170 Ind. Eng. Chem. Fundam., Vol. 17, No.

3, 1978

Vacuum Steam Stripping of Volatile, Sparingly Soluble

Organic Compounds from Water Streams

Edgar A. Rasquln, Scott Lynn,' and Donald N. Hanson

Department of Chemical Engineering, Unlversity of Cellfofnla, Berkeley, California 94 720

A mathematical model was used to study the effect of pressure, steam flow, and column length on the steam
stripping of volatile organic solutes from water. It was found that, for a given inlet water temperature, there exists
an optimum pressure of operation at which the steam flow required for effective stripping is a minimum. This
pressure is the vapor pressure of water at feed temperature. In addition, the degree of stripping was found to de-
pend almost completely on column length and to be insensitive to steam flow above the minimum amount re-
quired to achieve stable operation of the stripper. Saturated aqueous solutions of n-butyl acetate (6300 ppm) and
diisopropyl ether (6900 ppm) at 30 OC were used as representative systems. At these concentrations of solute,
the most economical method of operation is obtained by carrying out the process at a column pressure high
enough to allow condensation of the effluent vapor with cooling water, using heat interchange between the en-
tering and leaving water streams if necessary.

Introduction Modelling Procedure

In chemical plants it is common to find water streams that The packed tower was treated as a differential contactor
contain small amounts of organic substances. These sub- whose operation could be expressed by the following equa-
stances must usually be removed from the water for envi- tions: interphase flux for the dissolved organic component
ronmental or economic reasons. A frequent approach to this
problem is extraction with a relatively volatile organic solvent,
which, in turn, produces an effluent water saturated with the
solvent. If its concentration is significant, this solvent must gas-phase water concentration
then be recovered from the aqueous stream.
PW0
For example, phenolic compounds are extracted from the yw = -xw*
quench water in the Lurgi coal gasification process using di- P
isopropyl ether (Phenosolvan process: Wurm, 1969; Beychok, component mass balances
1974). Butyl acetate is an alternate solvent. Solvent recovery d(Lxi) - d(Vyi)
is accomplished through a three-step process. First, the sol-
dz dz
vent is stripped from the aqueous stream by an inert gas.
Second, the solvent is absorbed from the gas by phenol, and d(Lxw) - d(Vyw)
(3)
the phenol-solvent mixture is sent to the main separator for dz dz
phenol and the organic solvent. Third, the gas stream is enthalpy balance
scrubbed of phenol by the water stream entering the plant and
is reused. d[L(HL,iXi + H ~ , w ~ w -
) l d[V(Hv,iyi + Hv,w~w)I
(4)
A simpler process for recovery of the dissolved solvent from dz dz
the water stream leaving the extraction unit is steam stripping interphase heat flux
(Earhart, 1975; Mulligan and Fox, 1976). However, in the
previous work no particular consideration was given to opti- d[L(HL,iXi + H ~ , w ~ w =
) l -ha(TL - Tv)
(5)
mizing the operation of the steam stripper; it was assumed to dz
operate at 1 atm. In the analysis that follows it will be shown pressure drop
that operation at a lower pressure frequently offers attractive
advantages over atmospheric pressure operation, and that -d=P ot10PLV2Tv(yiMWi ywMWw) +
design of such processes can be based successfully on simple dz P
procedures. auxiliary equations
The present work is thus a study of the removal of sparingly
soluble, volatile organic liquids from solution in water by Xi + xw = 1
means of vacuum steam stripping in packed towers. The study
Yi+Yw=1
deals with the two solvents named above, which are sometimes
used for phenol extraction, but the conclusions derived apply For analysis the column was divided into a number of dif-
to the stripping of other organic substances having comparable ferential elements, and at each point nine equations were used.
volatilities and solubilities in water. A similar investigation The variables calculated a t each point were TL, Tv, P, L, V,
of processes for degassing such components as COz, 0 2 , and and two mole fractions in each of the two phases. In writing
Nz from water was done by Rasquin et al. (1977). The same the equations, the assumption was made that the mass
mathematical approach has been taken in this work. A model transfer is controlled by liquid-phase diffusion. The further
of the packed column has been utilized to study the effect of assumption was made that the heat-transfer resistance was
the different operating parameters: pressure, steam flow, and entirely in the liquid phase because of the small heat capacity
column length. of the vapor stream. Thus the composition and temperature
0019-7874/78/1017-0170$01.00/0 0 1978 American Chemical Society

Table I. Values of Less Common Parameters Used in
Steam-Stripping Calculations
nvstem
parameter DIPE BuAc
Kow 0.018 s-l 0.018
ha 2.0 X lo6 J/s m3 K 2.0 X lo6 J/s m3 K
AHv @ 30 O C 35.4 X lo6 J/kg-mol 28.6 X lo6 J/kg-mol
D @ 30 "C 9.1 X m2/s 8.8 X mz/s
Po @ 30 O C 25.5 kN/m2 2.25 kN/m2
of the vapor at any point in the column were assumed to be the
values for the vapor a t the interface, and the vapor phase was
taken as saturated a t interface conditions. The pressure-drop
equation used is the correlation developed by Leva (1954). The
vapor temperature a t the bottom was set a t the saturation
temperature of water and the vapor at that point was assumed
to be pure water. The values of the less common parameters
used in the calculations are listed in Table I.
The equations were expressed in terms of the variables
chosen, linearized, and approximated by their finite-difference
forms. The resulting set of equations, together with the ap-
propriate boundary conditions, was solved by the method of
Newman (1968) for coupled ordinary differential equations.
Details of the procedure are given by Rasquin (1977).
During the present study, the liquid to be treated was as-
sumed to enter the vacuum column at 30 "C. However, the
conclusions reached are applicable across a wide range of feed
temperatures. The superficial liquid mass velocity in the
column was set a t 0.7535 kg-mol/m2-s (10 000 lb/ft2.h). The
value of the mass-transfer coefficient for the dissolved com-
ponent was obtained from the correlation by Sherwood and
Holloway (1940). The mass-transfer coefficient was obtained
for 2-in. Raschig rings but can be considered typical for the
same size packing in other forms such as Pall rings. The
heat-transfer coefficient was obtained from the Chilton-
Colburn analogy, using an exponent of 0.5 on the ratio of
Schmidt number to Prandtl number. In all calculations, the
concentration of solvent in the entering water was the satu-
ration concentration at 30 "C. These values for butyl acetate
(BuAc) and diisopropyl ether (DIPE) are 6300 and 6900 ppm,
respectively. Activity coefficients for the dissolved compo-
nents were obtained from mutual solubility data correlated
with the van Laar equation. At 30 "C and saturation concen-
tration the activity coefficient is 925 for BuAc and 809 for
DIPE. Pressure drop calculations were based on data for 2-in.
Pall rings (Eckert et al., 1958). The value for the desired
concentration of solvent in the purified water was taken to be
50 ppm.
Process Description
The process under study is similar in many ways to other
steam stripping operations. However, the concept of minimum
steam requirement here is considerably different from that
of a classic textbook stripper, and the normal interchange-
ability of column length and steam flow as means for accom-
plishing a desired degree of stripping is much reduced. How
these characteristics of the process arise can best be seen by
considering operation of the process, first with no steam flow
and then with increasing amounts of steam.
For the process to operate a t all with no steam admission,
the column pressure must, of course, be below the saturation
pressure of the liquid stream a t the temperature a t which it
enters. At such a pressure, as the liquid flows through the
column, the organic compound will transfer from the liquid
phase to the vapor phase. Because the organic compounds
being considered are reasonably volatile and because they
exhibit very large activity coefficients a t their typical liquid
concentrations, they resemble insoluble gases to a large extent.
Ind. Eng. Chem. Fundam., Vol. 17, No. 3, 1978 171
It is helpful to think of the vapor stream rising in the column
as a light organic gas saturated with water at the local tem-
perature.
If no steam is admitted a t the bottom, the amount of solute
that transfers into the vapor phase is primarily dependent on
the energy balance. The energy to vaporize the solute, and to
vaporize the water that accompanies it, must come from the
liquid. As a result the liquid temperature falls rapidly as the
liquid flows down through the column, even at the low organic
concentrations being considered here. As the temperature
drops, the vapor pressure of water drops, the local concen-
tration of the organic component in the vapor phase rises, and
the driving force for transfer of the solute from the liquid
drops, in general effectively stopping the process a t levels of
solute in the liquid that are unacceptably high.
Adding energy by heating the incoming liquid is unavailing.
Consideration shows that this energy is largely lost a t the top
of the column in simple flashing of the liquid, and is thus not
available further down in the column. On the other hand, if
the process is operated so that the vapor and liquid flow
concurrently, the vapor formed when the liquid flashes effects
some stripping as the liquid flows down the column. However,
the amount of vapor that must be generated in order to
achieve a high degree of stripping of the solute is so large that
the energy requirements are prohibitive. Rasquin et al. (1977)
show that this process is economical for degassing COa and 0 2
from water; in that particular case the concentration of the
dissolved light components is an order of magnitude or more
smaller than the concentration of organic compounds being
considered here.
Returning to consideration of the countercurrent process,
one may first assess the result of the addition of a small
amount of steam at the bottom of the column. Since the liquid
stream at this point is substantially subcooled relative to the
column pressure, the steam immediately condenses, accom-
plishing nothing but an increase in the effluent liquid tem-
perature commensurate with the amount of steam fed. As the
amount of steam is increased this temperature rises, until fi-
nally it reaches the saturation temperature of water at column
pressure. Any substantial increase in steam above this amount
causes essentially the entire steam flow to propagate com-
pletely through the column, and the heating of the liquid
stream takes place at the top of the column rather than a t the
bottom. The amount of steam flow associated with this mode
of operation is, in general, sufficient to accomplish any rea-
sonable degree of stripping. The relative volatility of the solute
is high, the driving force for mass transfer is therefore more
than adequate, and hence any further increase in steam flow
past this value is of only marginal usefulness in increasing the
mass transfer. The degree of stripping achieved is then almost
wholly dependent on the length of the column. Since the so-
lutions under consideration are quite dilute, the source of the
steam will make little difference to the behavior of the column;
the steam may be sparged in directly or generated in a re-
boiler.
Results a n d Discussion
The anticipated variations in column performance with
steam flow are shown in Figure 1 as calculated for stripping
butyl acetate from water in a 4-m column operating a t 5.1
kN/m2 (38 Torr). At low steam flows the stripping achieved
is almost the same as that obtained with no steam. As steam
flow is increased past a critical amount the degree of stripping
increases greatly, but then, at still higher steam flows, the
stripping is again only slightly affected by changes in the
amount of steam. Figure 2 shows the vapor flow profile
through the column for four values of steam flow and illus-
trates how the profile is altered strikingly by small changes
172 Ind. Eng. Chem. Fundam., Vol. 17, No. 3, 1978

10,000 i i I.

Feed temp 3 0 T
Feed C O ~ C6300ppm

P \,/Equation 19)

1000 - -
-
I

-
?
.E 0.01 - -
1
I
t1
c
1007 -
u

-
-
c
z O 4.5 5.0 5.5 6.0
Column pressure i k N / m 2 )
Figure 4. Effect of pressure on the minimum steam flow.

t
1 00 0.010 0.020 0.030
several column pressures are shown. The curves for 4.5 kN/m2
and 4.23 kN/m2 (the vapor pressure of water at 30 "C) coin-
Steom flow imoies/mole feed! cide. It is apparent that column pressure has an effect on the
Figure 1. Effect of inlet steam flow on column operation. value of the minimum steam flow. However, it is also apparent
that column pressure has little effect on the degree of stripping
obtained if the column is operated a t any steam flow reason-
ably greater than the minimum at a given pressure. This result
stems from the fact that the partial pressure of BuAc in the
vapor is low even at the highest column pressure considered,
and further reduction through lowering column pressure has
little effect since the diffusion is liquid-phase controlled.
The minimum steam flow is determined almost entirely by
the energy requirements. Calculations have shown that it can
Outlet BuAc: 950 ppm
be closely estimated from the following simple energy bal-
ance.

(m.ii;:iinimum) (
steam to heat entering
= water from inlet temp

)
0.0080
'3305ppm

to saturation a t the
Vopor f l o w lmoles/rnole f e e d ! bottom of the column
Figure 2. Effect of inlet steam flow on vapor-flow profile in column
1 steam to provide\ 1 steam to saturate the \
and on effluent concentration of butyl acetate.
the latent heat desorbed solute a t
of vaporization the top of the column
\ of the solute ' \ a t inlet temperature '
(9)
The pressure at the bottom of the column is not known
beforehand because of the unknown pressure drop in the
column. Hence the amount of steam required to heat the en-
tering water to saturation must be calculated by iteration. In
practical column designs, however, the pressure drop is a small
fraction of the total pressure.
Figure 4 shows the relation between the true minimum

401
0.010
'
0.014
I I
0.018
Steom f l o w (moles/moie feed)
'
0.022
Figure 3. Effect of inlet steam flow on the stripping of n-butyl acetate
from water.
in the amount of stripping steam supplied to the column.
It is apparent that a minimum steam flow exists above
which column operation is satisfactory, but that steam flows
much greater than the minimum are not productive in in-
creasing the stripping of the butyl acetate. Optimum operation
of the column thus entails use of a steam flow near the mini-
mum, and the determination of this quantity is important for
design calculations. Figure 3 again shows the effluent con-
centration of BuAc for a 4-m column as a function of steam
flow in the region of probable column operation. Curves for
0.026
' steam flow, as determined from Figure 3, and column pressure.
It also shows the minimum steam flow estimated from eq 9.
Agreement is good throughout the region of higher pressure.
However, the estimated minimum flow (eq 9) becomes much
too high as column pressure nears the vapor pressure of water
at inlet liquid feed temperature, approaching an infinite value
there. This result stems from the approximation in eq 9 that
the vapor phase leaving at the top of the column is saturated
with water vapor at the inlet temperature. In the more exact
calculations it is found that the vapor leaves the top of the
column either slightly above or below the feed temperature,
depending on column pressure and the amount of steam flow.
At steam flows near minimum, however, the vapor leaves
below feed temperature, and as a result, the sharp rise pre-
dicted by eq 9 does not occur. However, at column pressures
a t or above the pressure at which eq 9 displays a minimum,
the estimated minimum steam flow is only about 15%above

DIPE\‘iq
P r e s 5.1 kN/rnZ
Inlet Concentrotion
i eration is necessary in any event, and an economic balance
C o l u m n Lenqlh ( m i
Figure 5. Effect of column length on the stripping of n-butyl acetate
and diisopropyl ether.
the true value. The difference is caused by assuming that all
of the steam flows to the top of the column before any of it
condenses. The value predicted by eq 9 is thus conservative,
and can be used satisfactorily as a design value without the
need for the complex column calculation. For the region of low
pressures, in which the values predicted by eq 9 swing upward
with decreasing pressure, a reasonable value can be obtained
by simply taking the minimum in the curve.
Determination of minimum steam flow for other column
lengths shows only what would be expected from eq 9, a small
increase with increasing length due to the increased pressure
drop through the column.
The degree of stripping of both BuAc and DIPE from water
is shown in Figure 5 as a function of column length at a column
pressure of 5.1 kN/m2 (38 Torr). The curves show that the
concentration of either solvent in the effluent water decreases
rapidly with increasing column length. However, Figure 5
again shows that, for a given column length, the degree of
stripping obtained increases little with increasing steam flow;
for diisopropyl ether, increased steam flow has essentially no
effect. The lack of sensitivity of the degree of stripping to the
steam flow is, in general, due to the high relative volatility of
the dissolved solute. DIPE is substantially more volatile than
BuAc. These results show dramatically the futility of trying
to improve stripper performance for such systems by in-
creasing steam flow. Operation should be conducted with the
minimum amount of steam necessary to achieve stable
stripper operation, and it is clear that the only way to achieve
a particular degree of stripping is through a column of suitable
length.
Examination of Figure 5 shows that both lines for stripper
performance are essentially straight and extrapolate to zero
stripping a t zero column length, indicating that a relatively
simple calculation of the degree of stripping for various col-
umn lengths is possible. Equation 1 can be integrated as-
suming all terms except x i and z to be constants and the ap-
propriate average value of ( x i - x i * ) to be the log-mean av-
erage. For a system as volatile as DIPE, very accurate results
are obtained by simply assuming that the interface concen-
tration, x i * , of DIPE in the liquid is zero. For BuAc, use of a
zero interface concentration shows a required length of 3.6 m
to reach 50 ppm, whereas the detailed column calculations
show 4.2 m. Use of a log-mean driving force in eq 1gives a re-
quired length of 4.6 m, which is conservative, and accurate
enough for preliminary design.
Finally, consideration must be given to the condensation
of the overhead vapor from the column. For a feed a t a given
temperature, the calculations done here show that the steam
requirement is minimized by operation of the column at the
Ind. Eng. Chem. Fundam., Vol. 17, No. 3, 1978 173
vapor pressure of water at feed temperature. Operation below
the optimum pressure results in flashing of the feed and, in
effect, operation at the vapor pressure of the feed at a new,
lower temperature; the steam requirement remains essentially
the same. On the other hand, operation above the optimum
pressure requires additional steam; for an increase of about
20% the change is small, but a t higher pressures the steam
requirement is increased significantly.
However, if the column is operated with the feed near or
above the temperature of the available cooling water, the
overhead vapor cannot be condensed without compressing it.
For the case of highly volatile dissolved compounds such as
C02 or butane, compression of the overhead vapor or refrig-
between compression cost and increased steam cost must be
used to determine the optimum column pressure.
For dissolved solvents such as butyl acetate or diisopropyl
ether the attractive alternative is operation of the column a t
a higher pressure, specifically the pressure at which the
overhead vapor can be condensed with the available coolant.
For the two solvents considered here, and assuming conden-
sation at 30 O C , the column pressure would have to be 6.4
kN/m2 (48 Torr) for BuAc and 30 kN/m2 (223 Torr) for DIPE.
Steam requirements could be minimized by exchanging heat
between the effluent liquid and the incoming feed to raise the
feed temperature as close as economically feasible to the
boiling point of water at column pressure. While this use of
heat exchange would allow operation a t essentially any pres-
sure, higher pressures would require a higher temperature
excursion by the liquid feed and a higher duty in the ex-
changer.
The column diameter is not affected significantly by the
pressure of operation. I t is determined by L and the total
liquid flow rate in the column since vapor velocities are small
even a t the lowest pressures of interest. The optimum oper-
ating pressure will thus be determined by minimizing the sum
of the costs of the condenser and the heat exchanger for
heating the feed with the effluent water.
Acknowledgment
One of the authors (E.A.R.) is grateful to the Hydrocarbon
Research Fund of Venezuela (FONINVES) for their financial
support.
Nomenclature
ha = liquid-phase heat-transfer coefficient, J/m3-s-K
H = molal enthalpy, J/kg-mol
KOLU = overall liquid phase mass-transfer coefficient, s-1
L = superficial liquid mass-velocity, kg-mol/m2.s
MW = molecular weight
P = column pressure, N/m2
Po = vapor pressure, N/m2
T L = liquid temperature, K
Tv = vapor temperature, K
V = superficial gas mass-velocity, kg-mol/m2.s
x = liquid mole fraction
x * = liquid mole fraction a t equilibrium with the vapor
phase
y = vapor mole fraction
z = columnlength, m
Greek Letters
a,/3 = constants of pressure drop equation
PM = molar liquid density, kg-mol/m3
Subscripts
i = dissolved organic component
w = water
V = vapor phase
L = liquid phase
174 Ind. Eng. Chem. Fundam., Vol. 17, No. 3, 1978

Literature Cited Rasquin, E. A., Lynn, S., Hanson, D. N., Ind. Eng. Chem. Fundam., 16, 103
(1977).
Beychok. M. R., "Coal Gasification and the Phenosolvan Process", presented Sherwood, T, K,, ~ , A,
~ L,, T l ~ i ~lnst, Chem,
~~ ~ ,~36,39-7~
~ ~
at the 168th National Meeting of the American Chemical Society, Atlantic (1940).
City, N.J., 1974. Wurm, H.J., Gluckauf, 104 (12),517 (1968).
Earhart, J. P., Ph.D. Thesis, University of California, Berkeley, Calif., 1975.
Leva. M., Chem. Eng. Prog. Symp. Ser., 50 (lo),51 (1954).
Mulligan, T. J., Fox, R. D.,Chem. fng., 83 (22),49 (1976).
Newman, J., Ind. Eng. Chem. Fundam., 7 , 314 (1968). Received f o r review April 11,1977
Rasquin, E. A., M. S. Thesis, University of California, Berkeley, Calif., 1977. Accepted April 20,1978

Modeling of Thermal Cracking Kinetics. 3. Radical Mechanisms

for the Pyrolysis of Simple Paraffins, Olefins,
and Their Mixtures

K. Meenakshi Sundaram and Gllbert F. Froment'

Laboratorium voor Petrochemische Techniek, Rijksuniversiteit, Gent, Belgium

Radical reaction schemes for the cracking of ethane, propane, normal and isobutane, ethylene, and propylene
were set up. The kinetic parameters of these schemes were determined by fitting experimental data obtained
under nonisothermal and nonisobaric conditions in a pilot plant. The set of continuity equations for both molecu-
lar and radical species was integrated using Gear's algorithm for stiff differential equations. The reliability of the
parameters was tested by simulating the cracking of binary and ternary paraffinic mixtures. A satisfactory fit of
the results of mixtures cracking was obtained with a reaction scheme derived from the superposition of the
schemes for single-component cracking.

Introduction gas temperature and total pressure profiles. It is assumed that

Thermal cracking reactions mainly proceed via free radical
mechanisms (Laidler, 1965). Many specific mechanisms have
been proposed to explain the cracking of simple molecules.
The majority of the mechanisms have been deduced from data
obtained at subatmospheric pressures, low temperatures, and
low conversions. Moreover, they were derived through the
pseudo-steady-state concept which assumes the radical con-
centrations to be constant. This condition is not fulfilled in
reality, neither in an industrial reactor nor even in an iso-
thermal bench scale reactor (Edelson and Allara, 1973). For
these reasons, at elevated temperatures the uncertainties in
the parameters are high and sometimes attain orders of
magnitude. In the present paper radical schemes for the
cracking of normal and isoparaffins, olefins, and their mix-
tures are developed. The determination of their kinetic pa-
rameters is based upon experiments conducted in a pilot re-
actor under conditions as close as possible to those used in
industry (Van Damme et al., 1975; Froment et al., 1976a,b,
1977).
Continuity Equations
Free radical reactions involve initiation, propagation or
H-abstraction, and termination steps. The continuity equa-
tion for t h e j t h species in an isothermal reactor with plug flow
may be written
d F, N adopted in this work. Gear's method can be applied to any
= -0Rj = -0 ,E (sijri)
dz 1-1
For nonisothermal and nonisobaric conditions the reaction
rate ri has to be computed for the experimentally measured
0019-7874/78/1017-0174$01.00/0
the reactions are elementary and therefore the order corre-
sponds to the molecularity. Also, the rate coefficients obey the
Arrhenius relationship within the temperature range cov-
ered.
The first-order differential equations represented by eq 1
are usually nonlinear and coupled, and hence analytical so-
lutions are not possible. The concentrations of the radicals are
much lower than those of the molecular species (e.g., vs.
10-2 M) so that the eigenvalues of the differential equations
differ by orders of magnitude. With classical integration
methods, an extremely small step size has to be used to ensure
the stability of the numerical integration. To overcome the
mathematical difficulties, pseudo-steady state for radical
concentration has been assumed. This assumption allows the
differential equations for the radicals to be replaced by alge-
braic equations (Snow, 1966; Pacey and Purnell, 1972b;
Blakemore and Corcoran, 1969). In a recent communication
the present authors (to be published) have quantified the
errors induced by this assumption and shown that for reliable
parameter estimates, the complete integration for the conti-
nuity equations for both molecular and radical species for the
entire conversion range is essential, because the radicals vary
significantly and continuously with conversion.
Of the many currently available methods for integration of
stiff differential equations (see Aiken and Lapidus, 1974,
1975a,b; Seinfeld et al., 1970; Sena and Kershenbaum, 1975a1,
the one proposed by Gear (1971) seems to emerge. It is also
degree of stiffness and allows for any degree of accuracy of
integration with moderate computer time. It essentially uses
the Adams-Moulten predictor-corrector method, which is an
implicit technique.
0 1978 American Chemical Society