amine resins for use with "Zeo- and "De-Acidite G" at about 20° and 80°C
Karb 226". Even higher effective capacities in solutions containing 500 ppm or 1,760
are given by an experimental cross-linked ppm of sodium chloride or calcium sul
polyvinylbenzylethylamine resin in a 1,760 phate. The data in the latter case are for
ppm salt solution. The data also confirm a hypothetical calcium sulphate solution.
the superiority of the poly (acrylic acid) They were obtained from the titration
resin "Zeo-Karb 226" over the poly (mctha- curves of "Zeo-Karb 226" versus calcium
crylic acid) resin "Amberlite IRG-50". It hydroxide in calcium chloride solution, and
can be seen from Figure 42 that increasing of "De-Acidite G" versus sulphuric acid in
the quaternary ammonium content of "De- sodium sulphate solution. The plots show
Acidite G" from 2.6 per cent to 26 per cent that divalent ions raise the pH values for
reduces its performance considerably. maximum effective capacities to slightly
higher values, and that, whereas at a con- of monovalent rather than in that of
centration of 1,760 ppm, the maximum divalent ions, the converse is true at a
effective capacity is greater in the presence concentration of 500 ppm.

FIGURE 44. PREDICTED EFFECTIVE CAPACITY (20° TO 80°C)


VS pH AT OPTIMUM RESIN RATIO FOR "ZEO-KARB 226"/"DE-
ACIDITE G" MIXED BED AND HYPOTHETICAL CaSO,
SOLUTION.
Nad CaSO.
RESIN EQUILIBRIUM DATA
The performance of a distillation process ments show that this procedure is rigorous
can be predicted from an analysis of vapor- with accurately derived titration curve data
liquid equilibrium diagrams prepared at at about 20 °C, indicating that the resins
different pressures. The analogous data for behave independently in a mixed-bed (ref.
the "Sirotherm" process for a simple solu 6) . Accurate determination of the equilib
tion of sodium chloride are plots of amine rium diagrams at 80°C requires the direct
resin compositions versus acid resin com measurement of resin compositions.

FIGURE 45. CONSTRUCTION OF THE EQUILIBRIUM DIAGRAM


FOR A MIXED BED FROM THE SEPARATE RESIN TITRATION
CURVES IN 1,700 PPM SALINE AT ABOUT 20°C.
1. Titration curve of "De-Acidite G"
2. Titration curve of "Zeo-Karb 226"
3. Constructed equilibrium diagram for "Zeo-Karb 226"/ "De-Acidite G" mixed bed
X. Experimental points

positions at different temperatures and salt Equilibrium curves thus determined at


concentrations. As shown in Figure 45, such about 20°C and 80°C for sodium chloride
plots can be derived from the relevant solutions at concentrations of 500, 1,000,
titration curves, which express resin com 1,760, 3,000 and 5,000 ppm are given in
positions as a function of pH, by plotting Figures 46 and 47. From these curves it is
acid and base resin compositions that cor possible to calculate reliably the effective
respond to the same pH value. Experi- capacity at optimum resin ratio and pH

119
RC02Na RC02H

FIGURE 46. EQUILIBRIUM DIAGRAMS FOR "ZEO-KARB 226"/


"DE-ACIDITE G" MIXED BED AT ABOUT 20°C. CONSTRUCTED
FROM THE SEPARATE RESIN TITRATION CURVES DETER
MINED IN SOLUTIONS OF THE FOLLOWING SALT CONCEN
TRATION:
1. 5,000 ppm 3. 1,760 ppm 5. 500 ppm
2. 3,000 ppm 4. 1,000 ppm

120
FIGURE 47. EQUILIBRIUM DIAGRAMS FOR "ZEO-KARB" 226/
"DE-ACIDITE G" MIXED BED AT 80°C. DATA DETERMINED
DHtECTLY IN SOLUTIONS OF THE FOLLOWING SALT CON
CENTRATION:
1. 5,000 ppm S. 1,760 ppm 5. 500 ppm
2. 3,000 ppm 4. 1,000 ppm

121
I I
2000 4000 6000
SALT CONCENTRATION, ppm
FIGURE 48. EFFECTIVE CAPACITY (20° TO 80°C) UNDER OP
TIMUM CONDITIONS FOR "ZEO-KARB 226'7"DE-ACIDITE G"
MIXED BED AT VARIOUS SALT CONCENTRATIONS.

as a function of salt concentration. These XXI with similar data determined from the
data are given in Figure 48. experimentally derived equilibrium dia
The maximum effective capacity, opti grams. The results confirm the reliability of
mum resin ratio and pH, as determined the screening procedure for assessing major
from the titration curves used in the screen differences in performance.
ing experiments, are compared in Table

TABLE XXI. Data for "Zeo-Karb 226"/"De-Acidite G" Mixed Bed

Salt Source of 80°C Optimum* Optimum Optimum


concentration equilibrium effective capacity PH reain ratio
ppm data meq/g mixed bed value (acid/base)
500 A 0.78 5.5 S.S
500 B 0.97 6.4 4.0
1,760 A 1.12 6.0 2.6
1,760 B 1.45 5.9 2.2
A = Predicted from separate resin titration curves at 80°C.
B = Determined from the80°C equilibrium diagrams found by direct experiment.
* Capacities are expressed on a dry weight basis (ref. 3).

REVERSIBILITY
Mixtures of equivalent amounts of "De- in ampoules containing outgassed aqueous
Acidite G" and "Amberlite IRC-50", both solutions of sodium chloride. The mixtures
of particle size 2 to 50 microns, were sealed were subjected to 5,000 cycles of successive

122
heating (90°C, 8 min.) and cooling (about is possible with acids since protons are
20°C, 10 min.) without any loss in ex bound even more strongly. Elution in the
change capacity (ref. 3) . These experiments "Sirotherm" mixed bed is also affected by
show the high thermal stability of the resins protons since heating results in the transfer
in the absence of air, and the complete of protons from the amine salt to the car
reversibility of the adsorption-desorption boxylic resin salt. It is to be expected, there
cycle in solutions of sodium chloride. fore, that divalent as well as monovalent
It has been shown that the "Sirotherm" ions will be adsorbed reversibly in the cold
mixed bed is highly selective for divalent and hot cycles of the "Sirotherm" process.
ions, particularly magnesium and calcium This expectation has been confirmed for
ions (ref. 6) . The high selectivity of the sodium chloride over 1,000 cycles for a
carboxylic resin for calcium and magne variety of solutions containing magnesium,
sium ions is probably due to chelation with calcium, and sulphate ions (ref. 6) .
the carboxyl groups, but complete elution

MULTISTAGE OPERATIONS
Continuous countercurrent operation A comparison of the series I and 2 re
would be the most efficient way of conduct sults shows that slightly better peak con
ing the "Sirotherm" process to obtain max centrations and column capacity are
imum utilization of the resin. The data in obtained by regenerating with the 550
Figures 46 and 47 can be used to calculate ppm solution. However, as the pH value
the equilibrium performance of an ideal of the product water after regeneration
multistage system for various concentrations at 500 ppm was alxnit 0.5 of a pH
of sodium chloride and for different num unit lower than in the first series of experi
bers of stages of adsorption and regenera ments, it seems likely from a consideration
tion (ref. 12) . The ionic strength is differ of (he data in Figures 42 and 43 that a
ent in each stage so that the problem of better performance would have been ob
selecting an optimum resin ratio and an tained had the pH value of the column
optimum pH at a specified adsorption stage been adjusted to a higher value. Hence,
is complex. In practice, the problem with comparison of the two sets of experiments
actual waters is aggravated by the presence is not rigid. More experimental data, com
of divalent as well as monovalent ions. bined with an economic analysis of the
The simplest method of investigating the results, are required before it can be de
complexities of multistage operation on a cided whether the regenerant should be
laboratory scale is to use static columns product or feed water. Another series of
of resin in the usual cyclic fashion. Inter experiments with a feed of 1,000 ppm
pretation of the results requires the as sodium chloride (series 3) was performed
sumption that the peak concentrations at with the resins adjusted to lower pH values
tained could be realized as steady-state than used in the series 1 experiments.
conditions in a continuous countercurrent The results in Figure 49 and Table XXII
process, or approximated in a cyclic batch show that the column capacity was consid
operation using split elution, although the erably less than in the first series. A similar
experiments do not indicate the number of experiment (series 5) was performed at
theoretical stages required. higher pH values and shows that the
A series of column experiments was per column capacity was substantially reduced
formed with a mixture of "Zeo-Karb 226" by raising the pH to a value above that
(SRC 44) and "De-Acidite G" (SRA 102) used in the series I experiment. The re
with particle sizes less than 200 mesh (ref. sults thus confirm the importance of pH
12) . Details are given in Figure 49 and in determining effective resin capacity. The
Table XXII. The data show that during the data in Figure 49 also show that the process
adsorption cycle with a feed of 1 ,000 ppm works satisfactorily with a feed concentra
sodium chloride, a product is obtained with tion of 3,000 ppm sodium chloride (series 4).
a minimum concentration of about 230 to Another series of experiments (series 6)
250 ppm. Regeneration with the same feed was performed with a 1,000 ppm solution
water at 80°C yields an effluent with a of magnesium sulphate. The results show
peak concentration of 4,800 ppm (series 1) . that the process can treat a solution of
The equilibrium data show that resin per magnesium sulphate as well as one of
formance should improve, under equilib sodium chloride, but the operating pH was
rium conditions, with the use of product probably too low for optimum performance
rather than feed water for regeneration. as suggested by the data in Figure 44.

123
5 10 15 20 26 0 5 10 15 20 25
Bed Volumes
FIGURE 49. COLUMN EXPERIMENTS FOR CHROMATOGRAPHIC
GRADE "ZERO-KARB 226" SRC 44/"DE-ACIDITE G" SRA 102
MIXED BED, RESIN RATIO 2.5.
1. Feed 1,000 ppm NaCI, regenerant 1,000 ppm, pH 5.8-5.5
2. Feed 1,000 ppm NaCI, regenerant 500 ppm
S. Feed 1,000 ppm NaCI, regenerant 1,000 ppm, pH 5.1-4.6
4. Feed 3,000 ppm NaCI, regenerant 3,000 ppm
5. Feed 1,000 ppm NaCI, regenerant 1,000 ppm, pH 6.0-5.8
6. Feed 1,000 ppm MgSO„ regenerant 1,000 ppm

124
TABU XXII. Column Result* with "Zeo-Karb 226" (SRC 44) and "De-Acidite G"
(SRA 102)

Effective capacity"
PH» Concentration, ppm (20°C to 80°C)
pH of
Series Resin before adsorption of column
no. ratio adsorp trough Adsorp Regen- Second Second
tion Feed Regen- tion erant adsorp regenera
erant mini maximum tion tion
mum meq/ml meq/ml
j 2.5 6.7 5.8-5.6 1,000 1.000 230 4,800 0.20 (4.4) 0.20 (4.4)
(Nad)
2.5 6.8 5.7-6.0 1,000 600 260 6,200 0.21 (4.6) 0.22 (4.8)
(NaCl)
g 2.6 6.2 5.1-4.6 1.000 1,000 190 4.100 0.12 (2.6) 0.12 (2.6)
(NaCl)
4 2.6 (.8 5.9-6.4 3.000 3,000 660 8,060 0.19 (4.2) 0.18 (4.0)
(NaCl)
6 2.6 6.4 6.0-6.8 1.000 1,000 275 6.000 0.10 (2.2) 0.10 (2.2)
(NaCl)
S.0 6.2 6.2-6.7 1.000 1.000 110 5.600 0.13 (2.8) 0.14 (8.1)
(MkSO.) (MbSO.)
* A suspension of the resins in feed water was adjusted to this pH value by addition of acid before
fillincr the column
•• Data with resin.
in parentheses are in units of kilograms of calcium carbonate per cubic foot.

These experiments serve only to demon After completion of a final regeneration


strate that the process works in the labora- cycle in the series 6 experiments, the resins,
lory; many more experiments are required already loaded with magnesium ions, were
(o ascertain the optimum pH values and treated again at 80°C with a solution con
resin ratios for operation under different taining 800 ppm NaCl and 200 ppm MgSCv
conditions, and to permit rigorous com After a further adsorption (about 20°C)
parison of the results. and regeneration (80°C) cycle with the
Better results could be obtained by using same feed solution, a second pair of adsorp
a split elution technique in which only tion and regeneration cycles was com
the most concentrated effluent would be pleted. The results of the latter cycles,
rejected and the remaining less concentrated given in Figure 50, show that both sodium
fractions from the regeneration cycle would and magnesium ions arc adsorbed at the
be retained for use in the next cycle. beginning of the adsorption cycle. As more
Regeneration would be completed with a magnesium ions enter the feed solution,
volume of hot product or feed water equal the sodium ions that were initially adsorbed
to that rejected as the most concentrated are replaced by magnesium ions. Thus
effluent. A similar technique could be ap softening may be combined with demin-
plied to the adsorption stage. erali/ation (ref. 12) .

RATES OF ADSORPTION
Slow rate of reaction is the principal hydrogen ions is very small in a solution at
practical barrier to the use of mixed beds about pH 6. It is known that the rate of
of weak-acid and weak-base resins, but reaction of carboxylic acid resins increases
detailed kinetic studies are not available. with their acidity (ref. 8) .
It is known, from investigations of the Rate studies for mixtures of "De-Acidite
kinetics of the sodium-hydrogen exchange G" and "Zeo-Karb 226" with different
reaction in carboxylic acid resins in solu particle diameters show that the rate of
tions of sodium ion concentration from reaction increases considerably with a de
0.01 to 1.0N, that the rate of exchange is crease in particle size. Microbeads with
independent of the concentration of sodium diameters of 5 to 20 microns are currently
ions and varies inversely with the square being studied, and it has been found that
of the diameter of the resin bead (ref. 7) . the degTee of flocculation of the microbead
It seems probable therefore that the rate mixed bed has a considerable influence on
of reaction of the "Sirotherm" mixed bed the rate of exchange. The degree of cross-
will be determined by the rate of transfer linkage of the resins is also important. The
of protons between the resins and that this results so far obtained suggest that satisfac
rate is low because the concentration of tory rales of exchange will most likely be

125
obtained with microbeadv weak-acid snake, but the effective capacities
We have shown that fast rates of ex of these resins have so far been consider
change may be obtained with ion-retarda ably inferior to those of mixed individual
tion resins with a weak-base cage and a resins (ref. 9) .

126
SOME PROCESS CONSIDERATIONS
Our experimental study of the "Siro- There are insufficient data for making
therm" process has so far been confined al reliable estimates of the size of such a
most exclusively to a study of equilibrium plant, but the following hypothetical exam
conditions with the objective of defining ple shows the likely order of magnitude
resin specifications and optimum conditions involved for a plant producing 240,000 U.S.
for operation. The probable necessity of us gpd of water with a salinity of 500 ppm
ing microbeads to obtain satisfactory rates from a feed solution of 1,000 ppm. Our
of adsorption and of recovering heat from results suggest that if the regenerant ef
the bed means that the process cannot be fluent concentration were 4,000 ppm, it
operated with the procedures customary in ought to be possible to obtain about 17
ion-exchange technology. Although we have bed volumes of product per unit volume
not yet worked on process aspects, we have of resin, since this would only assume an
given the matter considerable thought. Our effective capacity (0.15 meq/ml) well below
tentative views on this subject will now be that attainable theoretically. Rate studies
presented. tentatively suggest that a complete multi
Beds of resin several feet deep are not stage adsorption and regeneration cycle
practical if microbeads are used to obtain might be completed within 6 minutes, in
satisfactory rates of adsorption, as the flow which case 8 cubic feet of resin would be
rate is too low owing to the high pressure required. If the resin were retained in a
drop over the bed. It is also difficult to layer 0.5 inch thick, a filter area of only
recover heat efficiently from a deep static 190 square feet would suffice.
bed of resin without destroying the concen An alternative procedure may be desir
tration gradient within the resin bed. able for plants treating more than one
One simple method for operating the mgd of water. One possibility is a series of
process on a small scale might be to retain mixer-filter units arranged countercurrently,
the microresins as a layer about 0.25 to I as shown in Figure 51. which warrants in
inch thick between the leaves of a plate vestigation. A mixture of "De-Acidite G"
and frame filter press. The individual units and "Zeo-Karb 226" with a particle size
in such a filter are in parallel so that the range of approximately 10 to 20 microns is
pressure drop over the bed will not be highly flocculated. Fresh resin filters at the
excessively high. The resin bed would func rate of, 8 gals/sq ft/min under a vacuum of
tion as only one reaction stage, but multi 20 inches of mercury and yields a cake one
stage countercurrent conditions could be quarter of an inch thick without cracking.
simulated by employing a split elution and If this filtration rate could be maintained,
split feed technique. Since the rate of ex the largest disc filter available, with 12
change at 80°C is at least ten times that at discs 12 feet 6 inches in diameter, would
20°C. it would be possible to regenerate, filter a flow of 10 mgd. In this flowsheet,
in the time required for performing a feed water is used for regeneration, but,
single stage of adsorption, with a consider depending on economic circumstances, prod
able number of successive equilibrations in uct water or a blend of both feed and
volving fractions collected from the preced product water could be used. The upper
ing regeneration cycle. As the quantity of limit to the salinity of the water that
resin used is small, the cycle time will be could be treated might be extended by
a matter of only a few minutes, so that the incorporating a wash cycle on the filters in
volumes of the different fractions to be the regeneration cycle, so that void water is
stored for use in the next cycle will be displaced by the solution from the next
small and could be retained in radial com stage of the process receiving the resin.
partments within a single tank. It should Efficient heat recovery is possible if the
therefore be practical to operate the process resins are transferred between the hot and
with several adsorption stages but with cold stages with similar flows of solution
many more regeneration stages. Since there so that the flows have the same heat ca
will not be a concentration gradient of any pacity on either side of the heat exchangers.
magnitude within the resin bed as it oper Success with the continuous process would
ates as a single stage, heat could be with require resins with a high degree of me
drawn or added by circulating a solution of chanical stability, but preliminary experi
appropriate composition through the resin
bed and a heat exchanger. ments are encouraging. A mixed bed of
microbeads of "De-Acidite G"4 and "Zeo-
• The water regain was 0.7. Karb 226",#, with particle diameters of
•* This ream contains i% per cent divinyl ben- about 10 to 20 microns, has been subjected
lene. but lower crosslinking is preferred.
127
to 6300 successive cold (32°C) and hot with particle diameters exceeding 20 mi
(about 70°C) cycles with changes of solu crons. A slurry of the separate resin beads
tion at each adsorption and desorption has also been subjected to violent agitation
cycle. A photomicrograph of the resins after for a month at room temperature by an
6,500 cycles given in Figure 52 shows that agitator designed for maximum shearing
there has been no major rupture of the stress. There was no visible cracking of any
resin beads. It was observed that the only of the minus 20 micron beads.
beads which had cracked were the few

O in
tf) i- CL
Ul < > "J 22 I
O a. . tr to <r o o i- in
< WO UJ z < Q- o or h
I- Zo tr i- tu > < t- (To UJ O
<S) uJo UJ f *- o X if) OO
, CD oo o < < O u , w ex
o tu UJ UJ X Z
CD X x tr uj e58 O
M
h
U
z> 5
q »
O ©
rpS- CC
CL w
O
<
H
5/5

is
u
5/5 O
2*
O Cm
P.

2M
O
U
O
^—
6/5
06'
O

H
w
w
X
C/5

z
UJ Q
3 UJ
-I UJ
U. Ll 0
U.
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128
FIGURE 52. PHOTOGRAPH OF MICROBEADS OF "ZEO-KARB
226" (STAINED DARK WITH FUSCHIN) AND "DE-ACIDITE G",
10 TO 20 MICRONS, AFTER 6,500 COLD ADSORPTION AND
HOT DESORPTION CYCLES.

It is well-known that colloids adsorbed ground waters which usually contain little
on the surface of ion-exchange resins can sediment, organic matter, or oxygen. Pre
reduce the rate of exchange substantially. treatment with a (macroporous) macro-
Colloids might enter the system in the feed reticular organic trap resin and a polishing
water, from which they could be removed filter might be all that is required. It is
by pretreatment. They might also arise in advisable to prevent aeration of the water
the continuous process from a gradual attri until after treatment in order to avoid
tion of the resin, in which case it would precipitation of iron and manganese; the
be necessary to remove them by backwash low oxygen content will favor resin stabil
ing, or by chemically treating a small side ity. Acidification of the feed water to about
stream of the resin flow. pH 6 will be necessary and the optimum
The heat requirements of the process are operating pH value will need to be main
potentially low, since the energy required tained by insuring that the number of
for performing thermodynamic work is protons entering the plant equals the
negligible, compared with the sensible heat number leaving it.
required for heating the solution and resins, In most waters, acidification will result
and sensible heat can be recovered to an in the liberation of free carbon dioxide
extent dictated solely by economics. Heat which should be retained in the water in
recovery will be easier in the continuous the adsorption stage in order to dissolve
than in the batch version of the process. any calcium carbonate that might tend to
Cheap and efficient heat recovery is likely deposit during regeneration. Acidification
to require the development of novel heat can be achieved by the addition of sulphuric
transfer techniques, which use cheaply de acid, carbon dioxide, or sulphurous acid.
rived interfaces, and becomes increasingly Flue gas from the heater in the plant
important as the desalination load increases. might provide an inexpensive source of the
If the process is to be used in an inte latter two acids, provided its use does not
grated municipal supply system, as described contaminate the water with organic matter
in Figure 32. it will be treating under which fouls the resins.

129
CONCLUSIONS
Proper integration of surface and under the process is reversible for monovalent and
ground water supplies, coupled with the divalent ions, and that the resins have
use of a demineralization process to main adequate thermal stability in the absence of
tain the salinity balance of the system, pro oxygen. It has also been shown that a multi
vides a feasible long-term approach to stage system with thermal regeneration can
maintaining water quality in an arid region produce water of good quality from pure
at low cost. Low cost demineralization for salt solutions, with an adequately concen
this purpose might best be achieved by the trated effluent to meet the requirements of
development of an ion-exchange process a practical process. The results suggest the
with thermal regeneration of the adsorbent. possibility of operating with microbeads to
It has been conclusively demonstrated in obtain satisfactory rates of reaction. It has
principle that thermal regeneration of a yet to be shown that the process can be
mixture of ion-exchange resins of the weak operated with a resin life of at least 10,000
electrolyte type is feasible and the condi cycles. An experimental study of the factors
tions for maximum thermal effect have been determining resin life will be required.
defined. Equilibrium studies make it pos The main deficiency of existing homo-
sible to write the following specifications functional amine resins is their low total
for the ideal "Sirotherm" resins: capacity. It would be valuable to have a
(11 The acid and base resins should be homofunctional resin of adequate stability
homofunctional, and the overlap of their with the capacity of the heterofunctional
titration curves, determined at a given ionic resin, "Duolite A-30T", whose capacity is
twice that of the present homofunctional
strength and two given temperatures, should amine resins.
be as large as possible. There is room for considerable improve
(2) Maximum thermal reduction of the ment in the properties of carboxylic acid
acidity and basicity of the respective resins resins, as their titration curves show that
is desired. they are heterofunctional and lack good
(3) The position of the titration curves thermal effects, but such improvements will
of the acid and base resins with respect to be difficult to make at low cost. Existing
the pH axis should alter as little as possible resins have excellent capacities and stabili
with changes in ionic strength. ties and are potentially cheap as they can
(4) The resins must be stable at 80° to be made, in fewer stages and from cheaper
90-C. intermediates than polystyrene amine resins.
(5) The total exchange capacity should The simplest avenue for improvement may
be as high as possible. therefore be to seek means for reducing
Our experiments have demonstrated that their cost.

APPLICATION OF THE PROCESS


A useful feature of the "Sirotherm" proc with concentrations of at least 3,000 ppm.
ess is its ability to soften and demineralize There is no doubt that the process will
simultaneously. In many waters, removal of become increasingly attractive with reduc
the hardness salts alone would suffice to tions in the salinities of the feed and prod
prevent the accumulation of salinity within uct waters, and in this respect it differs from
a regional supply system. Since the effluent electrodialysis and reverse osmosis.
from the process (when operating on a The lowest practical salinity of the prod
softening cycle) will consist mainly of uct water from electrodialysis is 350 to 500
divalent ions, it may be of value in arid ppm. as the electrical resistance of the cells
regions for the displacement of sodium becomes excessively high at lower concen
from alkaline soils in soil reclamation trations. There may, therefore, be merit in
projects. using electrodialysis to reduce the salinity
Until engineering feasibility is established, of sea water or highly brackish waters to
and economic data become available from a level such that these waters could l>e fed
a pilot plant operation, it will not be pos to a "Sirotherm" unit. Haven's process of
sible to define the maximum salinity of the reverse osmosis, and possibly other similar
feed water likely to be treated in economic processes, operate in two stages (rcf. 10) .
competition with other processes, although In the first, the salinity of sea water is
our laboratory experiments show that it is reduced from 35,000 ppm to about 2.000
certainly technically feasible to treat waters ppm. This product is an ideal feed for the
"Sirotherm" process, as colloids have pre ment of the principles outlined above, which
sumably been completely removed. It would show for the first time that it is possible
be possible to utilize essentially all the fuel to use heat to perform reversible work at
energy of a heat engine for desalination by an adsorbent interface. As discussed else
combining the "Sirotherm" process with where (ref. 1) , a process which can com
electrodialysis or reverse osmosis, since most bine the utilization of the cheaply derived
of the energy of the fuel that is not con interface of an adsorbent with that of low-
verted to mechanical or electrical energy grade heat, the cheapest available energy
for use in the latter processes would be source, has excellent long-term prospects
available as heat energy from the cooling for achieving low demineralization costs.
system at a suitable temperature for Furthermore, if the solar pond development
use in a "Sirotherm" unit. Thus electricity in Israel (ref. II) becomes operational, it
need not necessarily be a byproduct of will offer the attractive long-term prospect
efficient sea water desalination of performing a cheap demineralization op
These possibilities present a major chal eration in arid regions by the use of solar
lenge for the inventive use and develop energy.

ACKNOWLEDGEMENTS
We are indebted to many people and Henry York, Pty., Ltd., Melbourne, for
firms for assistance with the "Sirotherm" samples of "Lutonal" polymers and "Lewa-
project: to Union Carbide Australia for tit" resins; to Gardinol Chemical Co.
sponsorship of the project and for the sup (A/asia) Pty., Ltd., for samples of acrylic
ply of some monomer chemicals; to the monomers; and to Dr. K. VV. Zimmermann
Permutit Company, Ltd., London, for for performing microanalyses of the resins.
samples of their ion-exchange resins and for We are also grateful to Messrs. D. Lawrie
preparing microbead resins to our specifica and N. Blesing of the Australian Mineral
tions: to the Dow Chemical Company, the Development Laboratories, Adelaide, who
Rohm and Haas Company, and the Western assisted with some aspects of the project
Division of Diamond Alkali, U.S.A., for under a C.S.I.R.O. development contract.
samples of their ion-exchange resins; to

REFERENCES
1. Weiss, D. E.; Bolto, B. A.: McNeill, R.; 6. Weiss. D. E.; Bolto, B. A.; McNeill. R.:
Macpherson, A. S.: Siudak, R.; Swinton, Macpherson, A. S.; Siudak, R.: Swinton.
E. A.: Willis, D.: Part I submitted to E. A.; Willis, D.: Aust. J. Chem., Part
the Institution of Engineers, Australia, IV submitted for publication.
for publication. 7. Conway. D. E.; Green, J. H. S.; Reich
2. Report of the IJ.S.-Israel Desalting and enberg, D.: Trans. Farad. Soc. no. 50
Power Team, (Oct. 1964) , U.S. Dept. (1964) p. 511.
of the Interior. 8. Kunin, R.; Vassiliou. B.: lnd. Eng.
3. Weiss. D. E.; Bolto, B. A.; McNeill, R.; Chem., "Process design and develop
Macpherson, A. S.; Siudak. R.; Swinton. ment" no. S (1964) p. 404.
E. A.; Willis, D.: Aust. J. Chem., Part 9. Unpublished work.
II submitted for publication. 10. Water and Water Eng. (1964) p. 414.
4. Weiss. D. E.; Bolto, B. A.; McNeill. R.; 11. Tabor, H.: J. Solar Energy, no. 7
Macpherson, A. S.: Siudak, R.; Swinton, (1961) p. 189.
E. A.; Willis, D.: Aust. J. Chem., Part 12. Weiss, D. E.: Bolto, B. A.; McNeill, R.:
III submitted for publication. Macpherson, A. S.; Siudak, R.; Swinton,
5. Kunin, R.; Fisher. S.: /. Phys. Chem.. E. A.; Willis, D.: Aust. J. Chem., Part
no. 66 (1962) p. 2275. V submitted for publication.

SUMMARY OF DISCUSSION
It was stated that water in California con on the market which will remove these ions
tains both boron and fluorides, and it was but that their removal by the process de
asked how the process presented in this scribed in this paper is inadequate.
paper would remove these ions. The reply A question was asked concerning the
stated that there is an ion-exchange resin energy requirement of the process pre-
sented. The author stated that this re tory. A high energy recovery in the process
quirement must be evaluated on a larger is expected; however, heat transfer rates
scale—possibly at the pilot plant level- must first be determined.
since it cannot be determined in the labora

Procède "Sirotherm" de Déminéra

lisation — Procède Par Echange

D'Ions Avec Regeneration

Thermique

D. E. Weiss, B. A. Bolto, R. McNeill, A. S. Macpherson,


R. Siudak, £. A. Swinton, et D. Willis

Australie

Du fait que les adductions d'eau muni charge de déminéralisation se trouverait


cipales deviennent de plus en plus coûteuses ainsi réduite. L'application de la déminé
et que la qualité se détériore en raison de ralisation au contrôle de la salinité est
la ré-utilisation extensive, il existe quatre digne d'une attention étendue, car le retrait
étapes successives logiques pour l'aménage de petites quantités de salinité pour 10
ment des ressources hydrauliques, en vue de cents par mille gallons (moins de $0,02
réduire les frais: par m') est plus vraisemblable, et est plus
1) Amélioration des méthodes de conser urgent, que ne l'est le traitement d'approvi
vation; sionnements fortement pollués comme l'eau
2) Récupération des effluents pour leur de mer. Ceci rendrait possible l'utilisation
ré-utilisation; complète des approvisionnements existants
3) Déminéralisation des eaux de qualité d'eau fluviale. Des considérations fonda
marginale qui sont trop salines pour mentales indiquent que le procédé le meil
l'usage général; leur marché dans ce but serait l'utilisation
4) Une fois que l'eau est utilisée d'une de résines échangeuses d'ions régénérées par
façon efficace, on doit utiliser des ad la chaleur plutôt que des produits chi
ductions coûteuses provenant de pipe miques.
lines de longue distance, ou de la Ce mémoire présente une étude de labo
déminéralisation de l'eau de mer ou ratoire montrant qu'un mélange de résines
des eaux fortement saumâtres. d'acide carboxylique et d'amine faiblement
Il se produit une accumulation de sels électrolytiques adsorbe le sel à la tempéra
minéraux lorsque l'eau des fleuves est ré ture ambiante et peut être régénéré avec
utilisée extensivement dans un climat aride. de l'eau d'alimentation ou de l'eau douce
Le contrôle régional de la salinité exige la à 80°C. Le chauffage désorbe le sel de la
séparation des eaux de drainage d'irriga couche mixte en réduisant la basicité de la
tion et des eaux fluviales et un procédé de résine à base faible. Jusqu'à maintenant les
déminéralisation bon marché pour retirer travaux ont porté principalement sur des
la salinité que s'accumule avec chaque études d'équilibre.
cycle d'utilisation urbaine ou industrielle. Les résines amines possèdent des combes
Celle-ci est généralement inférieure à 500 de titrage avec soit un plateau, soit une
ppm. Si la déminéralisation était appliquée pente; la pente de la courbe et la basicité
aux eaux souterraines proches, un espace de la résine peuvent varier considérable
serait ainsi créé qui pourrait être rechargé ment en modifiant la structure de la résine,
avec des surplus d'eau de bonne qualité mais- les résines d'acide carboxylique, dis
pendant les périodes pluvieuses, et la ponibles jusqu'ici, possèdent des courbes
de titrage inclinées. La différence dans la 1.000 ppm de NaCI a donné un produit
quantité de sel absorbé des solutions avec une concentration minimum de 230
froides et chaudes (capacité effective) est ppm, et un effluent avec une concentration
la plus grande pour une paire de résines de pointe de 4.800 ppm, en utilisant l'ali
dont les courbes de titrage, mesurées dans mentation à 80°C comme régénérateur. De
les solutions chaudes et froides, se super meilleurs résultats furent obtenus en se
posent autant que possible. L'augmentation servant d'un régénérateur contenant 500
de la proportion de la résine acide par ppm de NaCI. Une solution contenant
rapport à la résine basique augmente la 3.000 ppm de NaCI a été déminéralisée
quantité de sel pouvant être désorbé par avec succès. Une solution à 1.000 ppm de
chauffage, et pour chaque valeur de pH MqSO, a donné un produit avec une con
pour l'adsorption il existe un rapport centration minimum de 110 ppm et une
optimum des résines. Un changement dans concentration d'effluent de 5.500 ppm. Il a
la force ionique modifie la position rela été démontré que l'adoucissement pouvait se
tive des courbes de titrage et influence faire simultanément avec la déminéralisa
ainsi de façon marquée la capacité effective tion. Il est nécessaire d'effectuer d'autres
et les conditions de performance optimum. expériences en colonnes pour définir les
D'après les courbes de titrage, on peut conditions optimums de fonctionnement, si
tracer des graphiques montrant, en tant bien qu'une comparaison rigoureuse des ré
que fonction du pH, les capacités effectives sultats n'est pas encore justifiée.
approximatives des différentes combinaisons Des études utilisant des micro-perles avec
de résines estimées aux rapports optimums des diamètres d'environ 5 à 10 microns
des résines. Ces courbes sont utiles dans suggèrent que leur taux de réaction sera
des buts de sélection, car la sélection des acceptable pour un procédé pratique, mais
nombreuses combinaisons de résines dis les résultats concluants doivent attendre
ponibles exige d'effectuer des comparaisons l'issue des études en cours sur l'influence
à une force ionique donnée dans des condi de la floculation et de la réticulation. Les
tions optimums de pH et de rapport des études en colonnes classiques en discontinu
résines. Les courbes de titrage fournissent décrites ci-dessus sont la manière la plus
donc une méthode simple pour la caractéri- simple d'examiner en laboratoire le com
sation des différentes résines. portement d'un procédé à étages multiples,
Les expériences montrent que l'équilibre, mais une telle méthode ne serait pas utili
pour beaucoup de paires de résines, dépend sée en pratique. Sur une grande échelle,
d'une façon critique du pH et que, de il peut être possible d'exploiter le procédé
celles examinées jusqu'à maintenant, la dans des ensembles de filtres-mélangeurs
meilleure paire disponible commerciale disposés à contre-courant, car une couche
ment se compose de "De-Acidite G" et mixte floculée de micro-perles filtre rapide
"Zeo-Karb 226". Des études détaillées ont ment, et il n'y a aucun fendillement dé
été faites de cette paire de résines à tectable des micro-perles de 5 à 10 microns
environ 20 et 80°C, dans des solutions con après agitation vigoureuse dans 6.500 cycles
tenant 500, 1.000, 1.760, 3.000 et 5.000 ppm chauds et froids successifs. Il serait néces
de chlorure de calcium. La nature réversi saire de prévoir des moyens pour éliminer
ble de l'équilibre a été démontrée dans des les colloïdes. Une autre méthode, pour une
échantillons scellés sur 5.000 cycles chauds utilisation sur une plus petite échelle, serait
et froids pour les ions monovalents, et sur d'utiliser les résines dans un seul étage de
1.000 cycles pour les ions calcium, mag réaction à couche fixe fonctionnant dans
nésium et sulfate. Les résines sélectionnées un système cyclique intermittent et en
se sont avérées stables à 90"C dans des imitant les conditions de contre-courant
solutions ne contenant pratiquement pas par des techniques d'alimentation dédou
d'oxygène. Il nous reste encore à démontrer blée et d'élution. Avant de disposer de
que le procédé peut être utilisé avec une données d'installations pilotes, il n'est pas
vie utile des résines d'au moins 10.000 possible d'estimer quelle sera la concentra
cycles avec changement de la solution à tion maximum de l'alimentation pouvant
chaque cycle. être traitée d'une manière économique,
Les résultats suivants, avec des mélanges mais le coût augmentera avec l'accroisse
de "Zeo-Karb 226", SRC 44, et de "De- ment de la salinité de l'eau d'alimentation.
Acidite G", SRA 102 démontrent que l'effet Si une centrale thermique fournissait l'éner
thermique entre 20 et 80°C est suffisant gie pour la déminéralisation partielle de
pour l'accomplissement d'opérations utiles l'eau de mer, ou des eaux fortement sau-
de déminéralisation. Le traitement en co mâtres, par électrodialyse ou osmose inversée,
lonnes d'une eau d'alimentation contenant la chaleur d'échappement serait disponible

133
pour la régénération thermique d'un pro thermique pourrait ainsi être utilisée, il
cédé par échange d'ions pour achever la ne serait pas nécessaire de produire de
déminéralisation. Comme toute l'énergie l'électricité en tant que sous-produit.
d'entrée de combustible de la centrale

Опреснительный Процесс «Сайротерм» —

Ионообменный Процесс с Термической

Регенерацией

Д. Е. Вейсс, Б. А. Болто, Р. МакНейлл, А. С. Макферсон, Р. Сюдак,


Е. А. Суинтон и Д. Уиллис

Австралия

В то время как стоимость дополни ную нагрузку. Применение местного


тельного снабжения городов водой не опреснения в целях регулирования со-
прерывно возрастает, а ее качество лесодержания заслуживает всеобщего
ухудшается при широко применяемом внимания, так как удаление небольших
повторном использовании, существуют количеств соли вероятно можно до
четыре логических, следующих одна за стичь за 10 центов/ 1.000 галлонов, и
другой стадии водяного хозяйства для оно более срочно требуется, чем обра
снижения расходов. ботка сильно загрязненных источников,
(1) Улучшение методов консервации; как например морской воды. Это бы
(2) Регенерация сбросных вод для позволило полностью использовать су
повторного использования; ществующие речные ресурсы. Основ
(3) Опреснение вод маргинального ные соображения наводят на мысль,
качества, которые слишком со что наиболее дешевым процессом для
лоны для общего употребления; достижения этой цели является приме
(4) По эффективном использовании нение ионообменных смол, регенери
воды надо утилизировать отда руемых не химикалиями, а теплом.
ленные ресурсы с помощью до В этом докладе приводится лабора
рогостоящих трубопроводов или торное исследование, указывающее,
опреснять морские и сильно-со что смесь слабо-электролитных амино-
лоноватые воды. кислых и карбонокислых смол адсор
Когда в засушливых областях речная бирует соль при температуре окружа
вода усиленно и повторно использует ющей среды и может регенерировать
ся, то накапливаются неорганические ся с помощью исходной или опреснен
соли. Районные органы, наблюдающие ной воды при 80°С. Нагрев десорби-
за солесодержанием, требуют отделе рует соль из перемешиваемого слоя,
ния от реки идущих на орошение сбро уменьшая основность смолы слабого
сных вод с применением дешевого основания. Работа до настоящего вре
опреснительного процесса для удаления мени была преимущественно посвяще
из них соли, которая накапливается с на изучению равновесия.
каждым повторным муниципальным Кривые титрования аминовых смол
или промышленным циклом. Солесодер- либо плато-образны, либо наклонны.
жание обыкновенно не достигает 500 Форму кривой и основность смолы мо
мг./л. Если бы опреснялись, находя жно сильно изменить путем изменения
щиеся поблизости, подземные воды, то структуры смолы, но, у находящихся
создавалось бы пространство, которое сейчас в продаже смол карбоновой ки
в дождливые периоды снова бы запол слоты, кривые титрования наклонны.
нялось избыточными водами хорошего Самое большое различие в количествах
качества, уменьшая этим опреснитель адсорбированной соли из холодных и
134
горячих растворов (эффективная спо и сброс с максимальной концентрацией
собность) бывает у двух таких смол, 4.800 мг./л. пользуясь в качестве реге
кривые титрования которых, измерен нератора исходной водой при 80JC.
ные в горячих и холодных растворах, Лучшие результаты были получены с
как можно больше перекрываются. регенеративным раствором 500 мг./л.
Увеличение соотношения кислоты к хлористого натрия. Удачно опреснялся
основной смоле увеличивает количе рассол с содержанием 3.000 мг./л. хло
ство соли, которое может десорбиро- ристого натрия. Раствор 1.000 мг./л.
ваться посредством нагрева и при каж MgS04 давал продукт с минимальной
дом отдельном значении pH для ад концентрацией ПО мг./л. и концентра
сорбции существует оптимальное со цией сбросного раствора 5.500 мг./л.
отношение смол. Изменение ионной Было установлено, что одновременно
силы меняет относительное положение с опреснением можно достичь и смяг
кривых титрования и тем самым замет чения воды. Для определения оптималь
но влияет на эффективную способность ных рабочих условий потребуются
и на условия оптимальной характери дальнейшие опыты с применением ко
стики. Из кривых титрования можно лонок, а потому еще нельзя вынести
получить диаграммы, где приблизитель заключение в связи с полученными ре
ные эффективные способности различ зультатами.
ных комбинаций смол, при их опти Исследования с микро-шариками, ди
мальных соотношениях, могут быть аметром около 5-10 микронов, дают
представлены, как функции pH. Такие основание полагать, что скорость ре
кривые ценны для производства отбо акции будет приемлемой для практи
ра, так как ввиду наличия многих ком ческих целей, но с окончательными вы
бинаций смол приходится делать срав водами придется обождать, пока не
нения при заданной ионной силе и оп окончено ведущееся сейчас изучение
тимальных условиях pH и соотношения влияния флоккуляции и поперечной
смол. Поэтому кривые титрования об связи. Вышеописанные исследования,
легчают возможность составления ха производимые с помощью обычных
рактеристик отдельных смол. колонок периодического действия, яв
Опыты показывают, что равновесие ляются самым простым лабораторным
многих пар смол целиком зависит от методом для ознакомления с ходом
pH и, что среди изученных и находя многоступенчатого процесса, но такие
щихся в продаже, наилучшими сейчас приемы неприменимы на практике. На
являются "De-Acidite G" и "Zeo-Karb работе большого масштаба может ока
226". Эта пара смол была детально ис заться возможным проводить процесс
следована при 20-80°С и в растворах, в противоточно установленных ме-
содержавших 500, 1.000, 1.760, 3.000 и шально-фильтрационных агрегатах, так
5.000 мг./л. хлорида кальция. Обрати как флоккирующий перемешиваемый
мая сущность равновесия была нагляд слой микро-шариков быстро фильтрует
но показана на закрытых образцах при и не было замечено их растрескивания
более, чем 5.000 горячих и холодных после сильного перемешивания в те
циклов с моновалентными ионами, и чение 6.500, следовавших один за дру
при более, чем 1.000 циклов с ионами гим, горячих и холодных циклов. При
кальция, магния и сульфатов. При дется принять меры для удаления кол
90°С выбранные смолы оказались ста лоидов. Альтернативным методом ма
бильными в растворах, почти не содер лого масштаба могло бы быть приме
жавших кислорода. Но нам все же при нение смолы в одной стадии реакции
дется показать, что процесс сможет с неподвижным слоем, входящей в
функционировать при минимальном циклическую систему периодического
сроке службы смолы в 10.000 циклов и действия, где условия противотока мо
перемене раствора при каждом цикле. гут симулироваться разделенным (на
Нижеследующие результаты, полу двое) потоком исходной воды и элюи-
ченные со смесями "Zeo-Karb 226", рованием. Пока не получены данные с
SRC44 и "De-Acidite G", SRAI02, на помощью пробной установки, невоз
глядно показывают, что термический можно подсчитать максимальную кон
эффект между 20°С и 80°С подходит центрацию исходной воды, поддающу
для производства важной опреснитель юся экономичной обработке, но ее сто
ной работы. Обработка в колонке ис имость будет возрастать с увеличением
ходной воды, содержавшей 1.000 мг./л. солесодержания. Если тепловая маши
хлористого натрия, давала продукт с на будет давать энергию для частич
минимальной концентрацией 230 мг./л. ного опреснения морской или сильно-
135
солоноватой воды методом электроди ком использовано горючее, израсходо
ализа или обратного осмоса, то для за ванное тепловой машиной, и отпадает
вершения опреснения можно будет ис надобность производить электрическую
пользовать сбросное тепло для терми энергию, являющуюся побочным про
ческой регенерации ионообменного дуктом.
процесса. В этом случае будет цели

El Proceso de Desmineralizacion

"Sirotherm" un Proceso de Inter

cambio Iónico con Regeneración

Térmica

D. £. Weiss, В. A. Boite, R. McNeill, A. S. Macpherson, R. Siudak,


E. A. Swinton y D. Willis

Australia

A medida que incrementos de suministro control de salinidad justifica amplia aten


municipal de agua se encarecen progresiva ción dado que la eliminación de pequeños
mente y la calidad sufre deterioro debido grados de salinidad de logra, probable
a un reuso más generalizado, hay cuatro mente, por 10 centavos cada rail galones y
etapas en la administración de aguas para es más urgentemente necesaria que el trata
reducir costos: miento de aguas de fuentes altamente im
1) Mejora de los métodos de conversación. puras tales como el agua de mar. Ello
2) Recuperación de efluentes para reuso. podría hacer posible una completa utiliza
S) Desmineralización de aguas de calidad ción de las fuentes existentes en los ríos.
marginal por su alta salinidad para Razones fundamentales sugieren que el pro
uso general. ceso más económico para esta finalidad
4) Una vez logrado un uso eficiente del podría basarse en resinas permutadoras de
caudal disponible, se deberán usar iones regeneradas por calor más que por
fuentes de abastecimiento más caras, medios químicos.
por bombeo mediante tuberías muy Este trabajo presenta una investigación de
extensas o por desalinización de agua laboratorio mostrando que una mezcla de
de mar o aguas muy salobres. amina débilmente electrolítica y resina de
Cuando agua de río es reusada extensiva ácido carboxílico absorbe sales a tempera
mente en climas áridos se produce una tura ambiente y puede ser regenerada con
acumulación de sales inorgánicas. Un con aguas de alimentación o aguas resultado del
trol regional de salinidad requiere la sepa proceso a 80°C. El calor provoca desabsor
ración de aguas de drenaje de irrigación de ción de sales de la mezcla por reducción
las del río y un proceso económico de des de la alcalinidad de la resina débilmente
mineralización para eliminar la salinidad básica. Hasta la fecha los trabajos se han
que se acumula en cada ciclo de uso muni limitado mayormente a estudios de equi
cipal o industrial. Salinidad ésta, que es librio.
generalmente menor de 500 ppm. Si se des- Las resinas amínicas poseen curvas de
mineralizaran aguas subterráneas cercanas, valoración de forma horizontal o inclinada;
podrían establecerse depósitos que podrían la forma de la curva y la basicidad de la
ser rellenados con excedentes de aguas de resina pueden ser variadas considerable
buena calidad en tiempos de abundancia, mente por alteración de la estructura de la
reduciéndose de este modo el volumen que resina, pero las resinas de ácido carboxílico,
debe ser producido por desmineralización. disponibles hasta ahora, tienen curvas de
l.i utilización de la desmineralización en el valoración inclinidas. La diferencia en la

I 36
cantidad de sal absorbida de soluciones como regenerante. Mejores resultados fueron
Was y calientes (capacidad efectiva) es obtenidos mediante el uso de una solución
mayor para un par de resinas cuyas curvas regeneradora conteniendo 500 ppm de NaCl.
de valoración, medidas en soluciones frías y Una solución conteniendo 5000 ppm de
calientes, se sobre-montan tanto como es NaCl ha sido desmineralizada con éxito.
posible. Incrementando la relación de resina Una solución de MgSO, con concentración
acida a la básica, incrementa la cantidad de 1000 ppm de un producto con una con
de sal que puede ser desabsorbida por ca centración de 110 ppm y un efluente de
lentamiento y para cada valor de pH de 5500 ppm. Se ha demostrado que simultá
absorción hay una proporción de resinas neamente con la desmineralización puede
óptima. Un cambio en la fuerza iónica lograrse ablandamiento. Se requieren más
altera la posición relativa de las curvas de experimentos en columna para determinar
valoración y de ese modo influye marcada las condiciones óptimas de operación, de
mente en la capacidad efectiva y en las manera que no se justifican por el momen
condiciones para un trabajo óptimo. De las to comparaciones rigurosas.
curvas de valoración pueden derivarse gráfi Estudios usando microperlas con diáme
cas que muestran las capacidades efectivas tros de aproximadamente 5-10 micrones
aproximadas de diferentes combinaciones de sugieren que su velocidad de reacción será
resinas como función del pH determinadas aceptable para un proceso práctico, pero
a proporciones óptimas de resinas. Tales para alcanzar resultados concluyentes, de
curvas son valiosas como guias de selección berá esperarse los resultados de los estudios
dado que la selección entre distintas com en proceso sobre la influencia de la flocula-
binaciones de resinas disponibles requiere ción y enlaces cruzados. Los estudios con
comparaciones que deben ser hechas a una columna convencional descriptor consti
fuerza iónica dada, bajo condiciones ópti tuyen el medio de laboratorio más simple
mas de pH y de proporción de resinas. Las para examinar el comportamiento de un
curvas de valoración, por lo tanto, sumini proceso de múltiples etapas pero tales pro
stran un método simple para caracterizar cedimientos no se usarían en la práctica.
Tesinas individuales. A escala mayor puede ser posible operar
Los experimentos demuestran que el el proceso mediante mezcladores-filtros dis
equilibrio para muchos pares de resinas puestos en contracorriente dado que un
depende del pH y que, de aquéllas exami lecho floculado de microperlas filtra rápida
nadas hasta el presente, el mejor par co- mente y no hay rompimiento observable de
mercialmente producido consiste de "De- las microperlas de 5 a 10 micrones después
Acidite G" y "Zeo-Karb 226". Se han hecho de vigorosas agitaciones en 6.500 ciclos ca
estudios detallados de este par de resinas lientes y fríos sucesivos. Sería necesario
a aproximadamente 20 y 80°C en soluciones contar con medios para remover los co
conteniendo 500, 1000. 1760 y 5000 ppm de loides. Un procedimiento alternativo para
cloruro de calcio. La naturaleza reversible empleo en pequeña escala podría ser el
del equilibrio ha sido demostrada en usar resina en una sola etapa de reacción
muestras selladas sobre más de 5000 ciclos en un lecho fijo, funcionando en un sistema
en frío y caliente para iones monovalentes de partidas cíclicas y simulando condiciones
y sobre 1000 ciclos para iones de calcio, de contracorriente mediante técnicas com
magnesio y sulfato. Las resinas seleccionadas binadas de alimentación y elución. Hasta
han demostrado ser estables a 90°C en solu contar condatos de planta piloto, no es
ciones casi exentas de oxigeno. Nosotros posible estimar la concentración máxima
tenemos aún que demostrar que el proceso del agua de alimentación que podría ser
puede ser operado con una resina cuya vida tratada económicamente pero el costo
sea de por lo menos 10.000 ciclos con aumentará al aumentar la salinidad. Si un
cambio de solución en cada ciclo. motor térmico proporciona fuerza para la
Los siguientes resultados con mezclas de desmineralización parcial de agua de mar o
"Zeo-Karb 226", SRC 44 y "De-Acidite G", aguas muy salobres, por electrodiálisis u
SRA 102, demuestran que el efecto térmico osmosis invertida, el calor de escape podría
entre 20 y 80°C es adecuado para la efi ser usado para la etapa de regeneración
ciencia de operaciones de desmineralización. térmica de un proceso de intercambio iónico
Tratamiento de columna con agua de ali para completar la desmineralización. Dado
mentación conteniendo 1000 ppm de NaCl que todo el insumo de combustible del
da lugar a un producto con una concentra motor térmico podría entonces ser usado,
ción minima de 230 ppm y un efluente con no sería necesario producir electricidad
una concentración máxima de 4800 ppm, como subproducto.
usando el agua de alimentación a 80°C

1S7
An Appraisal of Scale Control

Methods at the O.S.W. Flash

Evaporator Plant in San Diego,

California

Stewart Mulford, Julius Glater, J. W. McCutchan

United States of America

INTRODUCTION
The reliability of large-sized land-based This also results ultimately in an increase
distillation equipment has been well estab in the ratio of energy input to product. In
lished during the past decade. It would either case there is a strong economic in
appear that distillation, especially the multi centive to prevent the deposits from becom
stage flash process, is presently the best ing very thick, or better yet, to completely
developed method for application to large- prevent their forming. As an illustration of
scale demineralization of saline waters, es these effects, deposits of scale and organic
pecially those of high salinity. Feasibility sludge which occurred in the brine heater
studies are currently underway for nuclear and condenser
i tubes of the Office of Saline
powered plants with capacities on the order Water Demonstration Plant in San Diego,
of 50 to 150 mgd. California, which were barely detectable by
The success of flash distillation arises from observation of he surfaces, were neverthe
inherent mechanical simplicity of design less sufficient to cause an increase in the
and comparatively high resistance of equip specific fuel consumption of the plant in
ment to scale formation. This is due, in the order of 10 per cent.
part, to the separation of evaporating and Although flash distillation appears favor
heating functions in this type of plant. One able from a scale point of view, measures
of the most important economic obstacles must still be taken to restrict the accumula
to low cost distilled water is the accumula tion of these troublesome mineral deposits.
tion of mineral scale. Scale deposits can In this paper, we shall report on a series of
have two important effects in an evapora experiments performed with a commercial
tion apparatus. First, scale on heat transfer size 36-stage flash evaporator of one mgd
surfaces offers a resistance to the flow of capacity. This water conversion plant, lo
heat which can be of the same order of cated in San Diego, California, was built
magnitude as the other major resistances in and operated under the auspices of the
the thermal circuit. The lower the original Office of Saline Water Demonstration Plant
"clean surface" resistance is, the less the Program in cooperation with the California
amount of scale required to produce a Department of Water Resources, and was
noticeable effect. The effect of increasing "on stream" over a period of about twenty-
the resistance to heat transfer is usually to four months. In March of 1964, the plant
increase the ratio of energy input to product was dismantled and shipped to the U.S.
from the apparatus. Second, scale deposits Naval Base at Guantanamo Bay, Cuba. This
can accumulate in pipelines, orifices, and experimental program had two basic objec
other flow passages to the extent that the tives. First, we were interested in evaluating
flow of process fluids is seriously impeded. current methods of alkaline scale control.
139
Second, we wished to study the performance accumulation because of certain unique de
of this equipment at elevated temperatures sign features of the flash system. The effects
and salinities where calcium sulfate scale of these features on plant performance will
usually presents a problem. The San Diego be discussed later.
plant showed excellent resistance to scale

SCALE FORMATION AND CONTROL


At this point we would like to review deposited on a metal surface, calcium sul
briefly the chemistry of scale formation, fate produces a hard tenacious coating
commenting on current practices in scale which is difficult to remove mechanically.
control. The vast literature on this subject Whereas alkaline scale is easily controlled
goes back over one hundred years and is by chemical additives and can be removed
often confused and controversial. Silver (ref. with acid, the only proven method for pre
1) emphasized the importance of scale con venting calcium sulfate scale is by control
trol in his statement, "The history of dis of evaporator operating conditions.
tillation is the history of control of scale All three varieties of calcium sulfate have
formation." Reviews of both old and cur been found in scales from saline water
rent literature have been presented by evaporation. Gypsum occurs only in low
Partridge (ref. 2) . Badger (ref. 3) . and temperature evaporators, since it become';
McCutchan and Glater (ref. 4) . a short-lived metastable phase above 99°F.
In an engineering sense, scale consists of The most often encountered scales consist
a mineral deposit of inorganic salts whose of hemihydrate, anhydrite, or a mixture of
solubilities decrease with increasing tem these forms. Langelier (ref. 5) was the first
perature. Scale deposited from sea water to define stability limits for hemihydrate
and most brackish waters is classified as and anhydrite in boiling sea water at 212T.
alkaline scale or calcium sulfate scale, de His work predicts hemihydrate formation
pending on the mechanism of formation. and offers a clear explanation for the pre
Alkaline scale results from thermal break cipitation of this compound in distillation
down of the bicarbonate ion found in all equipment operating at the atmospheric
natural waters. This process gives rise to boiling point. Although this solid hydrate
carbonate and hydroxide ions in the brine, is metastable above 99°F, it reaches equilib
producing insoluble precipitates with dis rium with dissolved ions more rapidly than
solved calcium and magnesium ions respec anhydrite. In supersaturated boiling brine
tively. The overall chemical mechanisms are solutions containing calcium and sulfate
summarized in Figure 53. The relative ions, hemihydrate l>egins to deposit almost
amounts of calcium carbonate and mag immediately and complete equilibrium with
nesium hydroxide deposited depend on the the solid phase is reached in about 2 hours.
temperature and rate of carbon dioxide evo Anhydrite is clearly the most stable phase
lution from evaporating brine. Alkaline above 99°F, but approximately 17 hours are
scale can. in fact, form in unconcentrated required before any transition of hemi
sea water as a result of heating alone: re hydrate to anhydrite occurs. Complete phase
lease of carbon dioxide is the onlv require transition is accomplished in about 40
ment. Calcium sulfate, on the other hand, hours. At 212°F, saturation with respect to
will not deposit until some critical concen hemihydrate occurs at a concentration fac
tration is reached at a given distillation tor of 3.1; for anhydrite the value is 1.5.
temperature. No chemical changes are in The latter figure is only hypothetical since
volved in this deposition process. You will in actual practice a residence time of 17
observe from Figure 54 that three different hours would be an unrealistic value in
crystalline modifications of calcium sulfate most distillation processes. Langelier's often
may exist in equilibrium with dissolved quoted threshold value of 3.1 has long been
calcium and sulfate ions. used as a guideline for the design of dis
Calcium sulfate encrustations pose a seri tillation equipment. It must be remembered,
ous problem in sea water distillation. Unlike however, that this value was derived from
alkaline scale, these deposits: (1) are in pure equilibrium considerations based on
soluble in most common laboratory rea bulk brine concentration. The effect of heat
gents: (2) cannot be controlled by simple transfer rate, local concentration effects, or
pH adjustment; and (3) present an es type of distillation process was not con
pecially serious problem at high tempera sidered in his studies. Although pure hemi
tures due to the steeply sloped inverted hydrate crystals are often found (as pre
solubility curves shown in Figure 55. Once dicted) in scale samples, Mcllhenny (ref. 6)
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WATERS.
SALINE

Mineral
Name Hemihydrate
Aragonite Anhydrite
Calcite Brucite
Gypsum

CaSO^-i^O CaSO^I^O
Compound
Mg(0H)2 CaSO,.
CaC03
has consistently identified anhydrite scale in Langelier's work was carried out at 140° and
high temperature effects at the Freeport and 212°F only. Since modern distillation equip
Roswell Office of Saline Water demonstra ment is designed to operate at 250° to
tion plants. The exact mechanism of an 275°F, there is a pressing need to extend
hydrite deposition is not clearly understood these equilibrium and kinetic studies to
and could not be predicted fom Langelier's higher temperatures.
stability diagrams (ref. 5) . Unfortunately, The equilibrium solubilities of anhydrite
and hemihydrale in pure water have been been extensively studied in the United
documented by several independent workers States and Japan (refs. 12, IS) and have
(refs. 2, 7) at temperatures between 212° l>cen successfully applied in a number of
and 400°F. Since calcium sulfate solubility chemical processing industries. Basically,
varies markedly with ionic strength, such these techniques involve the introduction
data cannot be applied directly to natural of small quantities of fine "seed" crystals
brines. Very little work has been carried into the hot brine. Suspended crystals with
out at temperatures above 212°F. Some large surface areas may thus compete with
recent studies by Marshall (ref. 8) and heat transfer surfaces in precipitation of
Power (ref. 9) , however, present high tem scale. The sludge thus formed remains sus
perature solubility data for calcium sulfate pended in the blowdown, leaving no residue
in pure sodium chloride solutions. MarshaH in the evaporator. A modification of this
hopes to use his data to make predictions of method, called the sludge recycle system,
calcium sulfate solubility in natural brine involves recirculating a small portion of
solutions of varying ionic composition. At blowdown into the makeup water. In this
present, there has been no experimental manner, seeds are generated in situ once
verification of his predictions. the distillation process is underway. Al
From an engineering viewpoint, the phase though the economics of seeding appear
diagram submitted by Standiford and Sinek attractive, no large-scale application has as
(ref. 10) is the only practical data which \et become operational. A unique, self-
has appeared to date. Although not rigor generating, seeding technique recently de
ously developed, the diagram shown in Fig scribed by Fisher and Cilbert (ref. 14) uses
ure 55 represents an attempt to predict a pilot plant multistage flash evaporator.
scaling limits in sea water up to 825°F. When acidified dearcated sea water is con
Work at the San Diego plant involved, centrated rapidly to a C F. between 5 and
among other things, a study of scale re K. a milkv slum of calcium sulfate crystals
sistance in a large flash evaporator at tem forms in the blowdown. Scale free operation
peratures up to 250°F. In these experiments, is realized at temperatures below 140°F.
our interest was focused on establishing the Between CF. 3 to 5. scale formed readily:
validity of the Standiford and Sinek curves above this concentration barrier, nucleation
for this plant. look place preferentially in the evaporating
brine. The slurry was not analyzed but
Control of scale is the key to low cost probably consisted of gypsum crystals (since
distilled water and presents a challenging the temperature approached the stable re
problem to both the chemist and the chemi gion for gypsum shown in Figure 55) . This
cal engineer. The most popular methods phenomenon mav also indicate a positive
of alkaline scale control are polyphosphate slope for the gvpsum solubility curve. Such
based additives and acid injection. Both an orientation would favor more precipita
methods arc effective and economical in tion at lower temperatures. The explanation
Hash evaporators. The first retards scale but for these results is unknown at this time,
does not completely inhibit it. The use of but the development is interesting and
polyphosphate additives is also limited to bears close scrutiny.
temperatures below 200°F. Hagcvap L.P.
(ref. 11), the leading proprietarv polyphos The reduction of calcium ion content in
phate formulation, was used successfully in saline waters by cation-exchange columns
the San Diego program. The second method has been studied extensivelv by the Dow
may give rise to some corrosion and re Chemical Company (ref. 15) . Good results
quires effective gas ejection equipment. De in the laboratory and pilot plant have led
tails of results with these methods will be to the installation of a large ion-exchange
presented later. system for the Office of Saline Water demon
stration plant at Roswell. Xew Nfexico. In
Calcium sulfate scale control is best ac spite of favorable predictions, this system
complished by operating outside the "un
stable region" of potential scale formation. has been plagued by numerous operational
The limit of this region undoubtcdlv varies problems and limitations. Anv method for
with the type of equipment used and dis economically reducing the concentration of
tilling conditions. F.lforts were directed to calcium ion. sulfate ion, or both in evap
ward finding a better definition of the orator feed water would permit higher
boundary of this critical region for a large temperature operation of distilling plants.
multistage flash evaporator. Other promis Until good low cost demineralization sys
ing methods for control of calcium sulfate tems can be developed, or seeding tech
scale are seeding and ion-exchange de- nology is further advanced, we are faced
mineralization. Seeding techniques have with the problem of better defining the
144
limits of temperature and concentration to this end that the experimental efforts at
factors permitting scale-free operation. It is the San Diego plant were directed.

EXPERIMENTS WITH ALKALINE SCALE CONTROL


The San Diego flash plant was the second chambers although this area is prone to
distillation unit built under the Office of corrosion and accumulation of silt or other
Saline Water demonstration plant program. suspended material. The San Diego plant
Active operation began in March 1962 and normally operated in a range of concentra
was terminated in March 1964, when the tion factors between 1-5 and 2.0, but in some
plant was dismantled and shipped to Guan- tests of short duration concentration factors
tanamo Bay during the Cuban water crisis. as high as 2.9 were achieved. Brine concen
Study and evaluation of two different meth tration was regulated by altering the por
ods of alkaline scale control were carried tion of blowdown recirculated through the
out during this period. Experiments were brine loop.
also performed to determine the effect of Initial runs at San Diego were carried out
temperature and brine concentration on at a maximum temperature of 200°F and a
deposition of calcium sulfate. The theory concentration factor of 1.5. Under these cir
and practice of multistage flash distillation cumstances, only alkaline scale formation is
have been discussed by Frankel (réf. 16) , anticipated. During the first 5,399 hours of
Silver (réf. 1) . Mulford (réf. 17) , and plant operation, scale was effectively con
Leitncr (réf. IR) . Specifications for the San trolled with Hagevap L.P. Hagcvap is a
Diego plant were prepared by the Fluor mixture of sodium polyphosphates, lignin
Corporation of Los Angeles and the final sulfonic acid derivatives, and various esters
design by Westinghouse Electric Company. of polyalkylene glycols. These ingredients
Design and operating data for this installa act synergist ically to prevent alkaline scale
tion have been described in several reports formation by a mechanism not clearly
(refs. 19, 20) . Ambient sea water passes understood since Hagevap is effective even
through the heat recovery section of the at very low concentrations (S to 5 ppm) .
evaporator where it picks up heat from The molar concentration of Hagevap in
condensing vapor. It then enters the steam gredients is only a small fraction of the
heated brine heater where the temperature molar concentration of scale-forming ions.
is raised to about 200°F under nonboiling Good results were obtained with Hagevap
conditions.^ Hot brine now enters the first but a slight decrease in output was noted.
of a series of 36 flashing chambers main This decrease, due to light scale deposits,
tained at progressively reduced pressures. In was reflected in a rise in pressure and tern
each chamber, a portion of steam is "flashed perature of steam supplied to the brine
off" and condensed, thereby reducing the heater and a fall in gain ratio." It is inter
pressure in the system and the temperature esting to note that thermal performance is
of the brine. This process is repeated 35 actually the most sensitive criterion of scale
more times until the discharge brine achieves formation. Deposits which drastically affect
a temperature of about 90°F and the pres heat transfer rates were often hardlv visible
sure in the final chamber reaches about 0.05 when the plant was shut down for cleaning
atm. The plant was designed to operate at purposes. During two long runs with Hage
a maximum temperature of 250°F and a vap (6 and 4 months) , a slow, steady de
brine discharge temperature of 90°F. Since terioration of performance was noted at a
scale-forming salts show inverted tempera rate of less than 5 per cent per month. After
ture solubility curves, the region of most shutdown, deposits were analyzed and found
severe potential scaling is at the exit of the to consist primarily of alkaline scale (i/j
brine heater which is the point of highest CaCO, and 2/¡ Mg (OH),) along with small
temperature in the brine loop. This was quantities of silica. The silica was believed
shown during plant shutdowns. In one test, to result from mechanical entrapment of
heavy scale was encountered in the last foot fine sand particles in the scale matrix.
of brine heater tubes and lighter scale At the close of the six-month Hagevap
throughout the rest of the heater length. run, the plant was shut down and com
Scale is rarely found in the flashing pletely descaled by an outside contractor.
Toward the end of the second run (4
* One of the distinguishing features of flash months} . an acid injection system was in
distillation is the fact that sufficient pressure is stalled. In addition to Hagevap, sulfuric
maintained throughout the brine heater to pre
vent boiling. acid was introduced for the last 168 hours
, ratio
••Gain . = lb distillate
тт-— of running time. This in situ descalinj;
lb steam
145
operation was apparently successful, as 56 summarizes thermal performance for the
shown by a return of thermal performance entire four-month run.
to the levels of clean tube operation. Figure
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In September 1962, the Hagevap treat and the pH rose to 7.5, as measured at the
ment was discontinued and sulfuric acid discharge side of the brine recycle pump.
injection was used as the sole method of The rapid reaction between acid and bicar-
alkaline scale control. Acid injection was Ixmate was enhanced by a very effective
continued for the duration of the plant's deaeration system which caused the follow
stay in San Diego, a total of 8,649 hours of ing reaction to proceed nearly completely
running time. This change was introduced to the right.
in an attempt to operate at or near the
maximum design temperature of 250°F. HCO," + H* ;± H.O + CO, (g)
Such experiments could not be conducted With acid injection, the volume of non-
with Hagevap since it undergoes rapid condensable gases vented from the evap
chemical decomposition above 200°F. As a orators was nearly doubled; about half this
result of acid injection, excellent thermal volume was carbon dioxide. In order to
performance was maintained in the normal avoid excess corrosion, most plants using
range of temperatures and brine concentra acid injection are equipped with a system
tions. It was also found that scale-control for neutralizing excess unreacted acid. This
costs, using either Hagevap or sulfuric acid, is done by introducing sodium hydroxide
were approximately equal. The cost of at some point downstream from the acid
either method is about three cents per 1,000 source. The San Diego plant was provided
gallons distilled water. There is a very little with such an installation but neutralization
additional cost for a mi foam agent with acid was unnecessary due to rapid recovery of
treatment. pH values. Acid injection worked excep
Concentrated sulfuric acid (tech grade) tionally well without abnormal corrosion
was introduced directly into the feed water since excess acid (above stoichiometric
at a measured rate to give 120 ppm by quantity) was never required. These good
weight (stoichiometrically equal to bicar results were probably due to uniform mix
bonate ion concentration) . The ambient ing of brine with acid and to rapid dissipa
pH of about 8.3 dropped drastically at the tion of carbon dioxide from acidified brine.
point of acid addition and rose rapidly due It might be noted that acid injection was
to mixing and deaeration. After reaction regulated by flow control rather than level
with bicarbonate ion, the residual alkalinity control at this plant. A summary of alkaline
was reduced from 140 ppm to about 12 ppm scale control runs is presented in Figure 57.

EXPERIMENTS IN THE CALCIUM SULFATE SUPERSATURATED REGION


Although alkaline scale can be controlled perature experiment, for example, water
easily and at low cost, the calcium sulfate might be distilled at 250°F with an initial
problem is by no means near solution. Seed concentration factor of 15. This is repre
ing or ion-exchange may provide an answer sented by operating line triangle CD,F.,.
but neither is operational at this writing, Similar triangles could be drawn through
and we must still rely on effective control of other points representing higher tempera
distillation parameters. When the San Diego tures and concentration factors. Points D,
plant was found to operate efficiently and through D, correspond to actual cycle con
reliably with acid injection at approxi ditions for several different tests.
mately 200°F and C.F. of 1.7, it was decided Short successful explorations into the high
to explore higher temperatures and concen temperature region were made by running
tration factors (known to be in the calcium at points D, and D4. It is interesting to note
sulfate range) . These experiments were de that maximum output was achieved during
signed to collect badly needed data and also these runs. In a single 24-hour period, dis
to check the position of the Standiford and tilled water production totaled approxi
Sinek curves (ref. 10) . The lines in Figure mately 1,400,000 gallons, limited only by
55, passing through points A, B, C, and D, the capacity of the product pump Cdesigned
represent the heating and concentrating of to handle only one mgd) . The plant was
the brine by recirculation. Details of this then operated continuously in the range
cycle have been presented by Mulford (ref. represented by point Dt. This test was
21). Segment DE shows the change in tem carried out under scale-free conditions at a
perature and concentration factor during point just under the hemihydrate curve for
the flashing process. Operational triangles a period of 884 hours. It was then decided
similar to CDE can be drawn through other to check the apparent position of this curve
points representing higher temperatures and by exploring the supersaturated region as
concentration factors. In a given high tem represented by points D„ D„ D„ and D„.
The plant was run for 350 hours at point deposit rapidly in the unstable region even
D, and 357 hours at D, with no decline in if nonboiling operation was resumed. The
thermal performance due to scale. D, and last series of experiments and explorations
D, represent short runs of 57 and 24 hours, could not be completed because the plant
respectively- When normal operation could was dismantled and shipped to Cuantanamo
be maintained at C.F. 2.5 (Da) , the concen Bay, Cuba.
tration factor was again increased to 2.9 The reader will note that points D3
(D,) . A few hours after this condition was through D5 are in the unstable region for
reached, a rapid fall in thermal performance anhydrite and D is right on the line. Ex
was observed. Scale was not appreciably perience at San Diego tends to support
diminished by "throttling back" to 200°F Langelier's position since scale-free opera
and C.F. of 1.35. The plant was ultimately tion was consistently achieved in this region.
shut down and inspected. Heavy deposits Although the anhydrite precipitation thresh
were noted in the downstream side of the old is exceeded, this scale would not be
brine heater tubes with the most intense anticipated because of the short residence
scaling in the last foot. The deposit aver time of the supersaturated brine. The long
aged i/£ inch thick, but some tubes were scale-free runs at points D, and D, appear
completely plugged. Attempts to dissolve to be conclusive and would lend to chal
this material indicated that it was probably lenge the position of the hemihydrate curve
calcium sulfate: no crystallographic analyses (Fig. 55) in this region. These results would
were made. shift the Standiford and Sinek curve up
It would appear that an effective scaling ward and to the right at 250° F for this
threshold had been reached at point D„ but flash plant. Data indicated by points D» and
operating circumstances raise doubts that D, are inconclusive due to short duration
this was the case. The uneven distribution runs and boiler malfunctions accompanying
of scale deposits indicated the probability them. It would appear that the hemihydrate
that boiling had occurred in the brine line reaches point D7 or possibly higher.
heater tubes just prior to this run. This What about points D, and D„? Is it possible
suspicion was borne out by certain recorded to carry out scale-free operation in this
operational difficulties in the boiler and region, or were these tests of such short
turbine-driven pumps. These malfunctions duration that equilibrium conditions could
resulted in a pressure drop in the brine not be achieved? Hopefully, these opera
heater tubes below the saturation pressure tional areas will be re-explored at the flash
corresponding to 250°F. Under these con plant planned to replace this facility. Only
ditions, the resultant higher wall tempera then can these experimental results be con
tures could initiate premature scale forma firmed. The work thus far at San Diego,
tion as compared with nonboiling operation. however, indicates a steeper slope for the
Once nucleation was begun, scale would hemihydrate curve in the region investigated.

CONCLUSIONS
The reliability of two different methods previously described unstable range for
of alkaline scale control has been clearly anhydrite. Explorations in the hemihydrate
demonstrated by this work at San Diego. region gave scale-free performance at 250°F
Both Hagevap and sulfuric acid injection and a concentration factor of 2.1. Operation
gave good results on long continuous runs. under more severe conditions may also be
Although periodic acid cleaning was neces possible, but results are inconclusive at this
sary with Hagevap, it could be accomplished time.
while the equipment remained "on stream". Several interesting questions are raised by
Acid injection was found preferable to the high temperature data presented in this
Hagevap, however, since no maintenance paper:
was required under normal operating con 1. Is the hemihydrate curve of Standiford
ditions. The acid system worked without and Sinek (Fig. 55) incorrect for equilib
excessive corrosion, requiring no back neu rium conditions? We might conclude that
tralization with sodium hydroxide. Its chief this line was correctly drawn and that oper
advantage was the extended range of pos atton of the San Diego plant was carried
sible operating temperatures. High tem out in a metastable supersaturated region
perature experiments could thus be carried above the curve.
out (in the calcium sulfate range) without 2. If, in fact, we were operating in a
complications from alkaline scale. Scale-free supersaturated region, how long would it
operation was consistently achieved in the be possible to continue without scale
deposit? hydrate as well as with respect to anhydrite.
3. Can flash plants operate at higher tem Thus, there is some danger in taking a
peratures and concentration factors because threshold curve developed on one type of
of the nonboiling conditions in the brine apparatus and under one set of conditions
heater? The effect of ebullition on scale and applying it indiscriminately to a com
nucleation is probably an important factor pletely different apparatus and different
in defining threshold conditions. operating conditions. This makes it neces
Further experimentation is imperative. sary to test each type of apparatus sepa
Based on our findings to date, certain rately in order to determine its limitations,
recommendations can be made to plant at least until the phenomenon of scale for
operators. mation is better understood than at present.
It has been shown that the precipitation It should also be noted that operation of an
threshold measured under laboratory con evaporator in the supersaturated region may
ditions of slow evaporation may not be the be tricky and certainly will require close
same as that found in an evaporator operat control of plant operating conditions. Gen
ing under industrial loading conditions. The eral experience (possibly confirmed in these
point made earlier for the anhydrite curve tests) has been that once precipitation
may also be true for the hemihydrate curve, starts, for whatever reason, it is necessary to
i.e., it may be possible for an industrial back down out of the supersaturated region
evaporator to operate far into the super completely and probably to remove the
saturated region, with respect to hemi crystals which have deposited.

REFERENCES
1. Silver, R. S.: "A review of distillation E. V.: "Aqueous system at high tem
processes for fresh water production peratures". /. Chem. and Engr. Data,
from the sea", Proceedings of the Euro 9:187-91 (Apr. 1964) .
pean Federation of Chemical Engineers 9. Power, W. H.; Fabuss, B. M.; Satter-
(May 28-June 2, 1962) Athens, Greece, field, C. N.: "Transient solubilities in
Dechema Monographien, Nr. 718-834, the calcium sulfate—water system", /.
Band 47, pp. 1<M2. Chem. and Engr. Data, 9:437-41 (July
2. Partridge, E. P.: "Formation and prop 1964).
erties of boiler scale", Univ. of Michi 10. Standiford, F. C; Sinek, J. R.: "Stop
gan, Dept. Engr., Research Engr. Re scale* in sea water evaporators", Chem.
search Bulletin no. 15 (June 1930) . Engr. Prog., 57:58-63 (Jan. 1961) .
3. Badger, W. L., et al: "Critical review 11. Liddell, R. W.: "Method of treating sea
of literature on formation and preven water", Hagan Corp., Pittsburgh. Pa.,
tion of scale", Office of Saline Water U.S. Patent 2,782,162 (Feb. 19. 1957) .
RtD Progress Report no. 25 (July 12. Gainey, R. J.; Thorp, C. A.; Cadwalla-
1959) . der, E. A.: "Calcium sulfate seeding
4. McCutchan, J. W.; Glater, J.: "Scale prevents calcium sulfate scale", Ind. and
formation in saline water evaporators", Engr. Chem. 55:39-^3 (March 1963) .
UCLA Department of Engineering Re 13. Sugi, J., et al: "On the scale prevention
port no. 64-5 (Jan. 1964) . by addition of crystal seeds", Bull. Soc.
5. Langelier, W. F.; Caldwell, D. H.; Salt Science, vol. 9, no. 1, Japan (March
Lawrence, W. B.: "Causes and preven 1955) p. 38.
tion of scale and corrosion in thermo- 14. Fisher, D. A.; Gilbert, F. W.: "Recent
compression equipment when employed developments in flash distillation". Am.
for the distillation of sea water", Univ. Chem. Soc. Div. of Water and Waste
of Calif., Berkeley, IER Series no. 4, Chem. Preprints (Apr. 1965) pp. 1-8.
Issue no. 12 (Aug. 1950). 15. Mcllhenny, W. F.: "Sea water softening
6. Mcllhenny, W. F.: "Calcium sulfate by ion-exchange as a saline water pre-
scale in sea water evaporators", Am. ireatment". Office of Saline Water R &
Chem. Soc. Div. of Water and Waste D Progress Report no. 62 (May 1962) .
Chem. Preprints (Apr. 1965) pp. 42-47. 16. Frankel, A.: "Flash evaporation for the
7. Kelley, K. K.; Southard, J. C; Ander distillation of sea water", Proc. Inst.
son, C. T.: "Thermodynamic properties Mech. Engrs., vol. 174, no. 7 (1960) .
of gypsum and its dehydration prod 17. Mulford, S. F.: "Low temperature flash
ucts", U.S. Bureau of Mines Tech. distillation of sea water", Proceedings
Paper 625 (1941) . of Symposium on Saline Water Con
8. Marshall, W. L.: Slusher, R.; Jones, version, Office of Saline Water in co
operation with NAS-NRC. NRC Publ. 19. First Annual Report Saline Water Con
568 (Nov. 4-6, 1957) pp. 91-102. version Demonstration Plant No. 2, San
18. Leitner, G. F.: "Operating experience Diego, California, Office of Saline Water
with a multistage flash type sea water R&D Report no. 102 (1964) .
evaporator and its effect on future de 20. Saline Water Conversion Report for
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28-June 2, 1962) Athens, Greece, 21. Mulford, S. F.: "Scale control in sea
Dechema Monographien, Nr. 781-834, water evaporators", M.S. Thesis, UCLA
Band 47, pp. 99-112. Department of Engineering (Aug. 1964) .

SUMMARY OF DISCUSSION
There was no discussion.

Evaluation Des Méthodes de Lutte

Contre L'Entartrage Utilisées Dans

L'Installation a Vaporisation Par

Detente de L'Office of Saline Water,

a San Diego, Californie

Stewart Mulford, Julius Glater, J. W. McCutchan

Etats-Unis d'Amérique

D'excellents résultats dans les méthodes tation de sulfate de calcium. Cette opéra
de prévention de l'entartrage ont été ob tion a dépassé les conditions de seuil dé
tenus à l'installation à multiples effets de crites par d'autres chercheurs. Le pro
distillation et vaporisation par détente de gramme expérimental se composait de trois
l'Office of Saline Water, à San Diego, Cali parties: 1. Lutte contre les incrustations
fornie. D'une manière générale, les systèmes alcalines à l'aide de l'Hagevap L.P. 2. Lutte
à évaporation par détente font preuve contre les incrustations alcalines en appli
d'une bonne résistance aux incrustations. quant des traitements à l'acide sulfurique,
Cet avantage résulte probablement de la et 3. Expériences dans la zone d'instabilité
séparation des fonctions de chauffage et du sulfate de calcium.
d'évaporation, de sorte que l'ensemble du Les premiers essais ont été effectués à une
circuit de chauffage n'est pas soumis aux température maximum de 200°F et à un
conditions d'ébullition. L'installation de facteur de concentration de la saumure de
San Diego avait pour caractéristiques mar 13- Dans ces conditions, on ne s'attendait
quantes un système de mélange d'acide et qu'à un entartrage alcalin. Au cours des
un désaérateur. Ces éléments parfaitement 5.399 premières heures de fonctionnement
mis au point permettaient d'assurer le de l'installation, l'entartrage fut efficacement
contrôle adéquat des incrustations alcalines contrôlé grâce à l'Hagevap. L'Hagevap est
à faible concentration d'acide. Le fonc un mélange de polyphosphates de sodium,
tionnement à une température élevée de de dérivés d'acide sulfonique de lignine et
250°F et des facteurs de concentration de divers esters de glycols polyalcylènes.
supérieurs à deux ont permis d'obtenir un Ces trois ingrédients agissent de manière
rendement efficace sans formation d'incrus synergique et empêchent la formation d'in-

151
crustations, d'après un mécanisme dont on l'emploi d'un système d'injection caustique.
ne comprend pas très bien le fonctionne L'installation de San Diego fut dotée d'un
ment étant donné que l'Hagevap est efficace semblable système, mais la neutralisation se
même à des concentrations très basses (3 à révéla inutile étant donné le redressement
5 ppm) . L'Hagevap n'a pas réussi à empê rapide des valeurs du pH. La nécessité d'u
cher complètement l'entartrage mais en a tiliser un excédent d'acide (au dessus de la
radicalement ralenti la vitesse d'accumula quantité stoïchiométrique) ne s'est jamais
tion, ainsi qu'on l'a constaté par la baisse présentée dans la lutte contre l'entartrage.
du rendement de l'installation. Cette baisse, Ces résultats étaient probablement dûs au
due à de légères incrustations, était reflétée mélange uniforme de la saumure avec de
d'une part par un accroissement de la l'acide et à la dissipation rapide de bioxyde
pression et de la température de la vapeur de carbone.
du réchauffeur à saumure et, d'autre part, Lorsque l'on s'aperçut du bon fonctionne
par une chute du rapport rendement. Les ment de l'installation avec une injection
dépôts qui ont une influence néfaste sur les d'acide à environ 200°F et un facteur de
coefficients de transmission de la chaleur concentration de 1,7, on décida de pour
étaient souvent à peine visibles lors de la suivre l'expérience avec des températures et
fermeture provisoire de l'installation en vue des facteurs de concentration plus élevés.
d'assurer le nettoyage. Au cours de deux La zone de recherche avait été décrite
longues périodes de marche avec Hagevap comme étant une région instable pour les
(6 et 4 mois) une baisse du rendement incrustations de sulfate de calcium. Les
lente mais continue fut observée, dont le expériences effectuées à San Diego avaient
taux était inférieur a 5% par mois. Vers la pour but de réunir des données qui faisaient
fin de la seconde période (4 mois) on sérieusement défaut et de vérifier en outre
installa un système d'injection d'acide. la position des courbes du sulfate de cal
Outre l'Hagevap, de l'acide sulfurique fut cium proposées par Standiford et Sinek en
introduit dans le système pendant les 108 1961. On parvint à un fonctionnement libre
dernières heures de temps de marche. Cette de dépôts pendant de longs essais dans la
opération de détartrage "in situ" fut appa zone de l'anhydrite. Ces résultats correspon
remment couronnée de succès à en juger dent bien aux données recueillies par Lan-
par un retour du rendement thermique gelier et peuvent être expliqués par de
aux niveaux atteints lorsque les tubes longues périodes d'équilibre nécessaires au
étaient libres de toute incrustation. dépôt de l'anhydrite. A la suite de ces
A la suite de cet essai, le traitement à expériences, il fut décidé de vérifier la posi
l'Hagevap fut interrompu et l'injection tion apparente de la courbe de l'hémi-
d'acide sulfurique fut utilisée comme seul hydratc en procédant à des recherches dans
moyen de lutte contre les incrustations la région sursaturée où l'on espérait pouvoir
alcalines. On a eu recours à ce changement obtenir d'aussi bons résultats. L'installation
de méthode en vue de parvenir à un niveau fut mise en marche pendant 357 heures à
de marche égal ou proche à la température 250°F et à un facteur de concentration de
maximum projetée de 250°F. L'instabilité 2,1 sans que le rendement thermique
thermique de Hagevap avait interdit tout n'accuse de baisse par suite de l'entartrage.
fonctionnement dans de pareilles conditions. Lorsque l'on s'aperçut qu'un fonctionne
De l'acide sulfurique concentré fut intro ment normal pouvait être maintenu dans
duit directement dans l'eau d'alimentation ces conditions, le facteur de concentration
selon un dosage destiné à donner 120 ppm fut porté tout d'abord à 2.5 puis à 2,9.
par poids. Le pH ambiant qui était d'en Quelques heures plus tard, une chute
viron 8,3 accusa une baisse sensible au rapide du rendement thermique se pro
point d'injection d'acide puis s'éleva rapide duisit. L'entartrage ne diminua pas de façon
ment sous l'influence du mélange et de la notable après le "renversement" du procédé
desaération. A la suite de la réaction pro vers les températures et les facteurs de
duite à l'aide d'ions bicarbonates, l'alcali concentration plus faibles. Il fallut en fin
nité tomba de 140 ppm à environ 12 ppm de compte fermer l'installation pour pro
et le pH se stabilisa à 7,5, selon les indica céder à son inspection. On observa d'im
tions relevées au tuyau de décharge de la portants dépôts du côté aval des tubes du
pompe de recyclage de la saumure. La réchauffeur de saumure. Les incrustations
réaction rapide entre l'acide et le bicarbo atteignaient en moyenne une épaisseur de
nate fut accélérée par un système de desa î/J de pouce tandis que certains tubes
ération très efficace. Afin d'éviter une corro étaient complètement obstrués. Les tenta
sion excessive, la plupart des installations tives faites pour dissoudre ces matières
recourant à l'injection d'acide doivent neu laissèrent supposer qu'il s'agissait de sulfate
traliser l'excédent d'acide non réactif par de calcium, mais on ne procéda à aucune

152
analyse cristallographique. tantes de l'appareillage. Il est à espérer que
Il semble qu'un seuil d'entartrage effectif ces études pourront se poursuivre dans
ait été atteint. Cependant les circonstances l'installation de remplacement d'une capa
de l'exploitation permettent de douter qu'il cité de 1 million de gallons par jour dont
en soit ainsi. La répartition inégale du on envisage l'implantation. D'autres inves
tartre indiquait que l'ébullition s'était tigateurs sont en train d'étudier les condi
probablement produite dans le réchauffeur tions limites de l'hémihydrate dans des
à saumure juste avant la dernière période appareils à évaporation par détente de
de marche. Cette conclusion reposait sur le dimensions plus réduites. Il sera certes inté
mauvais fonctionnement de la chaudière ressant de comparer les résultats qu'ils
enregistré au cours des expériences. Dans auront obtenus avec les nouvelles données
ces conditions, les températures plus éle émanant d'une grosse installation.
vées des parois engendrées par cet état de Pour le moment, les travaux effectués à
choses pourraient amorcer un entartrage l'installation de San Diego permettent de
prématuré, par contraste avec une exploita tirer les conclusions suivantes:
tion où l'ébullition serait absente. Le début 1. La courbe de fonctionnement pratique
de la cristallisation laisse supposer une relative à l'hémihydrate a une pente plus
accumulation rapide du tartre même si l'on forte que la courbe calculée pour des condi
revenait au fouctionnement sans ebullition. tions d'équilibre par Standiford et Sinek.
La dernière série d'expériences n'a pu être 2. Il est possible que les installations à
menée à bonne fin en raison du démontage évaporation instantanée soient en mesure
et du transfert de l'installation à Guanta- de fonctionner pendant de longues périodes
namo Bay pendant la crise survenue à Cuba dans une zone sursaturée métastable, en ce
au sujet de l'alimentation en eau de cette qui concerne à la fois l'anhydrite et
base. l'hémihydrate.
Les bons résultats d'exploitation obtenus 3. Des courbes d'exploitation différentes
dans la zone de l'anhydrite ont été confirmés peuvent s'avérer nécessaires pour décrire
à San Diego. Des périodes de fonctionne les conditions limites du sulfate de calcium
ment prolongées sans formation d'incrusta dans divers types d'évaporateurs.
tions dans la zone de l'hemihydrate ten De toute façon, nous devons réaliser que
draient a remettre en question la position de l'on ne saurait appliquer au hasard à tout
la courbe de Standiford et Sinek à 250°F. autre procédé de distillation la courbe de
Des essais de fonctionnement dans des con seuil mise au point pour un appareil par
ditions plus rigoureuses se sont révélés peu ticulier réagissant à une série de conditions
concluants en raison de pannes concomi données.

153
Оценка Методов Борьбы с Накипью

на Установке Мгновенного Испарения,

Принадлежащей У. С. В. (Управление

по Делам Соленых Вод) в Сан Диего,


Шт. Калифорния

Стюарт Молфорд, Юлий Глетер, Дж. У. МакКотчан

Соединенные Штаты Америки

На многоступенчатой установке мгно ние первых 5399 часов работы уста


венной дистилляции в Сан-Диего, шт. новки появление накипи эффективно
Калифорния, которая принадлежит У. устранялось с помощью Hagevap'a.
С. В., были достигнуты прекрасные ре Hagevap представляет собой смесь по
зультаты в области предупреждения лифосфатов натрия, производных суль-
накопления накипи. Системы мгновен фокислоты и лигнина и различных
ного испарения вообще хорошо сопро сложных эфиров полиалкиленовых гли-
тивляются образованию накипи. Это колей. Эти три компонента действуют
вероятно объясняется разделением синергетически, предотвращая образо
функций нагревания и испарения, вслед вание щелочной накипи посредством
ствие чего во всем тепловом цикле механизма, действие которого невпол
отсутствует состояние кипения. Кислот не понятно, так как Hagevap эффекти
но-смесительная система и деаэратор вен даже при очень низких концентра
принадлежали к замечательным особен циях (3-5 мг/л). Hagevap не останав
ностям установки в Сан-Диего. Эти хо ливал вполне накипь, но радикально
рошо спроектированные детали позво замедлял скорость ее накопления, что
ляли удачно бороться со щелочной на замечалось при замерах уменьшавшей
кипью при низкой кислотной концен ся производительности установки.
трации. Работа протекала в условиях Уменьшение, объяснявшееся неболь
действенной производительности и без шим отложением накипи, отражалось
отложения сульфата кальция, несмотря на 1) повышении давления и темпера
на высокую температуру 250°F и ко туры пара, подогревавшего концент
эффициенты концентрации более 2. рат, и 2) падение относительной про
Она превосходила высоту порога, опи дуктивности. При закрытии установки
сываемого другими исследователями. с целью чистки, часто бывало трудно
Экспериментальная программа состоя обнаружить следы отложений, кото
ла из трех частей: рые весьма сильно влияют на скорость
1. Предотвращение образования ще передачи тепла. В течение двух дол
лочной накипи с помощью состава гих испытаний с Hagevap-ом (6 и 4
"Hagevap L.P." месяца), было замечено медленно-рав
2. Предотвращение образования ще номерное снижение производительно
лочной накипи с помощью серной сти, достигавшее менее 5% в месяц.
кислоты, и К концу второго испытания (4 месяца)
3. Опыты в области неустойчивости была построена система кислотной ин-
сульфата кальция. жекции. В течение последних 168 часов
Первоначально испытания велись при кроме Hagevap-a вводилась тоже сер
максимальной температуре 200°F и ко ная кислота. Такой метод непосред
эффициенте концентрации рассола 1,5. ственного удаления накипи на месте ее
При этих условиях ожидалось только появления видимо был удачен, судя по
образование щелочной накипи. В тече тому, что тепловая производительность
154
вернулась на тот же самый уровень, и Сайнекем. При долгих опытах в ан-
где она была при чистых трубопрово гидритной области работа регулярно
дах. протекала в условиях отсутствия на
После этого опыта употребление кипи. Эти результаты хорошо согласо
Hagevap-a было прекращено и инжек вались с данными, полученными Лан-
тирование серной кислоты стало един джелиэр-ом, и могут быть объяснены
ственным средством борьбы со щелоч долгим временем уравновешивания, от
ной накипью. Это изменение было вве которого зависит отложение ангидри
дено из за попытки начать работать та. После этих опытов было решено
при максимальной или близкой к ней проверить кажущееся положение кри
температуре 250° F. Термическая неста- вой гемигидратов, исследовав область
бильиость Hagevap-a лишала возмож пересыщения, где надеялись получить
ности добиться этих условий. Концен одинаково хорошие результаты. Уста
трированная серная кислота непосред новку заставили работать 357 часов
ственно вводилась в исходную воду с при 250° F и коэффициенте концентра
таким расчетом, чтобы получить по ции 2,1, причем не было обнаружено
весу 120 частей на миллион. Показа понижения производительности из за
тель концентрации водородных ионов накипи. Когда выяснилось, что нор
окружающей среды pH, стоявший пе мальная работа может поддерживаться
ред этим на высоте около 8,3, в момент при этих условиях, коэффициент кон
инжектирования кислоты сильно падал, центрации был сначала увеличен до
но затем, вследствие перемешивания и 2,5, а затем до 2,9. Через несколько
деаэрации быстро поднимался. После часов по достижению этого условия
бикарбонатно-ионной реакции остаточ наступило быстрое падение термиче
ная щелочность уменьшалась со 140 ской производительности. Образование
частей на миллион до примерно 12 ча накипи ощутимо не изменилось, несмо
стей на миллион, a pH останавливался тря на «обратное дросселирование> к
на уровне 7,5, замеренном на выходной более низким температурам и коэффи
стороне насоса, рециркулировавшего циентам концентрации. В конце концов
концентрат. Быстрая реакция между установку пришлось остановить и про
кислотой и бикарбонатом ускорялась извести инспекцию труб, подогреваю
с помощью весьма эффективной де- щих концентрат. Были обнаружены
аэрационной системы. Во избежание большие отложения на низовой по те
чрезмерной коррозии на многих уста чению 'стороне. Отложение достигало
новках нейтрализуют избыточную не средней толщины 1/8", но некоторые
реактивную кислоту с помощью систе трубы были совершенно закупорены.
мы, инжектирующей каустическую со При попытках растворить этот мате
ду. Такая установка была также устро риал появлялась мысль, что он являет
ена в Сан-Диего, но нейтрализация ся сульфатом кальция, хотя кристалло
оказалась ненужной ввиду быстрой ре графические анализы не были произве
генерации величин pH. Для борьбы с дены.
накипью никогда не требовалось до Может показаться, что тогда был до
бавочной кислоты (превышавшей сте- стигнут эффективный порог образова
хиометрическое количество). Эти ре ния накипи, однако, условия работы вы
зультаты вероятно зависели от одно зывают сомнения, что это соответство
родного перемешивания рассола с ки вало действительности. Неравномерное
слотой и быстрого рассеяния двуокиси распределение накипи указывало на ки
углерода. пение, которое видимо происходило в
Когда выяснилось, что установка эф подогревателе рассола как-раз перед
фективно и надежно работает с кислот последним опытом. Это заключение
ным инжектированием приблизительно имело свое обоснование, ввиду неко
при 200° F и коэффициенте концентра торых недочетов в работе котла, заме
ции 1,7, было решено начать исследо ченных во время производства испы
вать более высокие температуры и ко таний. При этих условиях более высо
эффициенты концентрации. Обследо кие результирующие температуры по
ванная зона была описана, как неу сравнению с процессом без кипячения
стойчивая область накипи сульфата могли вызвать преждевременное оса
кальция. Опыты в Сан-Диего предна ждение накипи. Полагают, что раз об
значались для собирания весьма необ разование центров кристаллизации уже
ходимых данных, а также для проверки началось, то накипь станет быстро от
положения кривых сульфата кальция, кладываться, даже и при возобновле
предложенных в 1961 г. Стандифордом нии работы без кипения. Последнюю
155
серию опытов не удалось закончить, выми данными, полученными на круп
потому что установка была разобрана ной установке.
и отправлена в бухту Гуантанамо, вви В настоящее время, на основании
ду водяного кризиса на Кубе. работы установки в Сан-Диего некото
В Сан-Диего подтвердилась возмож рые выводы имеют свое обоснование.
ность удачной работы в ангидритной 1. Кривая для гемигидратов, полу
области. Продолжительные исследова ченная в рабочих условиях, имеет бо
ния, проводившиеся в гемигидратной лее крутой уклон, чем кривая, постро
области без образования накипи, выз енная Стандифордом и Сайнеком для
вали сомнение относительно положе равновесных условий.
ния кривой Стандифорда и Сайнека при 2. Возможно, что установки с мгно
температуре 250°F. Намеченные опыты венным испарением смогут подолгу ра
при более суровых условиях остались ботать в метастабильной области пе
неубедительными ввиду плохой рабо ресыщения, как в отношении к анги
ты оборудования, которая их сопро дритам, так и гемигидратам.
вождала. Приходится надеяться, что 3. Для различных типов испарителей
эти наблюдения будут продолжены на могут понадобиться различные рабочие
новой установке, намеченной к по кривые, чтобы охарактеризовать погра
стройке взамен прежней, которая будет ничные условия сульфата кальция.
производить один миллион галлонов Во всяком случае мы должны пом
пресной воды в день. Другие исследо нить, что нельзя применять без разбора
ватели, пользуясь меньшим оборудо пороговую кривую к любому дистил-
ванием, работающем на мгновенном ляционному процессу, если она была
испарении, сейчас изучают погранич построена при заданных условиях для
ные условия гемигидратов, и было бы оборудования определенного типа.
интересно сверить их результаты с но

Una Evaluación de Metodos de

Control de Incrustaciones en la

Planta de Evaporación Instantánea

de la Oficina de Agua Salada en

San Diego, California

Stewart Mulford, Julius Glater, N. W. McCutchan

Estados Unidos de Norteamérica

En la planta de destilación instantánea de dones en las que no existe ebullición en


etapas multiples que la O.S.W.• opera en ninguna parte del circuito de calentamiento.
San Diego, California, se han logrado re Las características más destacadas de la
sultados excelentes en la prevención de la planta de San Diego son el sistema de
acumulación de incrustaciones. En general, mezclado del ácido y el desaireador. Estos
los sistemas de destilación instantánea componentes, muy bien diseñados, permi
muestran una buena resistencia a las in tieron un buen control de las incrustaciones
crustaciones. Esto probablemente se debe a alcalinas a bajas concentraciones de ácido.
la separación de las etapas de calentamiento La operación a la elevada temperatura do
y evaporación, lo cual conduce a condi- 250°F y los factores de concentración mayo
res que dos, permitieron una eficiente labor
* Office of Saline Water — Oficina de Agua sin depósito de incrustaciones de sulfato de
Salada.
156
calcio. Esta operación excedió las condi día la operación bajo estas condiciones. Se
ciones iniciales descritas por otros investiga introdujo directamente ácido sulfúrico con
dores. El programa experimental se dividió centrado en el agua de alimentación a una
en tres partes: 1) Control de incrustaciones velocidad medida, con el objeto de dar 120
alcalinas con Hagevap L.P., 2) Control de ppm por peso. El pH ambiente de 8,3
incrustaciones alcalinas con acido sulfúrico, cayó radicalmente en el punto de inyección
y 5) Experimentos en la región de la inesta del ácido y luego creció rápidamente de
bilidad del sulfato de calcio. bido al proceso de mezclado y de desairca-
Las operaciones iniciales fueron llevadas ción. Luego de la reacción con el ion
a cabo a una temperatura máxima de bicarbonato, la alcalinidad residual se re
200°F y un factor de concentración de las dujo de 140 ppm, a cerca de 12 ppm y el
aguas madres de 13. Bajo estas condiciones, pH se niveló a 7.5, medido en el punto
sólo se anticiparon incrustaciones alcalinas. de descarga de la bomba de reciclaje de
Durante las primeras 5.399 horas de opera las aguas madres. La rápida reacción entre
ción de la planta, las incrustaciones se con el ácido y el bicarbonato fue aumentada
trolaron eficazmente con Hagevap. Hagevap mediante un sistema de desaireación muy
es una mezcla de polifosfatos de sodio con eficaz. A los efectos de evitar una corrosión
derivados del ácido sulfónico de lignina y excesiva, muchas plantas que usan la inyec
distintos ésteres de glicoles polialquilcnos. ción de ácido deben neutralizar el exceso
Los tres ingredientes actúan en forma si- de ácido no neutralizado durante la re
ncrgistica para prevenir la formación de acción mediante un sistema de inyección de
incrustaciones alcalinas, por medio de un sosa caústica. Tal instalación fue sumini
mecanismo no claramente entendido, dado strada a la planta de San Diego pero se
que Hagevap es efectivo aun a concentra encontró que la neutralización era innece
ciones muy bajas (3-5 ppm). El Hagevap saria debido a la rápida recuperación de
no previene completamente la formación los valores de pH. Para el control de las
de incrustaciones, pero disminuye radical incrustaciones nunca se requirieron excesos
mente la velocidad de acumulación, medida de ácido (por encima de la cantidad este-
a través de la disminución de eficiencia quiométrica). Estos resultados probable
de producción de la planta. El decrcmento, mente fueron consecuencia de la mezcla
debido a depósitos de incrustaciones livianas uniforme de las aguas madres con el ácido
se reflejó en: 1) Un aumento en la presión y de la rápida degradación del anhídrido
y temperatura del calentador de aguas carbónico.
madres, y 2) Una caída del porcentaje de Cuando se determinó que la planta ope
rendimiento. Depósitos que afectan consi raba en forma eficiente y estable con in
derablemente la velocidad de transferencia yección de ácido a aproximadamente 200°F
de calor con frecuencia apenas fueron visi y a un factor de concentración de 1.7. se
bles cuando se peró la planta para su decidió explorar temperaturas más altas y
limpieza. Durante dos períodos prolongados mayores factores de concentración. El área
de funcionamiento con Hagevap, (6 y 4 investigada había sido descrita como una
meses) se notó una lenta pero sostenida región inestable para la incrustación de
disminución de la eficiencia de operación, sulfato de calcio. Los experimentos en San
a razón de menos del 5% mensual. En Diego tuvieron la finalidad de recoger datos
postrim.rías del segundo período de funcio sumamente necesarios y también la verifica
namiento (4 meses), se instaló un sistema ción de la posición de las curvas de sulfato
de inyección de ácido. Además de Hagevap, de calcio propuestas en 1961 por Standi-
durante las últimas 168 horas de operación, ford y Sinek. Una operación libre de in
se introdujo ácido sulfúrico. Esta operación crustaciones se logró consistentemente en
de desincrustación "in situs" aparentemente corridas largas en la región de la anhidrita.
fue exitosa dado que se observó un retorno Estos resultados están de acuerdo con los
a la eficiencia térmica de los niveles de resultados obtenidos por Langelicr y pue
operación con tubos limpios. den explicarse por el largo período de
Luego de este período de funcionamiento, estabilización requerido para el depósito
se suspendió el tratamiento con Hagevap de anhidrita. Después de estos experimen
y solamente se usó la inyección de ácido tos, se decidió verificar la posición aparente
sulfúrico como único medio para combatir de la curva del hemihidrato mediante ex
incrustaciones alcalinas. Este cambio se in ploraciones en la región de sobresaturación
trodujo para tratar de operar a, o cerca de. donde se confiaba podrían obtenerse resulla-
la máxima temperatura para la que dos igualmente buenos. La planta operó
estaba diseñado el equipo, es decir 250°E. durante 357 horas a 250°F y a un factor
La inestabilidad térmica del Hagevap impe de concentración de 2,1, no registrándose
ninguna disminución de la eficiencia tér Bahía de Guantánamo durante la crisis
mica debida a incrustaciones. Cuando se cubana sobre el agua.
determinó que en estas condiciones podría La posibilidad de una operación exitosa
mantenerse una operación normal, se au en la región de la anhidrita fue confirmada
mentó el factor de concentración, primero en San Diego. Operaciones largas sin in
a 2,5 y luego a 2,9. Unas pocas horas crustaciones en la región del hemihidrato
después de haber alcanzado estas condi tenderían a poner en tela de juicio la
ciones, se produjo una sensible cafda de posición de la curva de Standiford y Sinek
la eficiencia térmica de operación. Las in a 250° F. Pruebas experimentales mediante
crustaciones no fueron disminuidas en operaciones intentadas a condiciones extre
forma apreciable mediante el retorno a las mas no son concluyentes debido al funcio
condiciones iniciales de temperatura y con namiento deficiente del equipo auxiliar.
centración. Finalmente, la planta tuvo que Se confía que estos experimentos podrán
ser parada e inspeccionada. Se notó la continuarse en la planta de reemplazo
existencia de gruesos depósitos en los tubos propuesta, de una capacidad de un millón
calentadores de la salmuera en la región de galones diarios. Otros investigadores se
del flujo descendente. Los depósitos medían, encuentran estudiando actualmente las con
en promedio, i/s de pulgada de espesor, diciones de la frontera del hemihidrato en
pero algunos tubos se encontraban total equipos más pequeños de destilación ins
mente tapados. Los intentos que se reali tantánea y podría ser de interés verificar
zaron para disolver este material indicaron sus resultados con nuevos datos obtenidos
que se trataba de sulfato de calcio, pero en una planta mayor.
no se efectuaron análisis cristalográficos. En este momento, se justifica la presenta
Parecía haberse alcanzado un punto de ción de ciertas conclusiones, derivadas de
partida para la eliminación efectiva de los trabajos de la planta de San Diego:
incrustaciones. Sin embargo, los datos expe 1. La curva práctica de operaciones de
rimentales crean dudas de que esto sea así. terminada para el hemihidrato tiene
Una distribución no uniforme de las incrus una pendiente mayor que la curva
taciones indicó que probablemente se había derivada de las condiciones de equili
producido ebullición en el calentador de brio de Standiford y Sinek.
aguas madres inmediatamente antes de la
última corrida. Esta conclusión se basaba 2. Podría ser posible para plantas de
en ciertas dificultades de funcionamiento destilación instantánea operar por
registradas mientras se realizaban los expe períodos largos en la zona metaestable
rimentos. Bajo estas condiciones, un reca- sobresaturada de anhidrita y del hemi
lentamiento de las paredes podría haber hidrato.
causado la formación prematura de las 3. Pueden ser necesarias curvas diferen
incrustaciones, en contraste con una opera tes de operación para describir las
ción bajo condiciones de no-ebullición. Una condiciones límites del sulfato de cal
vez iniciada la formación de depósitos, que cio para diferentes tipos de evapo-
actúan como núcleos de cristalización, radores.
puede suponerse que habrá una formación En todo caso, debemos tener presente
rápida de depósitos incluso si fuera reini- que no es posible aplicar indiscriminada
ciada una operación bajo condiciones de mente curvas desarrolladas inicialmcnte
no-ebullición. La última serie de experi para un determinado equipo, bajo un grupo
mentos no pudo completarse debido a que de condiciones dadas, a cualquier otro pro
la planta fue desmantelada y enviada a la ceso de destilación.

158
Improvement in Fabrication

Techniques for Reverse Osmosis

Desalination Membranes

S. Manjikian, S. Loeb, J. W. McCutchan

United States of America

INTRODUCTION
The term osmosis is used to describe in testing "Ultrafinc, Superdense" cellulose
spontaneous flow of water into a solution, acetate ultrafilters obtained from Schleicher
or from a dilute to a more concentrated and Schuell Company, Keenc. New Hamp
solution when the two are separated from shire, they undertook the fabrication of
each other by a semipermeable membrane. cellulose acetate membranes in the UCLA
In order to obtain fresh water from saline laboratory. Acetone was used as the solvent
water, the flow must be reversed from the and, based on work by Dobry (ref. 1) ,
solution into a fresh water stream, hence aqueous magnesium perchlorate was in
the term reverse osmosis. cluded in the casting solution as one of
Since 1952 when the first compendium the steps to control membrane porosity.
on "Existing and Potential Separation Loch and Sourirajan published the results
Processes," (ref. 11) was published, the of their development by which cellulose
search has gone on for a practical reverse acetate membranes with flow rates of from
osmosis desalination membrane. In this first 5 to 11 gal/ft=day could be made to produce
published list, two references were given, potable water from sea water at 1300 psig
Hassler (ref. 2) and an anonymous refer operating pressure.
ence. The next reported activity was from In essence, their technique is as follows:
Reid and Breton (ref. 12) , and Yustcr. 1. The casting solution is a quaternary
Sourirajan. and Bernstein (ref. 14) who. mixture of cellulose acetate-magnesium
although working along different paths, perchloratc-water-acetone in the proportions
arrived at the same conclusion, namely, 22.2-1.1-10.0-66.7 per cent by weight. Loeb
that cellulose acetate membranes have a and Manjikian (ref. 8) have reported im
high degree of semipcrmeability to saline provements with the addition of small
solutions. quantities of a fifth component such as
On the basis of the work of Reid and hydrochloric acid.
Breton, others (ref. 13) undertook improve 2. The membrane is cast on a glass plate
ments in membranes on the hypothesis having 0.025 centimeter side runners to
that the transport mechanism involved give this as-cast thickness to the membrane.
hydrogen-bonding. Membranes with large The casting solution and all casting com
numbers of known hydrogen-bonding sites ponents are at —5° to — 10°C.
were tried without success. It was also be 3. After an evaporation period of not
lieved that crosslinking of cellulose acetate- more than three minutes at this tempera
would improve the physical properties of ture, the membrane plate assembly is im
the membrane, but efforts in this direction mersed in ice water where it is kept for
seemed to be at the expense of permea about one hour.
bility. 4. The membrane is removed from the
Loeb and Sourirajan (ref. 9) took another plate and heated by immersion in water
approach. On the basis of experience gained for 5 minutes at 65° to 85°C.

159
PRESENT STUDY technique and reported on permissible mod
No fundamental improvement has been ifications thereto. It is the continuing
reported in the casting solution or other quest for a better and simpler system, both
fabrication steps since 1960, although a in the casting solution composition and the
number of investigators have considered fabrication procedure, that has led to the
the mechanisms involved in this fabrication advances reported in this paper.

PROCEDURE
CASTING SOLUTION CONSTITUENTS Additives may be characterized as flux-
inducing components of a casting solution
The various components of the casting for the preparation of semipermeable cel
solution may be considered in the light of lulose acetate membranes. To date, investi
their integration into the fabrication tech gations have been concerned mainly with
niques described above. On this basis, aqueous solutions of inorganic electrolytes
general requirements may be stated for the as additives. Since magnesium Perchlorate
various casting solution components. was one of the first to be used in this capac
1. Cellulose Acetate ity, it is not surprising to note that later
The cellulose acetate should have an efforts were directed toward the investiga
acetyl content, molecular weight, and mo tion of salts similar to magnesium Perchlo
lecular weight distribution in the same rate in their physical and chemical
general range as Eastman E-598-3 powder. properties. In addition, the successful prepa
(In a later section the influence of these ration of the high flux membranes was re
parameters on membrane performance for lated to the structural properties of these
the new casting technique developed is electrolytes.
described.)
2. Solvent Exhaustive experiments have increased
An appropriate solvent for the casting the number of inorganic electrolytes that
solution should meet the following mini serve as successful additives. Loeb (ref. 7)
mum requirements: has stated that these electrolytes, by virtue
(a) Miscibility with water, since the sol of their anions, have a common property in
vent is removed from the gel upon immer their ability to "break" the structure of
sion in water. water. Since this was the only common
(b) Lack of chemical reactivity with quality, he concluded that the modification
other casting solution components. of the structure of water was the primary
Binary solutions of cellulose acetate in role of electrolytic additive. Resting and
acetone and similar solvents will produce Keilin (ref. 4) in their consideration of the
an impermeable membrane, but a solvent additive as a swelling agent for cellulose
such as glacial acetic acid can produce a acetate have assigned the active role to the
permeable membrane (ref. 6) . These sol cation. Again the need for an electrolyte
vents may be defined as "nonswelling" and was emphasized.
"swelling" solvents, respectively. When the 4. Water
casting solution contains a "nonswelling" Water is a desirable component of cast
solvent, one or more "swelling" components ing solutions containing electrolyte (ref. 7) ;
or "additives" must also be included as however, it is not assumed in this study
discussed below. In such a casting solution, that water is essential in every cellulose
the solvent has two additional requirements: acetate casting solution. Although water
(c) Miscibility with the additive. constitutes a large fraction of a high per
(d) The capability of being leached out formance cellulose acetate desalination
of the water-immersed membrane prior to membrane, most of this water enters the
the additive. If the additive were removed membrane upon immersion, i.e., is over
first, the remaining casting solution would and above that contained in the casting
be an undesirable binary, consisting solely solution.
of cellulose acetate and "nonswelling"
solvent. EXPERIMENTAL PROCEDURE
3. Additives The casting solutions fabricated into
Additives should have requirements (a) membranes contained cellulose acetate as
and (b) above, plus: one component of a binary, ternary, or
(C) Miscibility with the solvent. quaternary mixture. The other compo
(d') The capability of being leached nents were always nonelectrolytes and usu
from the film subsequent to the solvent. ally organic. The casting procedure was
160
"mity-mite" PRESSURE GAUGE
BACK
PRESSURE
REGULATOR OSMOTIC CELL, 600psig

MEMBRANE

DESALINIZED WATER-7
(LESS THAN 7cm3/min.)
RETURN BRINE
V
TEN MICRON
CUNO FILTER

AIR-OPERATED PUMP

FEED BRINE
0.5% NQCI
300 cm3/min

FIGURE 58. FLOW SYSTEM SCHEMATIC.

similar to that already described, with inized water obtained. Membranes made
modifications as indicated by the results from the aqueous magnesium perchlorate
obtained. Membranes were tested in the modificd casting solution give fluxes up to
apparatus of Figures 58 and 59 at an ap 25 gal/ft*day and salt contents as low as
plied pressure of 600 psig and with a feed 300 ppm NaCl (ref. 8) . In this study efforts
brine of 0.5 per cent by weight (5.000 ppm) were not always made to optimize perform
sodium chloride. ance. Usually a membrane which delivered
Membrane performance was judged by a flux of 5 gal/ft'day at a salt content less
the flux and the salt content of the desal than 1,000 ppm was considered promising.

RESULTS
FORMAMIDE CASTING SOLUTIONS cause it possesses inadequate solubility for
Formamide was first tried in the fall of 1963 cellulose acetate. Manjikian (ref. 10) then
as a substitute for acetone in the quaternary considered formamide as a substitute for
casting solution cellulose acetate-magnesium water in the basic magnesium perchlorate
perchlorate-water-acetone.# Formamide was formulation. Membranes fabricated from
not useful for this purpose probably be- this casting solution gave acceptable per
formance. This result led him to experi
* Dr. Gordon Atkinson of the University of ment with formamide as a replacement for
Maryland suggested this use of formamide at an both water and magnesium perchlorate,
informal meeting during an ACS Symposium i.e., to try a casting solution consisting of
there. It was his opinion that formamide, with its
high dielectric constant, might be more useful the ternary mixture cellulose acetate-form-
than acetone with the aqueous electrolytes In the amide-acetone.
casting solution.

161
1 . Casting Solution Composition Thus, the range of casting solution studied
First, membranes were fabricated from was:
various combinations of the three compo Cellulose Acetate 20-30 wt %
nents to ascertain the region of best per Formamide 10-40 wt %
formance. The region of permissible casting Acetone 35-65 wt %
solutions was limited to a large extent by Table XXIII summarizes the work done
the physical properties of the casting solu with membranes prepared from casting solu
tion and the membrane obtained. Consider tions of various compositions. These mem
ing casting solution viscosity, cellulose branes were cast both at — 10°C and at
ambient temperature (23°C) . Figure 60 is
acetate concentrations were kept in the a ternary diagram of the casting system.
range 20 to 30 per cent. If formamidc The shaded area represents combinations of
concentration exceeded 40 per cent, solu the three components from which useful
tion solubility problems were encountered. membranes were prepared.

POROUS
STAINLESS STEEL
BACKUP PLATE
LOW
PRESSURE
0-RINGS
DESALINIZED 7
HIGH WATER OUTLET
PRESSURE OSMOTIC
0-RINGS MEMBRANE

RETURN BRINE FEED BRINE


OUTLET INLET
\\\\\\\\\\\\\\\\\\\\\\^

FIGURE 59. DESALINATION CELL-CROSS-SECTIONAL VIEW.

162
FORMAMIDE RANGE
10% -40%

ACETONE RANGE
35% -65%

CELLULOSE ACETATE FORMAMIDE


FIGURE 60. CASTING SOLUTION REGION
CELLULOSE ACETATE-FORMAMIDE-ACETONE SYSTEM.

Several important conclusions can be procedure was equivalent to adding varying


drawn from the results presented in Table quantities of formamide to a 45.4 per cent
00. First, as can be seen from consideration solution of cellulose acetate in acetone. The
of solution 1, the function of aqueous mag results of Table XXIV are shown in graph
nesium perchlorate cannot be carried out form in Figure 61. Three conclusions can
gram-for-gram by formamide. Second, the be drawn from this figure. First, it was
formamide concentration had to be 20 per indicated that the percentage of formamide
cent or higher to get successful membranes. should exceed 30 to 35 per cent for maxi
Third, good performance could be obtained mum flux. Second, the flux was primarily
from membranes cast at room temperature. a function of formamide content. Third,
Next, the influence of formamide concen the flux attains a maximum and then drops
off with further increase in formamide.
tration on flux was further explored in This must be attributed to weakening of
room temperature casting. The membranes the membrane due to an excess of forma
were tested without heating in order to mide in the casting solution. Thus, upon ihe^j. ~
eliminate this variable. Tabic XXIV shows application of pressure, the membrane
results obtained with casting solutions hav compacted excessively, increasing the resist
ing 25 per cent concentration of cellulose ance of the porous understructure.
acetate, the ratio of fonnamide:acetone
being varied. Also shown are results with 2. Evaporation Period
solutions for which the ratio cellulose The results of varying evaporation pe
acctateracetone was held constant at 5:11 riods for membranes cast at room tempera
while the quantity of formamide in the ture from composition 7 (standard) are
casting solution was varied. This latter shown in Table XXV and Figure 62. All of
163
TABLE XXIII. Performance of Membranes Cast From Various Ternary Mixtures of
Cellulose Acetate-Formamide-Acetone
Cast at — 10°C
Casting solution composition Evaporation Heating Desalinated water
Solution (wt %)
no. penoa
Cellulose Formamide Acetone (min.) CO Flux Salt content
acetate <gal/ft"day) (ppm)
1 22.2 11.1 66.7 10 78.0 12 810
2 21.4 14.2 64.4 10 78.0 30 610
8 81.1 11.1 67.8 10 Unbeated 6.5 880
4 25 10 65 10 68.5 4.6 270
6 25 20 65 10 77.0 17 220
6 25 25 50 6 79.5 27 480
7 25 SO 45 6 81.5 22 190
8 26 35 40 8 85.8 14 150
Cast at 23°C
9 29.1 16.7 54.2 1 Unheated 2.7 810
10 80 14.8 55.7 1 Unhealed 8.1 410
7 25 SO 45 1 74.0 80 410
6 25 25 60 1 71.6 15 270
6 25 20 56 1 66.0 15 860
Cell operating pressure: 600 psig
Feed brine: 0.5% (5.000 ppm) NaCl

TABLE XXIV. Effect of Formamide Concentration in Casting Solution on Desalinated


Water Flux Through Unheated Membrane
__ . . . ratio
VVemht Cellulose
.. —,-j-acetate _ , .„
Formamide acetone Constant at 1/8
Casting solution composition (wt %) Desalinated water
Solution no. Cellulose Flux
acetate Formamide Acetone (gal/ft* day)
4 25 10 66 0.6
11 25 15 60 3.0
6 25 20 66 9.5
6 25 25 60 76
7 25 80 45 160
8 25 36 40 170
12 26 40 35 160
m ■ «... ratio
Weight ». Cellulose
.—: acetate Constant
_ at 6/11
Acetone
13 29.4 6.9 64.7 0.48
14 27.7 11.1 61.2 0.90
15 26.2 16.2 67.6 8.0
6 25 20 65 9.5
16 23.8 23.9 52.8 43
17 22.7 27.8 60 110
18 21.8 80.4 47.8 200
19 20.8 83.3 45.9 200
20 20 86 44 190
Casting temperature: 23°C Cell operating pressure: 600 psig
Evaporation period: one-half minute Feed brine: 0.5% (6,000 ppm) NaCl
200 r- • CA: AC CONSTANT AT 5:11 PARTS BY WT TABLE XXV. Effect of Evaporation Period
O CA:(AC + F)CONSTANTAT 1:3 PARTS BY WT on Membrane Performance

Evaporation Desalinated water


period Flux Salt content
(mln.) (gal/ft" day) (ppm)
0.25 84 1,900
100 1 0.60 47 660
1.0 26 580
1.5 84 780
2.0 25 1,100
2.5 23 1.200
S.O 26 1,700
Casting solution composition No. 7:
26% cellulose acetate, 30% formamide,
46% acetone.
Casting temperature: 23'C
Heating temperature: 71.0° to 71.6°C
Cell operating pressure: 600 psig
Feed Brine: 0.6% (6,000 ppm) NaCl
z
<m modified membrane, except that a slightly
UJD higher heating temperature is required
with membranes made from the formamide
casting solution.
TABLE XXVL Effect of Heating Temper
ature on Membrane Performance

Heating Desalinated water


10 20 30 temperature Flux Salt content
WEIGHT PERCENT FORMAMIDE CO (gal/ft»day) (ppm)
IN CASTING SOLUTION Unheated 95 3,800
FIGURE 61. EFFECT OF FOR 70.0 45 800
76.0 80 250
MAMIDE CONCENTRATION 110
IN CASTING SOLUTION ON 78.0 17
81.0 12 85
DESALINATED WATER FLUX
THROUGH UNHEATED MEM Casting solution composition No. 7:
25% cellulose acetate, 30% formamide,
BRANE. 45^fc acetone.
See Table XXIV Casting temperature: 23°C
Evaporation period: one-half minute
Operating pressure: 600 psig Cell operating pressure: 600 psig
Feed brine: 0.5% (5000 ppm) Nad Feed brine: 0.6% (6,000 ppm) NaCl
4. Cellulose Acetate Specifications
the membranes were heated to 71.0° to
71.6°C. Evaporation periods longer than The development of a reliable room
one and one-half minutes were too long temperature-castable ternary mixture sim
since, for longer periods, salt content began plifies the examination of casting param
to rise for a given flux. With regard to eters. One parameter which was so exam
periods shorter than one-half minute, it ined was that of cellulose acetate type.
appears that higher heating temperatures Cellulose acetate desalination membranes
might bring performance into the desired have most frequently been fabricated from
range. By contrast, when membranes made Eastman 398-3. (The term_398 means that
from this composition were cast at — 10°C, the polymer_£QDXairis_aii average ot 39.8
the optimum evaporation period was 10 weipfrr~pe7rfnt nf arrLyl ei('ilp<r~Arpr"Y;-
minutes. mately 81 per_cem_-Qf_the. hydroxy! jjroups
have ^r^'axelylated. The term -3 refers
3. Membrane-Heating Temperature to a viscosity rating, which ultimately
The influence of heating temperature on reflects polymer molecular weight.)
membrane performance is shown in Table A study was undertaken with the stand
XXVI. The trend is similar to that obtained ard composition 7 to determine the influences
with the aqueous magnesium perchlorate on membrane performance of three cellu-

165
100

75 h-
£E o
UJ "O
< —
50
N_

<
tn 25H
UJ
Q

E °L
Q. 2000r
Q.

£ 1500 1-
o
o

1000 \

<
o 500
UJ
N

4
(A 1 1
UJ 0.0 1.0 2.0
o 3.0
EVAPORATION PERIOD, MINUTES
FIGURE 62. EFFECT OF EVAPORATION PERIOD OF FORMA-
MIDE-MODIFIED MEMBRANE PERFORMANCE.
See Table XXV.
Operating pressure: 600 psig
Feed brine: 0.5% (5000 ppm) NaCl

lose acetate variables, viz: molecular weight, slight trend toward a required lower heat
molecular weight distribution, and per cent ing temperature with higher molecular
acctylation. Cellulose acetate samples were weight, as shown by the results with E-594.
provided through the courtesy of Mr. The influence of molecular weight dis
William Gearhart, Eastman Chemical Prod
ucts, Kingsport, Tennessee. tribution is shown in Table XXVI II and
The results with regard to influence of Figure 63. As shown in this figure, the "nar
molecular weight are shown in Table row" distribution appeared to give a slightly
XXVII. Molecular weight did not markedly flatter flux-salt content curve than the
affect membrane performance. There was a "medium" and "wide" distributions. These

166
TABLE XXVII. Effect of Cellulose Acetate Molecular Weight on
Membrane Performance
Cellulose acetate Desalinated water
Molecular Heating
Acetyl Viscosity (wt«) temperature Flux Salt content
content indicator CO ( gal/ft' day) (ppm)
(per cent) ( Eastman )
39.4 - 30 50,000 79.0 34 660
- 45 51,000 79.0 32 510
(E-894) - 60 55,000 76.6 33 440
89.8 - 3 24,000 76.6 80 300
- 6 34.000 75.6 80 840
(E-S98) - 10 39,000 75.6 29 290
•From Mr. W. Gearhart, Eastman Chemical Products
Casting solution composition No. 7: 25% cellulose acetate, 80% formamlde, 46% acetone.
Casting temperature: 23°C
Evaporation period: one-half minute
Cell operating pressure: 600 psig
Feed brine: 0.5% (5,000 ppm) NaCl
curves were obtained by heating desalinated tion cellulose acetate may be slightly less
water to various temperatures. Therefore, it sensitive to heating temperature than those
appears probable that the performance of made from cellulose acetate having a wider
membranes made from a narrow distribu distribution.

TABLE XXVIII. Effect of Cellulose Acetate Molecular Weight Distribution on


Membrane Performance
Heating Desalinated water
Molecular wt Eastman temperature
distribution identification no. Flux Salt content
CO (Kal/ft-'/day) (ppm)
Narrow CAE-2196-1 72.0 82 370
Normal CAE-2 196-2 72.0 41 480
Wide CAE-2196-3 72.0 38 340
Narrow CAE-2196-1 74.6 27 240
Normal CAE-2 196-2 75.6 24 140
Wide CAE-2196-8 76.4 27 200
Narrow CAE-2196-1 77.8 24 120
Normal CAE-2196-2 77.8 22 100
Wide CAE-2196-8 77.8 22 100
Cellulose acetate similar in acetylation and molecular weight to E-398-3.
Casting solution composition No. 7: 26% cellulose acetate, 30% formamide, 45% acetone.
Casting temperature: 28°C
Evaporation period: one-half minute
Cell operating pressure: 600 psig
Feed brine: 0.5% (6,000 ppm) NaCl
The influence of acetylation on mem Of these materials only 602-C formed a
brane performance was examined by con homogeneous solution in the standard com
sidering two groups of polymers, one having position proportions. This composition gave
a higher degree of acetylation than the satisfactory performance. 25 gal/ft2/dav and
standard E-398-3. and the other a lower fiOO ppm when heated to 70°C.
degree of acetylation. The three samples of Results with polymers having a lower
higher acetylation, otherwise similar to degree of acetylation than E-398-3 are
shown in Table XXIX and Figure fit.
E-398-3, were designated as follows: These included:

Eastman Acetyl Degree of Eastman Acetyl Degree of


designation content acetylation designation content acetylation
per cent per cent per cent per cent
602-A 41.6 88 EMP-949-A 38.9 79
602-B 41.0 86 EMP-949-B 37.5 75
602-C 40.1 83 EMP-949-C 37.1 74

167
ACETATE
MCON
OF
EFFECT
63.
DFIGURE
WEIGHT
OIESLTERICUBLUOTIASOREN

(CAE
I)

2196
MNDWOIAESLTRI-CGBULOHTIATWRN 450

O«».R.MAL (CAE
N(CAE
O
-2)
-2196 A
-3)
W..IDE.
-2196

brine:
Feed
NaCl
0.5%
(5000
ppm)
amide-mbodrifainede
Form
DEppm
CONTENT
SALT
WATER
SALINIZED
150
250
350

PMERFMOBRMANCE.

psig
600pres ure:

X VI I

50 Table
See Operating
501~
^
!40 30- 5
20 ?
10
cr _i
D TJ o x3 o UJ N <
40 HEATING TEMP
О
тз

CT

Б 30

20

<
о
ш
У 10

<
СП

■69° С

Е
о.
800
ЕМР- EASTMAN
Z 949 -В
ш DESIGNATION EMP-
949 -А
о
и
600

со
к
ш
< 400 72е С

О
UJ
N

^ 200 •75вС

37 38 39
ACETYL CONTENT, PER CENT
FIGURE 64. EFFECT OF CELLULOSE ACETATE ACETYL ON
MEMBRANE PERFORMANCE.
See Table XXIX Feed brine: 0.5% (5000 ppm) NaCl
Operating pressure: 600 psig Formamide-modined membrane
169
TABLE XXIX. Effect of Cellulose Acetate Acetyl Content on
Membrane Performance
Desalinated water
Acetyl content Eastman Heating-
(per cent) Identification no. temperature Flux Salt content
CO <gal/ft»/day) (ppm)
88.9 EMP-949-A 69.0 33 940
87.6 EMP-949-B 69.0 34 940
87.1 EMP-949-C 69.0 20 860
88.9 EMP-949-A 72.0 24 480
87.Б EMP-949-B 72.0 29 640
87.1 EMP-949-C 72.0 14 440
88.9 EMP-949-A 76.0 18 210
87.6 EMP-949-B 76.0 16 810
87.1 EMP-949-C 76.0 7.6 250

Cellulose acetate similar in molecular weight to E-S98-3.


Casting solution composition No. 7: 26% cellulose acetate, 30% formamide, 46% acetone.
Casting temperature: 23°C
Evaporation period: one-half minute
Cell operating pressure: 600 psig
Feed brine: 0.6% (6,000 ppm) NaCl
The chief conclusion to be drawn from This membrane represents an advance
these curves is that the 37.1 per cent in efforts to develop a practical membrane
content appears to be outside the lower cast at room temperature. Resting (ref. 3)
limit for obtaining good performance. succeeded in casting aqueous magnesium
It may be concluded therefore that good Perchlorate membranes at room tempera
performance can be obtained between 37.5 ture by using p-dioxane as the solvent
and 40.1 per cent acetyl content. Within instead of acetone but had difficulty in
this range no specific correlation can be obtaining reproducible results.
stated between either flux or desalination
and acetyl content. CASTING SOLUTIONS CONTAINING
5. Reproducibility OTHER NONELECTROLYTES
The composition 7 formamide solution, Nonelectrolytic materials other than form
cast at room temperature, has completely amide have been used in casting solutions
replaced the cold-cast aqueous magnesium
Perchlorate solution as the standard casting to produce cellulose acetate desalination
solution for UCLA desalination membrane membranes showing promise. These solu
work, since membranes with reproducibly tions are listed in Table XXX in accordance
high performance and good physical prop with whether they are quaternary, ternary,
erties can be obtained. or binary.

170
Saltcontent
(ppm) o© o oo 88 St- Sti 8 3t- 2H
S5 5 S2 ion n lis!
!
1a
o
>.(0
! o u> T o M OO
Q Is AC4 _ td oo ci
r«» egO vhCO ts«B tm m o to us
m

£ Unheated Unheated Unheated


63.3 70.3 78.5 80.5 60.0 62.0 75.0 79.0 77.5 76.0 93.0 93.0 94.0
5|P
«|
Evaporation
period (min) ■oo
<0tO •Ht- OO
t-te-l COCO CO *HO C4 CN <0f-4 00 ©vH v-lvH

temperature
Casting OO O oo eoeo co04 COOJ CO<N O COCM
CO CJCN -Ho ofH fto flo
TT 7 77 1 1 1 1 1

sCoalsutiong CA14.S-
composit on

(%)
wt G4.6lyo-xal N13.0-M-2-P
Urea3.3- HaO18.2- 62.5Acet- Acet64.8- HiOj2.6- Acet65.0- DMF21.4- Acet64.8- DMSO87.6- Acet87.6- THFP20- Acet60- TEP25- Acet60- 68.4Acet— Acet65.0- DMF76- 80TEP-
CA21.0- CA- HiO9.2- CA22.0- HjO10.4-
21.5 25.0CA- 20CA- CA25- CA22.6- AA9.1- CA22.0- CA25- CA20- 80AA- 20CA-

ua
Tetrahydrofur- furylphosphate ■»*
Ad itive compound pyr olidone aDO AE
Hydrogen peroxide Dimethyl-formamide Dimeth-ylsulfoxide Triethyl-
phosphate acidAcetic N-methyl-2- Dimethyl- formamide acidAcetic Triethyl- phosphate
Glyoxal ■•o 9o
Urea Eo
1$ 8
Is
Quaternary component) 9 BU 3 8
Type of solution Ternary
(water fourth Binary " -J I *
being 13o u.* u< <w

171
With regard to the quaternaries of Table formate, acrylic acid, oleic acid, phenol,
XXX, hydrogen peroxide is of special inter propionic acid, diethanolamine, diethyl-
est as an additive. Since water itself is use phthalate, tetrahydrofuran, diethylaraine,
less as an additive, it is quite surprising that acetonitrile, and pyrocatechol.
partial replacement of the water by such a The inadequacy of some of these mate
closely related compound makes so much rials must be attributed to their failure to
difference in membrane performance. Since meet some of the previously stated neces
it has been shown that the utility of elec sary requirements of additives. However,
trolytic additives is independent of their compounds which met all four require
oxidizing capabilities, it is unlikely that ments and still were unsuccessful illustrate
the utility of hydrogen peroxide is due to the insufficiency of these requirements.
this effect.
As for the ternaries, tetrahydrofurfuryl ETHYL CELLULOSE MEMBRANES
phosphate is an incomplete solvent for cel This paper is concerned primarily with
lulose acetate, as is formamide. In contrast cellulose acetate membranes. However, it is
to formamide, dimethylsulfoxide, N-methyl- of interest to note that promising ethyl
2-pyrrolidone. dimethylformamide, methyl cellulose desalination membranes can be
phosphate, and acetic acid are complete cast from suitable ternary mixtures, whereas
solvents for cellulose acetate, and the latter it has not been found possible to use ethyl
three are useful in binary mixtures. cellulose satisfactorily in the aqueous mag
A number of organic compounds gave nesium perchlorate casting solution (ref.
clear homogeneous solutions in ternary 5) . On the other hand, a ternary mixture
mixtures with cellulose acetate and acetone, of ethyl cellulose:triethylphosphate:dioxane
but were not useful in producing good gave reasonably promising performance, as
membranes. This group included methyl shown in Table XXXI.
TABLE XXXI. Performance of Membranes Prepared from Ethyl Cellulose
Casting solution composition, wt (%) Evaporation Heating Desalinated water
Ethyl Triethyl- period temperature Flux Salt content
cellulose phosphate P-dioxane (mln) <°C) (nal/ftVday) (ppm)
11 9 80 20 Unhealed 4.S 600
11 9 80 20 81.0 o.e 400
18 14 78 20 Unheated 4.8 700
Casting temperature: 23°C
Cell operating pressure : 600 psig
Feed brine: 0.6% (5,000 ppm) NaCl

CONCLUSIONS
1. Reproducibly high performing cellu it is clear that no ion-ion or ion-dipole
lose acetate membranes can be cast at room interaction is required between casting com
temperature from ternary solutions of cellu ponents at any stage of fabrication. This
lose acetatc-formamide-acetone. The per latter statement also applies to casting
formance and physical properties are equal solutions containing water, as witnessed bv
to or better than those of membranes the utility of urea, glyoxal, or hydrogen
cold-cast from casting solutions containing peroxide in quaternary mixtures with cel
aqueous electrolytes. lulose acetate-water-acetone.
2. The development of successful binary 3. It is possible at the present time to
and ternary mixtures demonstrates unequiv state definitive necessary but insufficient
ocally that neither water nor electrolytes conditions for components in cellulose ace
are necessary as components of casting tate casting solutions.
solutions. As a corollary to this statement.

ACKNOWLEDGEMENTS
This study was supported by funds pro- versity of California Statewide Water Re-
vided by the California State Legislature. sources Center located on the Los Angeles
They are administered through the Uni- campus of the University.

172
REFERENCES
1. Dobry, A.: Bull, de la Société Chim. de sity Microfilms, Inc., Ann Arbor,
France, J« Serie, t. III, (19S6) pp. 312- Michigan (64-12525).
318. 8. Loeb, S.; Manjikian, S.: "Brackish
2. Hassler, G. L.: "The use of molecular water desalination by an osmotic mem
oil films in a pressure method (or brane," Univ. of California, Dept. of
obtaining irrigation water from the sea," Engr., Los Angeles, Progr. Rept. no.
Univ. of California, Dept. of Engr., Los 63-22 (May 1963) .
Angeles (Aug. 1950) . 9. Loeb, S.; Sourirajan, S.: Advan. Chem.
3. Resting, R. E.: /. Appl. Polymer Sei. Ser. no. 38 (1962) pp. 117-132.
vol. 9 no. 2 (Feb. 1965) pp. 663-668.
4. Resting, R. E.; Reilin, В.: "The mech 10. Manjikian, S.: "Semipermeable desali
anism of desalination by reverse nation membranes from organic casting
osmosis," U.S. Department of the Inte solutions," Univ. of California, Dept. of
rior, Office of Saline Water R&D Progr. Engr., Los Angeles, Rept. no. 65-13
Rept. 84 (Nov. 1963) . (May 1965) .
5. Loeb, S.: "Sea water demineralization 11. Office of Technical Services: "Deminer
by means of a semipermeable mem alization of saline waters, a preliminary
brane," Univ. of California, Dept. of discussion of a research program, with
Engr., Los Angeles, Progr. Rept. no. an outline and description of potential
61-42 (Aug. 1961) . processes and a bibliography," U.S. De
6. Loeb, S.: "Sea water demineralization partment of the Interior, PB 161373
by means of a semipermeable mem (Oct. 1952) .
brane," Univ. of California, Dept. of 12. Reid, С. E.: Breton, E. J.: /. Appl.
Engr., Los Angeles, Progr. Rept. no. Polymer Sei. no. 1 (1959) pp. 133-143.
63-32 (July 1963) . 13. "Saline water conversion report," U.S.
7. Loeb, S.: "Appropriate electrolytic ad Department of the Interior, Office of
ditives in a casting solution used for Saline Water (1960) .
the production of high performance 14. Yuster, S. T.; Sourirajan. S.; Bernstein,
cellulose acetate membranes used in R.: "Sea water demineralization by the
reverse osmosis desalination," Ph.D. Dis 'surface skimming' process," Univ. of
sertation. Univ. of California, Dept. of California, Dept. of Engr., Los Angeles.
Engr., Los Angeles (May 1964) , Univer- Rept. no. 58-26 (Mar. 1958).

SUMMARY OF DISCUSSION
There was no discussion.

173
Perfectionnement Des Techniques de

Fabrication Des Membranes Utilisées

Dans le Procède de Dessalement Par

Osmose Inversée

S. Manjikian, S. Loeb, J. W. McCutchan

Etats-Unis d'Amérique

Au cours de la dernière décennie, le mersion dans l'eau. Troisièmement, si le


procédé de dessalement par osmose inversée solvant se révélait incapable de produire à
a fait des progrès tels, qu'il est sur le point lui seul une membrane semi-perméable à
de devenir compétitif. Ces progrès sont, haut débit, au moins un composant com
pour une grande part, dus à la mise au plémentaire devait être ajouté à cette fin.
point d'une membrane ayant un rendement Ces additifs devaient être miscibles avec le
amélioré, du point de vue des qualités de solvant et avec l'eau, et être en outre
la membrane en ce qui concerne le dessale chimiquement inactifs. Quatrièmement, dès
ment d'une part et d'autre part le débit son immersion dans l'eau, l'additif devait
d'eau dessalée. Ce perfectionnement techno pouvoir être soumis à la lixiviation et
logique de la membrane utilisée dans l'os extrait du gel par la solution dans l'eau
mose inversée résulte de deux événements d'immersion, de préférence après le solvant.
capitaux: Pour ce qui est du reste de la technique
1. La découverte par Reid et Breton de fabrication des membranes, la gamme
que l'acétate de cellulose est fortement d'opérations qui avait antérieurement été
semi-perméable aux sels marins. Sourirajan retenue par Loeb et Sourirajan a été suivie.
parvint indépendamment à la même con Les étapes de ces opérations comprenaient:
clusion et ajouta l'acétobutyrate de cellulose l'immersion de la membrane, ordinaire
à la liste. ment dans de l'eau glacée, pendant une
2. La mise au point par Loeb et Souri durée déterminée à l'avance après l'étale
rajan d'une technique de fabrication en ment de la pellicule et, enfin, le chauffage
vertu de laquelle les membranes d'acétate de la membrane à la température requise
de cellulose ont un débit suffisamment élevé pour produire de l'eau douce selon le maté
d'eau potable pour rendre le procédé inté riel de dessalement utilisé. Les membranes
ressant sur le plan commercial. furent ensuite soumises à des essais dans
Dans leur technique de fabrication, Loeb une petite cellule de dessalement capable
et Sourirajan utilisèrent une solution de de faire passer rapidement de la saumure
coulée à l'acétone à laquelle, en se basant sous pression sur la surface de la membrane
sur les travaux antérieurs de Mlle Dobry. et d'évacuer l'eau dessalée avec un mini
furent ajoutés des électrolytes aqueux, tel mum de résistance à son écoulement.
que le perchlorate de magnésium. La pré La meilleure solution de coulée obtenue
sente communication traite de la mise au jusqu'à présent est un mélange ternaire
point de solutions de coulée utiles ne con d'acétate de cellulose-formamidc-acétone
tenant que des composants non électrolytes. dans la proportion de 25:30:45 pour cent
Les lignes directrices de l'étude ont été par poids. Les membranes obtenues à partir
obtenues sur la base de résultats antérieurs. de cette solution de coulée sont égales, voire
Tout d'abord, on a utilisé de l'acétate de supérieures aux meilleures membranes ob
cellulose similaire à l'F.astman 398-3. Deu tenues à l'aide de la solution de coulée
xièmement, le solvant de l'acétate de cellu modifiée par électrolytes qui était utilisée
lose devait être chimiquement inactif et auparavant. Les membranes modifiées à la
miscible avec l'eau, du fait que le solvant formamide donnent de bons résultats repro
est en grande partie retiré du gel par im ductibles et sont dotées de bonnes propriétés

174
physiques. Fait des plus importants, la solu Les mélanges quaternaires, qui avaient
tion à la formamide permet de procéder donné de bons résultats, contenaient un
rapidement à la coulée à la température composé d'acétate de cellulose-eau-acétone
ambiante, ce qui constitue une notable plus un quatrième composant (urée, gly-
simplification par rapport à la technique oxal ou eau oxygénée) . Cette dernière
antérieure, où il fallait couler à une tempé revêtait un intérêt particulier en raison de
rature de — 5 à — 10°C pour obtenir les son rapport chimique étroit avec l'eau,
meilleurs résultats. laquelle n'est d'aucune utilité en tant qu'ad
La solution à la formamide et les modi ditif. Les solutions de coulée ternaires
fications apportées à cette technique de retenues comme satisfaisantes contenaient
fabrication ont remplacé l'ancienne tech de l'acétate de cellulose-acétone plus un
nique employée pour les travaux de coulée troisième composant (phosphate de tétra-
ordinaires poursuivis par l'Université de hydrofurfuryle, oxysulfurc de diméthyle,
Californie, à Los Angeles. En voici un N-méthyle-2-pyrrolidone, formamide de di
exemple caractéristique: une membrane méthyle, phosphate de triéthyle, ou acide
modifiée à la formamide est plongée dans acétique cristallisable) .
de l'eau glacée après une période d'évapo- Le phosphate de tétrahydrofurfuryle est,
ration maximum d'une demi-minule à une au même titre que la formamide, un solvant
température ambiante. Par la suite, la incomplet pour l'acétate de cellulose. Par
membrane est chauffée dans de l'eau opposition à la formamide, l'oxysulfure de
chaude pendant 4 à 5 minutes. Pour ob diméthyle, le N-méthyle-2-pyrrolidone, la
tenir le dessalement de l'eau saumâlre formamide de diméthyle, le phosphate de
d'alimentation de, mettons, 5.000 ppm de triéthyle, et l'acide acétique sont des sol
chlorure de sodium, la membrane est vants complets pour l'acétate de cellulose,
chauffée à 75°C. On peut compter qu'une les trois derniers ayant leur utilité dans les
telle membrane fournira 25 à 30 gallons/ mélanges binaires.
pied carré-jour d'eau dessalée à 300 ppm Un certain nombre de composés orga
NaCl dans une cellule fonctionnant à 600 niques ont donné des solutions homogènes
livres par pouce carré de pression mano- claires dans les mélanges ternaires avec de
métrique. l'acétate de cellulose et de l'acétone, mais
La mise au point d'un mélange ternaire ne se sont pas révélés utiles pour la produc
sûr, susceptible d'être coulé à une tempéra tion de bonnes membranes. Ce groupe
ture ambiante, a simplifié l'étude des para comprenait la formiatc de méthyle. l'acide
métres de coulée. L'étude d'un de ces acrylique, l'acide oléique, le phénol, l'acide
paramètres s'est portée sur la spécification propionique, le diéthanolamine, le phtalate
de l'acétate de cellulose. Le poids molé de diéthyle, le tétrahydrofuranne, la di-
culaire, la répartition du poids moléculaire éthylamine, l'acétonitrile, et la pyroca-
et la teneur en acétyle (degré d'acétylation) téchine.
ont été examinés. Il a été constaté que dans L'imperfection de certains de ces maté
les limites prises en considération, le der riaux peut être attribuée a leur défaut de
nier facteur variable était le plus important, répondre aux exigences stipulées antérieure
les teneurs en acétyle entre 37,5 et 40,1% ment. Toutefois, certains d'entre eux ont
(degré d'acétylation entre 75 et 85%) con satisfait à toutes les exigences mais n'ont
venant le mieux à la production de bonnes cependant pas réussi à s'imposer, illustrant
membranes. ainsi l'insuffisance de ces exigences.
Il a également été observé que la tech La mise au point de mélanges binaires
nique relative à la solution de coulée et ternaires utiles démontre sans aucun
ternaire était applicable à la préparation doute que ni l'eau ni les électrolytes ne
de membranes éprouvées à partir d'éthylc- sont nécessaires à la composition des solu
cellulose. Dans ce cas particulier, la com tions de coulée destinées à la production
position de la solution de coulée était des membranes à l'acétate de cellulose
la suivante: éthylecellulose-phosphate de destinées à la déminéralisation. Cette dé
triéthyle-dioxane. monstration fait également largement res
sortir qu'aucune interaction, ion-ion ou ion-
Des matériaux non électrolytes autres que dipôle n'est nécessaire entre les composants
la formamide ont été utilisés dans les de la coulée à n'importe quel stade de la
solutions de coulée en vue de la production fabrication. Cette dernière démonstration
de membranes de dessalement à l'acétate de s'applique également aux solutions de
cellulose, offrant des perspectives intéres roulée contenant de l'eau, comme l'illustrent
santes. Ces solutions comprenaient des les solutions de coulée quaternaires dont les
mélanges quaternaires, ternaires et binaires. essais ont été couronnés de succès.

175
Усовершенствования в Методах

Промышленного Производства

Опреснительных Мембран, Работающих

Обратным Осмосом

С. Манджикиан, С. Леб, Дж. У. МакКотчан

Соединенные Штаты Америки

За последнее десятилетие обратный рых было установлено, что раствори


осмос подошел к той черте, за которой тель ацетата целлюлозы должен обла
он может стать конкурентоспособным дать химической неактивностью и сме
опреснительным процессом. Значитель шиваться с водой, так как в значитель
ная часть этого прогресса зависела от ной степени растворитель удаляется из
усовершенствования мембраны и ее гели посредством погружения в воду.
производительности, отразившейся на В-третьих выяснилось, что надо добав
опреснительных качествах мембраны и лять один или два дополнительных
интенсивности потока опресненной во компонента, если из растворителя са
ды. Эти достижения в области техно мого по себе невозможно выработать
логии мембран с обратным осмосом полупроницаемую мембрану с сильным
зиждились на двух основных усовер потоком. Такие добавки должны сме
шенствованиях. шиваться с растворителем и водой, и
1. Открытие Рейда и Бретона, что быть химически неактивными. В-чет
ацетат целлюлозы весьма прони вертых было обнаружено, что по по
цаем для солей морской воды. Су- гружению в воду следует иметь воз
рираджан нашел это независимо и можность выщелачивать из гели при
дополнил список ацетатным бути- садку растворением в иммерсионной
ратом целлюлозы. воде, и предпочтительно после раство
2. Усовершенствование Лебом и Су- рителя. Что касается остальных мето
рираджаном производственной те дов производства, то в общей сложно
хники, благодаря чему мембраны сти были использованы меры, ранее
из ацетата целлюлозы теперь вы рекомендованные Лебом и Сурираджа-
пускают достаточно большой по ном. К ним после распластания пленки
ток питьевой воды, чтобы сделать относилось погружение мембраны в во
процесс интересным с коммерче ду, обыкновенно ледяную, на заранее
ской точки зрения. установленный промежуток времени, а
Частью производственной техники затем нагревание мембраны до темпе
Леба и Сурираджана стало использо ратуры, необходимой для производства
вание ацетонного раствора для отлив пресной воды в зависимости от опре
ки, содержащего согласно предшество снительного оборудования. После этого
вавшей работе мадемуазель Добри, та мембраны испытывались в небольшой
кие водные электролиты, как перхло опреснительной ячейке, способной бы
рат магния. В настоящем докладе при стро пропускать сжатый концентрат в
ведено описание развития пригодных пространство над поверхностью мем
растворов для отливки, куда включены браны и выпускать опресненную воду
только не-электролиты. с минимальным сопротивлением по от
На основании предварительного опы ношению к ее протоку.
та были намечены вехи дальнейшей ис Наилучшим отливочным раствором,
следовательской работы. В первую который пока-что удалось получить,
очередь был использован ацетат цел оказалась тройная смесь ацетат целлю
люлозы, подобный Е -398-3. Во-вто лозы — формамид — ацетон с процент

176
яым соотношением 25 : 30 : 45 по весу. другие не-электролитические материа
Мембраны из этого раствора равноцен лы. К ним относились четверные, трой
ны или лучше самых лучших мембран, ные и двойные растворы. Удачные чет
которые делались из ранее употребляв верные растворы содержали ацетат
шегося электролитно-модифицирован- целлюлозы — воду — ацетон плюс чет
ного отливочного раствора. Формами- вертый компонент: мочевину, глиоксал
до-модифицированные мембраны, как или перекись водорода. Перекись во
правило обладают высоким коэффици дорода вызывала особый интерес, вви
ентом полезного действия и хорошими ду ее близкого сродства с водой ко
физическими свойствами. Весьма важ торая безполезна в качестве добавки.
но, что отливка из раствора формами- Удачные тройные отливочные раство
да всегда может происходить при ком ры содержали ацетат целлюлозы —
натной температуре, что является зна ацетон плюс третий компонент: тетра-
чительным упрощением по сравнению гидрофурфурил фосфат, диметилсуль-
с предшествовавшими приемами, при фоксид, Н-метил-2-пирролидон, диме-
которых отливка лучше всего произ тилформамид, трнэтилфосфат или ле
водилась при 5°С - 10°С ниже нуля. дяную уксусную кислоту.
Раствор формамида и соответствен Тетрагидрофурфурил фосфат явля
ные изменения методов производства ется неполным растворителем ацетата
заменили старую технологию стандарт целлюлозы, так же как и формамил.
ной отливки, выработанной Универси В противоположность формамиду ди-
тетом Калифорнии в Лос-Анжелосе. метилсульфоксид, Н-метил-2-пирролн-
Обычно формамидо-модифицированная дон, диметилформамид, трнэтилфосфат
мембрана после выпарки, берущей не и уксусная кислота являются полными
более 90 секунд и при температуре растворителями ацетата целлюлозы,
окружающей среды, погружается в ле причем последние три полезны в двой
дяную воду. После этого она нагрева ных смесях.
ется в течение 4-5 минут в горячей В тройных смесях ряда органических
воде. Для опреснения исходной воды, составов с ацетатом целлюлозы и аце
скажем, с содержанием 5.000 мг/л хло тоном получались светлые гомогенные
ристого натрия, мембрана нагревается растворы, но они не пригодились для
до 75°С. Такая мембрана может дать производства хороших мембран. В эту
25 - 30 галлонов/кв. фут х день обес группу входили метиловый эфир му
соленной воды с содержанием 300 мг/л равьиной кислоты, акриловая кислота,
хлористого натрия, имея ячейку, рабо олеиновая кислота, фенол, пропионо-
тающую при манометрическом давле вая кислота, диэтаноламин, диэтилфта-
нии 600 фунтов на кв. дюйм. лат, тетрагидрофуран, диэтиламин, аце-
Развитие надежной тройной смеси, тонитрил и пирокатехин.
отливаемой при комнатной температу Неприменимость некоторых матери
ре, упростило исследование параметров алов объяснялась их несоответствием
отливки. Одним из них явилась специ известным требованиям, которые были
фикация ацетата целлюлозы. Были изу раньше упомянуты. Однако, некоторые
чены молекулярный вес, распределение из них соответствовали вполне, но все
молекулярного веса и содержание аце же не были пригодными, что указывает
тила (степень ацетиляции). Было уста на недостаточность этих требований.
новлено, что в исследованных пределах Эволюция удачных двойных и трой
последняя переменная величина наибо ных смесей целиком подтверждает, что
лее важна, причем для производства ни вода, ни электролиты не являются
хороших мембран желательно иметь необходимыми компонентами отливоч
содержание ацетила 37,5% -40,1% (сте ных растворов для полезных опресни
пень ацетиляции 75% -83%). тельных мембран из ацетата целлюло
Технология тройного отливочного ра зы. В виде заключения к этому поло
створа оказалась также применимой жению можно сказать, что ни в одной
для изготовления многообещающих из стадий производства не требуется
опреснительных мембран из этилцеллю- междуионного или ионо-дипольного
лозы. В этом случае в отливочный ра взаимодействия между компонентами
створ входили этилцеллюлоза — три- отливки. Последнее положение отно
этилфосфат — диоксан. сится также к отливочным растворам,
Для производства многообещающих содержащим воду, как это было под
опреснительных мембран из ацетата тверждено удачными четверными от
целлюлозы, кроме формамида были ис ливочными растворами.
пользованы в отливочных растворах и

177
Mejoras en las Técnicas de

Fabricación de Membranas de

Desalinizacion por Osmosis Inversa

S. Manjikian, S. Loeb, J. W. McCutchan

Estados Unidos de Norteamérica

En el curso de la década pasada, la nales. Tales agregados debían ser miscibles


ósmosis inversa ha sido desarrollada al con el solvente y con el agua y debían ser
punto de convertirse en un proceso de químicamente inactivos. Cuarto, luego de
desalinización competitivo. Una gran parte ser sumergido en agua, el aditivo debía
de este progreso ha sido resultado del poder lixiviarse del gel por solución en el
desarrollo de una membrana de mayor efi agua de inmersión y preferiblemente des
ciencia, a juigar por las cualidades de la pués del solvente. Con respecto al resto de
membrana de desalinización y el flujo de la técnica de fabricación de la membrana,
agua desalinizada. Estos adelantos en la se utilizaron, en general, los pasos previa
tecnología de las membranas de ósmosis mente determinados por Loeb y Sourirajan.
inversa son consecuencia de dos desarrollos Estos pasos incluían la inmersión de la
básicos: membrana en agua, generalmente agua he
1. El descubrimiento de Reid y de lada, dentro de un determinado período
Breton de que el acetato de celulosa es muy después de la dispersión de la película y,
semipermeable a las sales del agua del mar. finalmente, calentamiento de la membrana
Sourirajan independientemente llegó a estas a la temperatura de trabajo del equipo de
mismas conclusiones y amplió la lista, in desalinización a ser usado en la producción
cluyendo el acetato butirato de celulosa. de agua fresca. Las membranas luego fueron
2. El desarrollo de una técnica de fabri comprobadas en una pequeña célula de
cación por parte de Loeb y Sourirajan, por desalinización capaz de permitir el pasaje
medio de la cual las membranas de acetato rápido de aguas madres a presión sobre la
de celulosa permiten un flujo de agua superficie de la membrana y de dar salida
potable suficientemente elevado para dar al al agua desalinizada, con una resistencia
proceso interés comercial. mínima a su flujo.
Como parte de su técnica de fabricación, La mejor solución de moldeo obtenida
Loeb y Sourirajan utilizaron una solución hasta ahora ha sido una mezcla ternaria de
acetónica de moldeo conteniendo, de acuer acetato de celulosa—formainida—acetona,
do con los trabajos previos de la Srta. en la proporción de 25:30:45 por ciento por
Dobry, electrolitos acuosos tales como el peso. Las membranas obtenidas a partir de
perclorato de magnesio. En este trabajo se esta solución de moldeo son iguales o me
informa sobre los resultados obtenidos con jores que las mejores membranas obtenidas
soluciones de moldeo que solamente contie de las soluciones de moldeo electrolíticas
nen no-electrolitos. modificadas utilizadas previamente. Las
Las pautas para el estudio se obtuvieron membranas de formamida modificada traba
con base en las experiencias anteriores. jan con una buena eficiencia reproducible
Primero, se utilizó un acetato de celulosa y tienen buenas propiedades físicas. Más
similar al E-398-3. Segundo, el solvente para importante que ello, el moldeo puede ha
el acetato de celulosa debía ser química cerse rápidamente a temperatura ambiente
mente inactivo y miscible con el agua dado con la solución de formamida, lo cual cons
que el solvente es separado en gran parte tituye una marcada simplificación respecto
del gel cuando es sumergido en agua. Ter de las técnicas previas, de acuerdo con las
cero, si el solvente era incapaz de producir, cuales el moldeo se hacía mejor a una tem
por sí solo, una membrana semipermeable peratura que oscilada entre —5 y — 10°C.
de alto flujo, para lograr tal objeto debían La solución de formamida y las modifica
agregarse uno o más componentes adicio ciones concomitantes en la técnica de fabri
ración han reemplazado a la vieja técnica cercana al agua que es inútil como aditivo.
para el trabajo de moldeo empleada común Las mezclas ternarias que han sido más
mente en la Universidad de California en exitosas contienen acetato de celulosa-
Los Angeles (UCLA) . Típicamente, una acetona, además de un tercer compuesto:
membrana de formamida modificada se su fosfato tetrahidrofurfurilo, dimetilsulfóxido,
merge en agua helada después de un periodo N-metilo-2-pirrolidona, dimetilformamida,
de evaporación máximo de medio minuto a fosfato trietílico o ácido acético glacial.
la temperatura ambiente. Posteriormente es El fosfato tetrahidrofurfurilo es un sol
calentada en agua caliente durante 4 ó 5 vente incompleto para el acetato de celulosa
minutos. Para desalinización de agua de al igual que la formamida. En contraste con
alimentación salobre, de 5.000 ppm de NaCI, la formamida el dimetilsulfóxido, el
la membrana se calienta a 75°C. Es de N-metilo-2-pirroIidona, el dimetil-formami-
esperar que tal membrana produzca entre da, el fosfato trietílico y el ácido acético
25 y 30 galones, por pie cuadrado por día, son solventes completos para el acetato de
de agua desalinizada a 300 ppm NaCI en celulosa y los tres últimos son útiles en
una célula que opera a 600 libras por pul mezclas binarias.
gada cuadrada, presión manométrica. Un cierto número de compuestos orgá
El desarrollo de una mezcla ternaria se nicos dieron soluciones homogéneas claras
gura, moldeable a temperatura ambiente, en mezclas ternarias con acetato de celulosa
simplifica el exámen de los parámetros de y acetona pero no resultaron convenientes
moldeo. Uno de los parámetros así exami para la producción de buenas membranas.
nados fue el de la especificación del acetato Este grupo incluye formiato de metilo,
de celulosa. Se consideraron el peso mole ácido acrílico, ácido oléico, fenol, ácido
cular, la distribución del peso molecular y propíonico, dietanolamina, dietilftalato, te-
el contenido acetílico (grado de acetilación). trahidrofurano, dietilamina. acetato de
Se encontró que dentro de la gama conside nitrilo y pirrocatecol.
rada, la última variable fue la más impor Lo inadecuado de algunos de estos mate
tante, siendo conveniente un contenido riales debe atribuirse a la circunstancia de
acetílico entre el 373 y el 40,1% (grado de que no satisfacen algunos de los requisitos
acetilación entre el 75 y el 89%) para previamente señalados. Sin embargo, algu
producir buenas membranas. nos de ellos llenan todos los requisitos a
También se determinó que la técnica de pesar de lo cual no dieron resultado, lo que
moldeo con solución ternaria resulta prác demuestra la insuficiencia de dichos requi
tica para la preparación de membranas, de sitos.
interesantes perspectivas, partiendo de la La formulación de mezclas binarias y ter
etilcelulosa. En este caso, la solución de narias demuestra inequívocamente que ni el
moldeo fue etilcelulosa-fosfato tri-etílico- agua ni los electrolitos son necesarios como
dioxano. componentes de soluciones de moldeo para
Otros productos no electrolíticos además membranas de desalinización de acetato de
de la formamida han sido usados en solu celulosa útiles. Como un corolario de esta
ciones de moldeo para producir promisoras afirmación resulta claro que en ninguna
membranas de desalinización de acetato de etapa del proceso de fabricación no se
celulosa. Estas soluciones incluyen mezclas requiere una interacción ion-ion o ion-
cuaternarias, ternarias y binarias. Las mez dípolo entre los componentes del líquido
clas cuaternarias más apropiadas contienen de moldeo. Esta última afirmación es apli
acetato de celulosa-agua-acetona, más un cable también a soluciones que contienen
cuarto componente, úrea, glioxal o peróxido agua, según lo demuestra el éxito de solu
de hidrógeno. El peróxido de hidrógeno es ciones cuaternarias de moldeo.
de especial interés por su relación química

179
Vapor-Compression Evaporation

With Direct Contact Heat Transfer

K. L. Pinder

Canada

The following paper is a description of a 1. In the direct refrigeration freeze de


proposed desalination process which has not salination process (refs. 13-16) , the heat is
yet been developed to the stage where esti removed from the water by the evaporation
mated operating conditions could be mean of an insoluble liquid which boils below the
ingful. Besides this, the vapor-compression salt water freezing temperature. The roles of
system proposed here may be carried out the two liquids in the evaporative process
with widely different types of equipment. are reversed (the water evaporates and the
The choice of equipment for any specific second liquid is cooled") but the experi
plant will be governed by the results from mental data and heat transfer correlations
future pilot plant studies. are still applicable.
This process, like certain others, has been 2. A similar desalination process uses a
designed to circumvent the evaporator prob gas hydrate instead of ice. In this case the
lems of scaling, size, and cost. Scaling has hydrate former is usually boiled to cool the
been eliminated by the use of liquid-liquid water to the hvdration temperature (refs.
heat transfer in both the evaporator and 17-19) .
condenser. The high heat transfer coeffi 3. The evaporation of water by heat
cients and large surface areas available in transferred directly from an immiscible heat
the direct contact heat transfer make the transfer medium is of a similar nature but
use of smaller equipment possible. Because very little has been published on it. In the
of these two considerations, it is expected flash evaporation processes (refs. 6, 20)
that appreciable cost reductions for desali which use direct heat transfer heat, the sea
nation of water will be shown by this process water is heated by the heat transfer medium
over the equivalent vapor-compression cycle without evaporation.
with conventional heat transfer surfaces.
Besides the possibility of cheaper water, PROCESS DESCRIPTION
this process has two other immediately ob Figure 65 is a schematic flow sheet of the
vious advantages. It lends itself to economi proposed desalination process for the case
cal design over a wide range of plant sizes— in which the heat transfer medium is denser
from household units to city units. Also, than the salt solution. In the evaporator,
outside the field of water recovery, it can be sea water, which has been preheated in
used to evaporate to dryness many solutions tube and shell heat exchangers by the prod
which are now dried only by batch multi- uct water and waste brine, is contacted in
step procedures. an atomized form with hot heat transfer
BACKGROUND medium. The water is evaporated from the
sea water droplets, producing superheated
Liquid-liquid heat transfer during evap steam which stirs the heat transfer medium
oration (refs. 1-12) and condensation (ref. and holds the total mass of liquid in a
6) has in the last few years come under turbulent state. After demisting in the
closer research scrutiny. The impetus for upper section of the evaporator, the steam
this activity has been three other desalina passes to a compressor which raises the
tion processes. steam pressure to that in the condenser.

181
DECANTER
COMPR
Steam Potable
Water

Heat Transfer Medium

FIGURE 65. DIRECT CONTACT VAPOR-COMPRESSION


EVAPORATION.

At the temperature corresponding to the As can be seen, this is an exceedingly


brine boiling point, the heat transfer me simple system which should lend itself easily
dium-brine mixture from the evaporator is to small low maintenance units. Only simple
drawn into a separator. From there the controls will be needed to hold this in bal
waste brtne goes to the sea water prcheater ance since the mass flow of heat transfer
and the heat transfer medium is pumped medium is so much greater than that of
to the condenser. The compressed steam is water. Also, since the main transfer of heat
condensed by direct contact with the heat is across liquid-liquid interfaces, there is no
transfer medium, which is heated to a tem scaling problem, the temperature difference
perature several degrees above the boiling between heat transfer fluids may be small,
point of the waste brine in the low pressure corrosion is negligible, and there is only an
evaporator. From the top of the condenser, economic limit to the final brine concen
the liquid mixture passes to a decanter tration.
where the potable water is decanted from It is this last point which widens the field
the heat transfer medium which is recycled of uses for this process immeasurably. Out
to the evaporator. side the field of desalination there are many
For heat transfer mediums which are solutions which are difficult to concentrate
lighter than water, the process operates in because of scaling, stickiness, or corrosion.
a similar fashion but minor alterations in By this process they could be evaporated to
the takeoff points for the various fluid dryness with very little loss of economy. The
streams must be made. high superheat produced in the steam by
this procedure is almost entirely recovered accumulative toxicity must be avoided.
in the condenser. Since the solids would 12. Price: Because of the large inventory
remain in the heat transfer medium, the of the heat transfer fluid in larger plants,
choice of heat transfer medium would be and because of the small losses which are
specific in each case. usually encountered in large-scale plants,
As mentioned earlier, the equipment de exotic high priced materials should be
sign and choice of heat transfer medium avoided.
will depend on their application and on
future pilot plant studies. Several alterna EVAPORATOR
tives may now be mentioned to show the In Figure 66 three of the possible evap
wide choice available. orator configurations are shown. F.ach con
figuration will have its particular field of
HEAT TRANSFER MEDIUM application. These are not design drawings
The criteria which have been considered but are meant to show the flow pattern of
in screening heat transfer media are: the three phases involved.
1. Vapor pressure: The heat transfer me 1. Water Spray: Rapid response to water
dium must have a low vapor pressure com flow rate may be obtained in an evaporator
pared to that of water at the boiling point which acts as a spray column (Fig. 66A) .
of the brine. Preheated water is sprayed into a large vol
2. Solubility: Water and the heat trans ume of hot heat transfer medium and evap
fer medium should be mutually insoluble. orates in the turbulent atmosphere caused by
3. Stability: The heat transfer medium the almost explosive nature of the process.
must not react with water or brine, nor Most of the heat transfer studies have
must it decompose at the temperatures en been made on such a system (refs. 10, 11,
countered in the process. 16) , and for this reason it would be the
4. Corrosion: For economy in construc easiest to design. Although the large inven
tion, the heat transfer medium must be tory of heat transfer medium is a disadvan
noncorrosive to ferrous metals. tage, this type of evaporator would be useful
5. Heat capacity: The heat capacity must for processes in which the solution is evap
be as high as possible, since the heat is orated to dryness.
transferred only as sensible heat. The circu 2. Heat Transfer Medium Spray: More
lation rate of the heat transfer medium is reminiscent of a calandi ia-type evaporator
inversely proportional to its specific heat. is the process shown in Figure 66B. Hot heat
6. Viscosity: The viscosity should be low transfer medium is sprayed into a pool of
at the temperatures encountered in the salt water, thus imparting its heat to the
process. water which will boil at the liquid-liquid
7. Density: The density may be either surface. This configuration will allow phase
greater or less than that of water, but in separation in the evaporator and will oper
either case there should be a large differ ate more quietly than the water spray sys
ence in density to enhance separation. tem because of the lower rate of heat
8. Emulsification: Since there is intimate transfer. For a given rate of heat transfer,
mixing in the evaporator and condenser, a much smaller inventory of heat transfer
the heat transfer medium must not have a medium would be necessary in this evap
tendency to emulsify with water or brine. orator than in the first case.
9. Freezing temperature: The tempera 3. Flow Contactor: Since heat transfer
ture should be low enough so that solidifi rate and nucleation are enhanced by turbu
cation does not occur in cold spots in the lence, the intimate mixing produced by
equipment. For equipment which is to have injecting the hot water into the throat of
intermittent use, the heat transfer medium a venturi would result in rapid evapora
should not be solid at ambient temperatures. tion. Disintegration of the steam from the
10. Combustibility: Even though the liquid mixture could be carried out by
vapor pressure criterion requires a mini centrifugal force (Fig. 66C) . The small size
mum of vapor from the heat transfer of this type of equipment and the low in
medium, the best fluid should have low ventory of heat transfer medium could make
combustibility so that special safety pre up for the reduction in efficiency which
cautions are not needed. might result.
11. Toxicity: Since no two liquids are In place of a venturi, any flow mixer
absolutely insoluble, a small amount (a few could be used to mix the two fluids inti
ppm) of the heat transfer fluid may appear mately. Because of the scrubbing effect of
in the product water. Therefore, fluids the boiling mixture, erosion of spirals or
which are highly toxic or which exhibit screens may be very rapid.
183
^ Steam
r

Brine < Cold H.T.M.

Hot H.T.M.

Steam
r
r
*******

Brine ♦ Cold H.T.M.

> Steam

I i
S*****S

Hot HT.M.

Sea Water

Brine «Cold H.T.M.


FIGURE 66. DIRECT CONTACT EVAPORATORS.
CONDENSER transfer medium by using the outlet fluid
from the condenser to desuperheat the
Figure 67 illustrates two of the possible steam. However, with liquid-liquid heat
condenser flow patterns. Other designs, such transfer the increase in condenser size due
as the one used for direct steam heated in to superheat is not as great as in tube-type
dustrial hot water supply systems, could heat exchangers.
also be used for this purpose. The final
design which is chosen in each case will BRINE REMOVAL
depend upon the results of pilot plant
studies and upon the purpose for which it Several operational factors will influence
is to be used. the design of the brine separator. If rapid
disengagement of the brine and heat trans
fer medium occurs by virtue of a large
Steam density difference and rapid coalescence,
then a simple gravity settler may be used.
For cases in which dry salt is produced or
coalescence is slow, a continuous centrifuge
may be used. Again, the choice will be made
Noncondantibltt from well-defined systems and will require
no special equipment.
, PotODlO
Wottr COMPRESSOR
.Hot H.T.M. The Office of Saline Water is presently
supporting a study of steam compressor de
sign. This newer data plus previous work
which has been done on the calandria-type
vapor -compression evaporators may be used
in the design of this portion of the equip
PotobH Wottr « ment.
Hot H.T.M Steam ejector-type compressors may also
be used for this purpose in locations where
the steam cost proves to be less than electric
power cost for the compressor motor. These
considerations have already been thoroughly
studied and are not considered problems in
this process.
ECONOMICS
Cold H.T.M. Because of the lack of reliable data on the
size and efficiency of the two main units of
equipment in this process, any economic
FIGURE 67. DIRECT CONTACT assessment could add very little to what can
CONDENSERS. be said about the vapor-compression evap
oration process in general. The differences
between this system and the standard system
1. Packed Condenser: Because of the are as follows.
large density difference between steam and 1. Once the water droplet has begun to
the heat transfer medium, a packed column boil, i.e., the boiling is nucleated, the differ
would be necessary to give the needed resi ence between its boiling temperature and
dence time. Noise, caused by the collapse of the heat transfer medium's temperature will
the steam, bubbles, may be a nuisance in a be quickly reduced by the high heat trans
condenser ot this design and could easily be fer coefficient and the large surface area
reduced by mixing the two streams in an available for heat transfer. This is also true
ejector at the bottom of the column. in the condenser. Since there arc no solid
2. Spray Condenser: A standard spray heat transfer surfaces, the high heat trans
condenser could be converted for this serv fer rates are not reduced by scaling.
ice. The closed system shown in Figure 67B 2. The temperature difference between
would be very efficient in heat and fluid the boiling solution and the heat transfer
inventory. medium is not limited by high temperature
Since the steam will be superheated after scale formation.
compression, it may be advantageous to S. Evaporation per pass of the sea water
produce a higher temperature in the heat through the evaporator can be very high
185
without fear of surface fouling. This would heat transfer medium, the rate of circula
reduce the size of the waste brine heat ex tion must be very high—between about 50
changers, the loss of heat in this stream, and and 100 pounds per pound of water pro
the power to pump the excess water. Where duced. The heat transfer medium circula
waste brine disposal is a problem, it may be tion rate is a function of the temperature
more economical to evaporate the salt to difference between the evaporator and con
dryness and sell the salt. denser and of its heat capacity. Because of
4. Because of the high heat transfer rates the relative cost of pumping a low viscosity-
across a boiling or condensing interface, fluid and compressing steam, it is expected
plant size and capital cost can be much less that when more data are available, a full
than that for calandria-type vapor com economic assessment will favor the highest
pression equipment. This will be especially circulation rate for any given fluid. Paraf
advantageous in smaller and portable units. fins tend to have higher heat capacities than
5. Power consumption will be a function do other liquids which are insoluble in
of the percentage evaporation, since the water, hence a material like paraffin wax
condenser pressure will increase as the final may prove to be the best heat transfer
boiling temperature of the solution in medium.
creases. A multistage vapor compression Although this process is still in the arm
process of this type would provide the most chair engineering stage, there do not appear
efficient power or steam consumption for to be too many problems left for the pilot
cases in which a large fraction of the water plant to solve. Work has been underway for
is to be recovered. Only in very large units, some time at the University of British Co
however, would the added equipment cost lumbia in Vancouver, British Columbia, on
be balanced by the reduction in power cost. the direct contact boiling and the direct
6. Since corrosion and scaling are neg contact condensation of a liquid. Support
ligible, the maintenance cost of the evap for this work has been given both by the
orator would be greatly reduced. university and by the National Research
7. Since all the latent heat of evaporation Council of Canada.
must be carried by the sensible heat of the

REFERENCES
1. Viskanta. R.; Lottes, P. A.: Proc. Heat 1289.
Transfer and Fluid Mechanics Inst., 11. Sideman, S.; Barsky, Z.: A.I.Ch.E. Pre
Seattle. Wash. (June 15-15. 1962) pp. print 33b, 55th National Meeting,
171-184. Houston, Texas, (Feb. 7-11, 1965).
2. Harriott, P.; Wiegandt, H.: Private 12. Otterman. B.: Proc. Heat Transfer and
communication from Cornell University, Fluid Mechanics Institute, Seattle, Wash.
Ithaca, N. V. (Oct. 1963) . (June 13-15, 1962) pp. 185-196.
3. Moore. G. R.: A.I.Ch.E. Journal, vol. 13. Bosworth, C. M.; Carfagno, S. S.: Bar-
5 no. 4 (1959) pp. 458-466. duhn, A. J.; Sandell. D. J.: Office of
4. Moore, G. R.: Ph.D. Thesis. University Saline Water, R&D Rept. no. 32 (Julv
of Wise. (1956) . 1959) .
5. Gordon, K. F.; Singh, T.; Weissman, 14. Karnofsky. G.: Chem. Eng. Prog., vol.
E. Y.: Int. J. Heat and Mass Transfer, 57, no. / (1961) pp. 42-46.
no. 3 (1961) pp. 90-93. 15. Wiegandt, H. F.: Office of Saline Water
6. Wilke, C. R.; Cheng, C. T.; Ledesma, R&D Rept. no. 41 (Aug. 1960)
V. L.; Porter, J. W.: Chem. Eng. Prog 16. Kawasaki, S.; Umano. S.: Kagaku Koga-
ress, vol. 59 no. 12 (1963) pp. 69-75. ku, vol. l.no. 1 (1963) pp. 69-74.
7. Sideman, S.: Shabtai, H.: Can. J. Chem. 17. Knox. W. G.: Hess, M.; Jones, G. E.;
Eng., vol. 42 no. 3 (1964) pp. 107-117. Smith, H. B.: Chem. Eng. Prog., vol. 57
8. Novakovic, M.; Stefanovic, M.: Int. J. no. 2 (1961) pp. 66-71.
Heat and Mass Transfer, no. 7 (1964) 18. Anonymous: Chem. Eng. \'ews, no. 60-
pp. 801-807. 61, (Dec. 12, I960) .
9. Harriott, P.; Wiegandt, H.: A.I.Ch.E. 19. Barduhn, A. J.; Towlson, H. E.; Hu.
Journal, vol. 10 no. 5 (1964) pp. 755- Y.: National A.I.Ch.E. Meeting. Lake
758. Placid, N. Y. (Sept. 24-27. 1961) .
10. Sideman, S.: Taitel, Y.: Int. J. Heat and 20. Knuth. E. L.: /. & E.C. Proc. Design
Mass Transfer, no. 7 (1964) pp. 1273- and Bevel., vol. ) no. 1 (1964) pp. 55-60.
SUMMARY OF DISCUSSION
It was asked how an emulsion was broken ppm. The author was asked for comments
in the event that one occurred. The author concerning his experience with Arochlor and
stated that there was concern about emul the lighter hydrocarbons. The author stated
sion formation but that when it formed it that his experience with Arochlor had been
broke readily and gave no difficulty. It was satisfactory and that the hydrocarbons used
stated that demislers will be used to over evaporated from the water. He stated further
come entrainment problems. that since this process is not run as a cyclic
In answer to a question concerning the process, appreciable time can be allowed for
salinity of the product, it was stated that separation. The thing they were looking for
the salinity of the product obtained by the in their experiments was good heat transfer
method presented in this paper is below 500 data.

Evaporation Par Compression de

Vapeur et Echange de Chaleur

Par Contact Direct

K. L. Pinder

La présente étude décrit un procédé de sations économiques dans une gamme de


dessalement projeté qui n'est pas encore tailles très étendue: depuis l'appareil mé
arrivé au stade où les prévisions d'exploita- nager jusqu'à l'usine municipale. Par
tation seraient significatives. En outre, le ailleurs, à part le dessalement, il peut servir
procédé par compression de vapeur envisagé à évaporer jusqu'à dessiccation complète
ici peut être appliqué dans une gamme bien des solutions qui ne peuvent être
d'appareils de types très différents. Le desséchées actuellement que par lots et
choix de l'équipement pour toute usine selon des procédés à stades multiples.
donnée dépendra des résultats obtenus par
la suite dans les essais en usines pilotes. DOCUMENTATION
Ainsi que d'autres, ce procédé a été L'échange de chaleur liquide-liquide pen
conçu pour éviter les difficultés d'entartrage, dant l'évaporation (refs. 1-12) et la conden
de dimension et de prix des évaporateurs. sation (réf. 6) a fait l'objet de recherches
L'entartrage a été éliminé par un échange plus poussées au cours des dernières années.
de chaleur par contact direct de liquide à Cet intérêt a été provoqué par trois autres
liquide, aussi bien dans l'évaporateur que procédés de dessalement.
dans le condenseur. Les coefficients élevés 1. Dans le procédé de dessalement par
d'échange de chaleur et les surfaces impor congélation directe (refs. 13-16) , la chaleur
tantes dont on dispose dans l'échange de est enlevée de l'eau par l'évaporation d'un
chaleur par contact direct permettent l'em liquide insoluble dont le point d'ébullition
ploi d'appareils de dimensions plus réduites. est inférieur à la température de congéla
En raison de ces deux facteurs, on s'attend tion de l'eau salée. Dans le processus d'éva-
à ce que ce procédé apporte une réduction poration, le rôle des deux liquides est
appréciable du prix de dessalement de l'eau inversé (l'eau s'évapore et le deuxième
par rapport au même cycle de distillation liquide est refroidi) , mais les données
par compression de vapeur, utilisant des expérimentales et les rapports d'échanges
surfaces d'échange de chaleur classiques. de chaleur restent applicables.
A part la possibilité de produire l'eau 2. Un procédé de dessalement analogue
à meilleur marché, ce procédé possède deux emploie l'hydrate d'un gaz à la place de la
avantages évidents. Il se prête à des réali glace. Dans ce cas, le producteur d'hydrate

187
est mis en ebullition pour refroidir l'eau à cipal s'effectue par contact direct des
la température d'hydratation. couches de liquide, il n'y a pas de problème
S. L'évaporation de l'eau par échange d'entartrage, les différences de température
direct de chaleur avec un véhicule d'échange entre les liquides d'échange de chaleur
non miscible est un procédé similaire sur peuvent être faibles, la corrosion est in
lequel peu de chose a été publié. Dans les signifiante et la concentration finale des
procédés d'évaporation éclair (refs. 6, 20) , saumures n'est bornée que par les considé
où la chaleur est appliquée par échange rations économiques.
direct, l'eau de mer est chauffée sans évapo- C'est ce dernier point qui étend immensé
ration par le véhicule d'échange de chaleur. ment le champ d'application de ce pro
cédé. Le domaine du dessalement mis à
DESCRIPTION DU PROCÉDÉ part, il existe de nombreuses solutions qu'il
Considérons la progression du procédé de est difficile de concentrer à cause de l'entar
dessalement envisagé, lorsque le véhicule trage, de l'adhésivité et de la corrosion.
d'échange de chaleur a une densité plus Avec ce procédé, elles pourraient être éva
élevée que la solution saline. Dans l'évapo- porées à dessiccation à peu de frais. L'in
rateur, l'eau de mer, chauffée au préalable tense surchauffe produite dans la vapeur
dans un échangeur tubulaire par l'eau par cette manière de procéder est presque
produite et les saumures résiduaires, est entièrement récupérée dans le condenseur.
mise en contact sous une forme atomisée Etant donné que les solides resteraient dans
avec le véhicule d'échange de chaleur porté le véhicule d'échange, il importerait que
à une haute température. L'eau s'évapore ce véhicule d'échange de chaleur soit choisi
des gouttelettes d'eau de mer, produisant spécifiquement dans chaque cas.
de la vapeur surchauffée qui agit le véhicule Comme on l'a mentionné plus haut, la
d'échange de chaleur et maintient la masse disposition des appareils et le choix du
liquide totale dans un état de turbulence. véhicule d'échange de chaleur dépendront
Apres avoir dégorgé sa buée dans la section de l'application visée et des résultats ob
supérieure de l'évaporateur. la vapeur passe tenus à l'avenir dans les usines pilotes.
par un compresseur qui élève sa pression Plusieurs options peuvent être citées ici
au niveau de celle du condenseur. pour montre l'étendue des possibilités.
Le mélange véhicule d'échange de Le véhicule d'échange de chaleur doit
chaleur-saumure, provenant de l'évapora être choisi pour chaque application, en
teur, à une température correspondant au considérant ses propriétés physiques: solu
point d'ébullition de la saumure, est dirigé bilité, tension de vapeur, stabilité, action
vers un séparateur. De là, les saumures corrosive, chaleur spécifique, viscosité, toxi
résiduaires sont envoyées au réchauffeur cité, etc.
d'eau de mer et le véhicule d'échange de Il y a plusieurs types d'évaporateurs qui
chaleur est pompé vers le condenseur. La peuvent être employés avec ce procédé. La
vapeur comprimée est condensée par con colonne à pulvérisation d'eau a fait l'objet
tact direct avec la véhicule d'échange de des recherches expérimentales les plus pous
chaleur qui a été porté à une température sées mais, du point de vue économique, il
supérieure de plusieurs degrés au point est plus que probable que le dispositif de
d'ébullition des saumures résiduelles dans mélange des fluides par injection (flow
l'évaporateur à basse pression. Du sommet contactor) se révélera le meilleur dans les
du condenseur, le mélange liquide passe grandes installations.
dans un décanteur où l'eau potable est En résumé, les avantages de ce procédé
séparée du véhicule d'échange de chaleur sur le cycle classique compression de vapeur-
qui va reprendre le cycle à l'évaporateur. évaporation sont les suivants:
Avec des véhicules d'échange de chaleur 1. L'absence de surfaces susceptibles de
plus légers que l'eau, le procédé fonctionne s'entartrer permet des différences de
de façon analogue mais certaines petites température élevées dans les échanges
modifications doivent être apportées aux de chaleur.
points d'extraction des différents liquides. 2. L'évaporation pour chaque passage
Comme on peut le voir, il s'agit là d'un dans l'évaporateur peut être très forte
procédé extrêmement simple qui devrait du fait qu'il n'y a pas à craindre
bien se prêter à de petites installations l'entartrage.
n'exigeant que peu d'entretien. Il suffit de 3. Les matériaux de construction sont
simples commandes pour maintenir l'équi bon marché étant donné que la corro
libre du système, par le fait que le débit du sion est insignifiante.
véhicule d'échange de chaleur est tellement 4. La dimension des installations est
plus élevé que celui de l'eau. En outre, réduite du fait des taux élevés
étant donné que l'échange de chaleur prin d'échange de chaleur.

188
5. Il peut être employé efficacement sur L'inconvénient principal de ce procédé
une gamme de capacités étendue. est d'exiger un taux élevé de circulation du
6. Au besoin, il peut évaporer des solu- véhicule d'échange de chaleur: de 50 à 100
lions jusqu'à dessiccation. litres par litre d'eau produite.

Испарительная Установка со Сжатым

Паром и Теплопередачей Прямого

Контакта

К. Л. Пайндер

Канада

Этот доклад является описанием может быть также использован для


предлагаемого процесса опреснения, полной упарки до состояния сухости
который еще не был развит до той многих растворов, которые в настоя
степени, когда намеченные рабочие щее время выпариваются только мно
условия становятся выполнимыми. Кро гоступенчатым способом периодическо
ме того, здесь предложенную систему го действия.
сжатия пара можно осуществить с по
мощью весьма различного оборудова Предшествовавшее Развитие
ния. Выбор оборудования для каждого Перенос тепла жидкостью к жидко
специфического объекта будет зависеть сти во время выпарки (указаний 1 -12)
от изучения результатов, которые по и конденсации (6) подвергся в течение
лучатся на будущей опытной установ нескольких последних лет более вни
ке. мательному изучению. Толчком к этому
Этот процесс был разработан с целью послужили три других опреснительных
обойти проблемы выпарки, состоящие процесса.
из образования накипи, больших раз 1. В опреснительном процессе (ука
меров и высокой стоимости. Образова заний 13-16) по способу прямого ре-
ние накипи было устранено посред фрижерационного замораживания теп
ством переноса тепла жидкостью к ло из воды отводится посредством ис
жидкости как в испарителе так и в парения нерастворимой жидкости, ко
конденсаторе. При теплопередаче пря торая кипит при температуре ниже
мого контакта, благодаря высокому точки замерзания соленой воды. В ис
коэффициенту теплопередачи и боль парительном процессе роли обеих жид
шим поверхностям соприкосновения, костей перевернуты (вода испаряется,
является возможным пользоваться обо а вторая жидкость охлаждается), но
рудованием меньших размеров. Ожи экспериментальные данные и корреля
дается, что в связи с этими двумя при ции теплопередачи все-же попрежнему
чинами будет достигнуто значительное применимы.
удешевление процесса опреснения во 2. В подобном предыдущему опре
ды по сравнению с эквивалентным снительном процессе пользуются вме
циклом сжатия пара при пользовании сто льда гидроокисью газа. В этом слу
обычными поверхностями теплопере чае образователь гидроокиси обыкно
дачи. венно находится в кипящем состоянии
Кроме возможности удешевить воду, для охлаждения воды до температуры
этот процесс имеет еще два других, гидратации (17, 18, 19).
сразу бросающихся в глаза, преиму 3. Выпаривание воды посредством
щества. Он экономически применим для прямого переноса тепла с помощью
установок самого разнообразного мас несмешивающегося теплоносителя име
штаба, начиная односемейными жили ет ту же самую сущность, но об этом
щами и кончая городскими водопрово имеется очень мало печатных матери
дами. Помимо регенерации воды он алов. В процессах мгновенного испаре
ния (6, 20), где используется тепло Последний факт сулит неограничен
прямой теплопередачи, морская вода ные возможности для расширения обла
нагревается теплоносителем без выпа стей применения этого процесса. Кроме
ривания. опреснения воды имеется много дру
гих растворов, которые трудно концен
Описание Процесса трировать ввиду образования накипи,
Морская вода, подогретая в трубча липкости и коррозии. С помощью вы
тых теплообменниках опресненной во шеописанного процесса они могут быть
дой и сбросом концентрата, приходит выпарены до состояния сухости с весь
в соприкосновение в распыленном виде ма малыми экономическими потерями.
с горячим теплоносителем. Из капелек Получаемый, благодаря этой процеду
морской воды испаряется чистая вода, ре, высокий перегрев пара почти це
образуя перегретый пар, который соз ликом регенерируется в конденсаторе.
дает перемешивание теплоносителя и Так как в теплоносителе будут оста
поддерживает во всей массе жидкости ваться вещества твердой фазы, для
турбулентное состояние. После «расту- каждого отдельного применения при
манивания» (отложение воды) в верх дется выбирать специфический тепло
ней части испарителя, пар поступает в носитель.
компрессор, который повышает его Как сказано ранее, проект оборудо
давление до уровня, поддерживаемого вания и выбор теплоносителя будет
в конденсаторе. зависеть от области применения и от
Теплоноситель, представляющий со будущего изучения работы опытной
бой смесь концентрата из испарителя, установки. В настоящее время можно
направляется в сепаратор при темпе упомянуть несколько альтернатив, что
ратуре, соответствующей его точке ки бы показать широту имеющегося вы
пения. Оттуда сбросный концентрат бора.
идет в подогреватель морской воды, а Теплоноситель должен быть выбран
теплоноситель перекачивается в кон для каждого отдельного применения,
денсатор. Сжатый пар конденсируется принимая во внимание его физические
посредством прямого соприкосновения свойства: растворимость, давление па
с теплоносителем, подогретым до тем ра, устойчивость, коррозионную актив
пературы, превосходящей на несколь ность, удельную теплоемкость, вяз
ко градусов точку кипения сбросного кость, ядовитость, и т.д.
концентрата в испарителе низкого дав Водораспылительная колонна лучше
ления. Из верхней части конденсатора всего изучена на опыте, но с экономи
жидкая смесь поступает в приемник, ческой точки зрения поточный контак
где опресненная вода декантируется из тор, весьма вероятно, окажется наилуч
теплоносителя, который обратно ре- шим для больших установок.
циркулируется в испаритель. Кратко говоря, преимущества опи
При теплоносителях легче воды ра санной системы по сравнению со стан
бочий процесс протекает аналогично, дартным испарением со сжатым паром
хотя придется немного изменить точки состоят в следующем:
ответвления различных потоков жид 1. Так как отсутствуют поверхности,
кости. подверженные образованию наки
Является очевидным, что эта крайне пи, можно пользоваться высокими
простая система могла бы хорошо по перепадами температур теплопере
дойти к маленьким установкам, не тре дачи.
бующим большого ухода. Понадобятся 2. Выпарка при проходе через испа
только простые регулирующие устрой ритель может быть большой, по
ства для удержания ее в равновесии, тому что нет образования накипи.
потому что основной поток теплоно 3. Так как коррозия незначительна,
сителя значительно больше потока во можно пользоваться дешевыми
ды. Кроме того, так как главный пере строительными материалами.
нос тепла происходит на поверхностях 4. Размер установок невелик, ввиду
раздела двух жидкостей, отсутствует больших скоростей теплопередачи.
проблема образования накипи, темпера 5. Процесс может быть эффективно
турные перепады между теплообмен- применен при проектировании
нымн жидкостями могут быть малого установок, емкость которых ко
порядка, коррозия незначительна и для леблется в широких пределах.
конечной концентрации соленого раст 6. Если желательно, можно выпари
вора существует только экономический вать растворы до состояния сухо
предел. сти.
190
Главным недостатком этой системы ход теплоносителя: 50 - 60 фунтов на
является большой циркуляционный рас- фунт пресной воды.

Evaporación por Compresión de

Vapor con Trasmisión Calórica

por Contacto Directo

K. L. Pinder

El trabajo que sigue es una descripción actualmente son evaporadas por procedi
de un proceso de desalinización propuesto mientos no continuos de varias etapas.
el cual no ha sido aún desarrollado al
punto que es puedan establecer condiciones ANTECEDENTES
de funcionamiento estimadas que resulten La transmisión calórica líquido-líquido
signiñcativas. Además, el sistema de com durante la evaporación (1,2,3.4,5,6.7,8,9,10.
presión de vapor propuesto aquí puede ser 11,12) y la condensación (6) han sido objeto
puesto en practica mediante el empleo de de mayor investigación durante los últimos
una gran variedad de equipo. La elección años. El impulso dado a esta actividad se
del equipo para cada planta en particular originó en otros tres procesos de desalini
se regirá por los resultados de los futuros zación.
estudios de planto piloto. 1. En el proceso de desalinización me
Este es otro proceso que está destinado a diante la congelación por refrigeración
solucionar los problemas que presenta el directa (13,14.15,16), el calor es extraído
evaporador en lo que se refiere a descascara del agua por la evaporación de un líquido
miento, tamaño y costo. El descascaramiento insoluble que hierve a una temperatura in
ha sido eliminado mediante el empleo de ferior a la de congelación del agua salada.
transmisión calórica líquido-liquido tanto Los papeles de los dos líquidos en el pro
en el evaporador como en el condensador. ceso de evaporación se invierten (el agua
Los altos coeficientes de transmisión de se evapora y el segundo líquido se enfría)
calor y las grandes áreas superficiales dispo pero los datos experimentales y las correla
nibles en la transmisión de calor por con ciones de transmisión calórica aún son
tacto directo hacen posible el empleo de aplicables.
aparatos de menor tamaño. Debido a las 2. Un proceso similar de desalinización
dos consideraciones que se acaban de men utiliza un hidrato gaseoso en lugar de hielo.
cionar, se espera que este proceso hará En este caso, generalmente se hace hervir
posible una apreciable reducción en el costo al formador de hidrato para enfriar el agua
de la desalinización del agua con respecto a la temperatura de hidratación (17,18,19).
al ciclo de compresión de vapor equivalen 3. La evaporación de agua por calor
te que empica superficies de trasmisión trasmitido directamente en un medio termo-
térmica convencionales. trasmisor inmiscible es de naturaleza simi
lar, pero muy poco se ha publicado al
Además de la posibilidad de agua más respecto. En los procesos de evaporación
barata, este proceso tiene dos ventajas más instantánea (6.20) que emplean calefacción
que se evidencian inmediatamente. Se presta por trasmisión calórica directa, el agua de
para el diseño económico en una gran va mar es calentada por el medio trasmisor de
riedad de escalas desde unidades caseras calor sin producirse evaporación.
hasta unidades para ciudades. Además,
fuera del campo de la recuperación de DESCRIPCIÓN DEL PROCESO
agua, el mismo puede ser empleado para Veamos el proceso de desalinización pro
evaporar a sequedad muchas soluciones que puesto, para el caso en que el medio

191
trasmisor de calor es más denso que la proceso. Fuera del campo de la desalini-
solución salina. El agua de mar, precalen- zación hay muchas soluciones que son difí
tada en intercambiadores de calor de car ciles de concentrar debido a problemas de
casa y tubos, por el agua y salmuera de descascaramiento, glutinosidad o corrosión.
deshecho producida, es puesta en contacto en Mediante este proceso dichas soluciones po
el evaporador, en forma atomizada, con el drían ser evaporadas a sequedad a un costo
medio trasmisor de calor caliente. El agua adicional muy reducido. El alto sobrecalen
es evaporada de las gotitas de agua de mar tamiento producido en el vapor por este
produciéndose vapor sobrecalentado el cual procedimiento se recupera casi totalmente
agita al medio trasmisor de calor y man en el condensador. Dado que los sólidos
tiene a la masa total de líquido en un quedarían en el medio trasmisor de calor,
estado turbulento. Después de separarse de la elección de éste sería específica en cada
la niebla en la sección superior del evapora caso.
dor, el vapor pasa a un compresor el cual Como se mencionó anteriormente, el dise
eleva la presión del vapor a la existente en ño del equipo y la elección del medio
el condensador. trasmisor de calor dependenrán de la apli
La mezcla de medio trasmisor de calor y cación y de los futuros estudios de planta
salmuera, a la temperatura de ebullición piloto. Pueden ahora mencionarse varias
de la solución salina, es transferida del alternativas para demostrar la amplia selec
evaporador a un separador. De allí la sal ción disponible.
muera de deshecho va al precalentador de El medio trasmisor de calor debe elegirse
agua de mar y el medio trasmisor de calor para cada aplicación teniendo en cuenta las
es transferido, mediante una bomba, al con propiedades físicas: solubilidad, presión de
densador. El vapor comprimido se condensa vapor, estabilidad, carácter corrosivo, calor
por el contacto directo con el medio tras específico, viscosidad, toxicidad, etc.
misor de calor que es calentado a una Varios diseños de evaporadores pueden
temperatura varios grados por encima del empicarse en este proceso. La columna
punto de ebullición de la salmuera de des atomizadora de agua ha sido objeto de
hecho en el evaporador de baja presión. De mayor experimentación, pero desde el punto
la parte superior del condensador la mezcla de vista económico es muy probable que el
líquida pasa a un decantador donde el agua contactor de corriente sea el mejor para
potable es separada por decantación del grandes instalaciones.
medio trasmisor de calor el cual es transfe Resumiendo, las ventajas de tal sistema
rido al evaporador para comenzar nueva sobre el ciclo convencional de compresión
mente el ciclo. de vapor y evaporación son:
En el caso de medios trasmisores de calor 1. Dado que no existen superficies que
que son mas livianos que el agua, el proceso se descascaren, pueden emplearse gran
funciona en forma similar pero deben efec des diferencias de temperatura en la
tuarse pequeñas alteraciones en cuanto a la trasmisión calórica.
ubicación de los puntos de derivación de
las distintas corrientes fluidas. 2. La evaporación por cada pasada a
Como puede verse, éste es un sistema través del evaporador puede ser gran
sumamente sencillo que podría aplicarse de debido a que no existe descascara
muy bien en unidades pequeñas que reque miento.
rirían escaso mantenimiento. Dado que el 3. Los materiales de construcción son
caudal de medio trasmisor de calor es tanto económicos dado que la corrosión es
mayor que el de agua, los controles necesa despreciable.
rios para mantener el sistema en equilibrio 4. Es posible construir plantas de tamaño
serán muy simples. Además, dado que la reducido debido a las altas velocidades
transmisión de calor principal tiene lugar de trasmisión calórica.
a través de interfaces líquido-líquido no 5. El proceso puede ser diseñado para su
hay problema de descascaramiento, la dife eficiente empleo en un amplio orden
rencia de temperatura entre Muidos trasmi de capacidades de diseño.
sores de calor puede ser pequeña, la 6. Si así se desea, el proceso sirve para
corrosión es despreciable y la concentración evaporar soluciones a sequedad.
final de la salmuera está sólo limitada por La principal desventaja de este sistema
consideraciones de orden económico. es la alta velocidad de circulación del medio
Es este último punto que amplía inmen trasmisor de calor, o sea, de 50 a 100 libras
samente el número de aplicaciones de este por libra de agua producida.

192
Evaporation of Sea Water in Solar

Stills and Its Development for

Desalination

R. L. Datta, S. D. Gomkale, S. Y. Ahmed, and D. S. Datar

India

Although quite a few techniques (such TABLE XXXII. Solar Radiation Intensity
as multieffect evaporation, multistage flash in Some Regions of Saurashtra and
evaporation, electrodialysis, etc.) have Kutch, Btu per sq ft per day
reached a fairly high stage of technological
development, the cost of converted water Mahuva Bhavnagar Kandla
does not compare favorably with that of Month (lat. 21° N) (lat. 22° N) (lat 23* N>
conventional water; the former is 4 to 6 Jan. 1.330 1.290 1.248
times higher than the latter. Feb. 1,568 1.682 1.490
Mar. 1.8C0 1,840 1.815
In the water-scarce coastal regions of Apr. 2,100 2,180 2.090
India like Saurashtra and Kutch (latitude May 2.240 2,246 2,240
June 2,290 2.292 2,810
21°-24° N) where the gift of nature in the July 2,278 2,266 2.282
form of solar energy is plentiful, the solar Ann. 2.180 2.18S 2,180
Sept. 1.990 1,974 1.960
still technique for desalination of sea water Oct. 1.720 1,690 1.666
has special significance. Common construc Nov. 1.480 1,395 1.355
Dec. 1.268 1.230 1.190
tion materials required for solar stills and
cheap labor are available for the develop
ment of solar stills in these regions. In per day is available during five to six
the other evaporation techniques, out of months of the year (ref. 1) .
the total cost of production of converted The cost of transporting water, particu
water, cost for energy alone is as high as larly to some of the salt works in these
30 or 40 per cent. The high energy cost of regions, is very high. Therefore, there is
other techniques is definitely an impetus ample scope for the development of solar
to the development of solar stills in India stills though the cost of water from solar
where free solar energy can be trapped in stills is higher than that of conventional
the stills. From Table XXXII, it is seen that water. The statistics from the Saurashtra
solar energy of about 2,000 Btu per sq ft and Kutch regions, given in Table XXXIII,

TABLE XXXIII. Cost of Water in Some Salt Works of the


Saurashtra and Kutch Regions

Location Distance from Approximate


of aalt Requirement works to the fresh Mode of coat of water
works (gpd) water source transportation (in Rs. per
(in miles) thousand gals)
Kuda 1,000 4.6 Trucks 80
Mundra 6.000 7.5 Tank lorries 11
Port Albert 1,600 Trucks 25
Victor 1,400 -- Persons Not worked out
(will be still more)
Bherai 1,100 1 Bullock, carts, 18
and boats
Sikarpur 200 4 Bullock and carts 40

193
reveal that the cost ot water at these places found suitable in the laboratory studies is
is as high as Rs. 1 1 ($2.3) to Rs. 40 ($8.4) chosen, although for some unsymmetrical
per thousand gallons, whereas the calcu stills, as well as for experimental purposes,
lated cost of water even from the low higher angles are also used. The 500 gpd
capacity 500 gpd solar still of this institute capacity experimental solar still unit con
is Rs. 8.45 ($1.77) per thousand gallons. sists of four blocks, covering an area of
To obtain relevant design data, a study 8,415 sq ft (Fig. 68) .
was made of different angles of inclination In three of the blocks, there are 15 sym
of the glass cover and the depth of the sea metrical and unsymmetrical stills 55 ft by
brine. The covers are made of glass having 8 ft and 55 ft by 5.5 ft, and angles of
an Fe,Os content of less than 0.15 per cent. inclination of covers as 10°-10°, 15°-15\
The inside bottoms of the stills are painted 20°-20\ 10°-20°, 20°-40°. The fourth block
black. Sea brine of 2° Be is used for the has 6 stills 55 ft by 8 ft, all symmetrical,
experiments until it attains nearly 10° Be. namely 10°-10°. The bottoms of the stills
Ambient temperature varies between 83° of the first three blocks are of cement
and 85°F, the maximum temperature inside concrete, painted with black anticorrosive
the stills being 135° to 148°F. Typical data tank mastic piant; 2° Be sea brine in these
on solar stills having surface areas between stills is at levels of 2 inches, 6 inches, and
3.4 sq ft and 34.5 sq ft were reported 12 inches. The fourth block has its still
earlier (ref. 2) . Calculations were also made bottoms lined with epoxy paint, asphalt
after Bloemer, Collins, and Eibling (ref. mat, tar, gravel mixture, and stabilized soil.
3) for the percentage of incident solar (Fig. 69 shows portions of blocks 2 and
radiation utilized for evaporation in the 4.) Provision exists for collection of rain
solar stills (Table XXXIV) . These calcula water. Glass sheets 4 ft by 3 ft by ys inch
tions show that less than one-third of the are supported by precast, reinforced cement
incident solar energy is used for evapora concrete beams and channels: the latter,
tion, the remainder being dissipated by re together with aluminum channels, is used
flection, absorption by the cover and con to collect product water and rainwater as
densate film, radiation from brine surface, shown in Figure 70. Glass joints are sealed
internal convection, conduction of heat to by putty (Shalibond-E) , and glass faces by
the ground, and reevaporation of conden waterproof adhesive tape. The cost of the
sate. Increasing the angle of inclination of solar still unit, construction of which is
the covers further reduces such utilization Hearing completion, is estimated in Table
for evaporation. XXXV. Of the total cost of the unit, the
major share, namely 65 per cent, is for civil
DESIGN OF 500 GPD CAPACITY engineering materials and work, which in
SOLAR STILLS volves preparation of the soil bed and its
The average annual production rates of stabilization, blackening the stabilized soil
fresh water from sea brine of 2° Be, as surface with asphalt material, and founda
obtained by laboratory solar stills, are 0.06 tion work. Cost of materials such as glass,
to 0.08 gallons per sq ft per day. For scal asphalt, and sealing materials accounts for
ing up to 500 gpd, the lower value, namely, 25 per cent of the total cost; the remaining
0.06 gallons per sq ft per day, is taken. 10 per cent is for miscellaneous expenses,
Inclination of 10° of the cover of the stills including labor and maintenance.

194
5SaltandC0at°e-nstrila CMRhaesrmeiacnrlcesh Pofsreaodcileantaiorgne
BInhsatvintaugtaer,

utilized
26.8 49.3 12.8 6.3 2.4 2.4

60°BtiU 0.023
81.5 101.4 86.4
90
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isaCthet(glass
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ofotosenmdpCOeunrmsaetuder
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TABLE
CBXin
Energy
SaltcXuialIlntVico.ens
Solar BInhsatvintaugtea,r
Sir-stil 0.026
102.1 86.4
B1.5 91 utilised 29.6 43.6 15.2 6.9 2.4 3.3

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(ref. 32 12 10 25 7 2 12
hrft
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(°F)

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