ESL-IE-83-04-129

FREEZE CRYSTALLIZATION PROCESSES:

EFFICIENCY BY FLEXIBILITY
James A. Heist, P.E.
Heist Engineering Corp.
Wilmington, NC

Thomas S. Barron, P.E.

Heist Engineering Corp.
Lafayette, CA
particularly efficient, especially when
compared to other types of freezing
methods, and neither scales well to
applications with very large heat loads.
The inability to scale to large sizes is
the major factor that has kept this
equipment from applications in the
chemical and petroleum industries.

ABSTRACT
Energy consumption in fractionating
solutions by distillation and evaporation
can be reduced by 70 to 90% by using
freeze crystallization processes. The
thermodynamic bases for the substantially
lower energy requirements include:
1) The phase change is required only
once in freeze processes, as opposed
to the high reflux ratios needed in
most distillation separations.
2) The latent heat of fusion is less
than the heat of vaporization, and
the process operates at a lower
temperature, so the entropy of the
separation is less.
3) A heat pump is used in the freeze
crystallization process to transfer
heat from the freezer to the melter,
providing advantages similar to the
vapor compression evaporator cycle.

TABLE 1

ENERGY USE COMPARISON

Energy Consumption
Application

INTRODUCTION
Freeze crystallization has been used
historically in those applications where
other separation processes are incapable
of effecting the separation; i.e.,
principally in isomer separations. Yet
the energy consumption with the freeze
process is substantially less than that of
alternative evaporative processes, as
shown in Table 1.
Guidelines can be formulated for
preliminary evaluations of new
applications, but none have been found
that are foolproof.
Therefore, any
analysis of a new application should
include a preliminary design sufficient to
estimate the energy consumption of the
proposed freeze separation process.

550

Fruit Juice Conc.

BTU/# water removed

365

85

Seawater Desalting,
(Multistage flash)
BTU/# water removed

100

60

Brine Concentration
120
(vapor comp, fall film)
BTU/# water removed

80

Black Liquor
(pre-conc, 15 to 25%)
BTU/# water removed

230

50

Acetic Acid Refining

(acetaldehyde route)
BTU/# acid produced

8800

500

Acrylic Acid Refining

(propylene oxidation)
BTU/# acid produced

1600

190

600

150

BTX Fractionation
(TeEG extraction)
BTU/# BTX produced

Existing commercial freeze crystallization

equipment is based on indirect heat
transfer - either through a scraped
surface exchanger or with a build-up of
crystallized material on the surface (in
batch operations). Neither is

Freeze
Cryst'n

3850

Sugar Production
(from Beets w/cogen)
BTU/# water removed

Freeze crystallization should be

considered an alternative to all
distillation and evaporation separation
processes. The factors which affect the
relative efficiency and economics of the
process are discussed in this paper.

Convent'l
Evap/Dist

Note: all electrical power converted to

BTU at 10,000 BTU/kw-hr.

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Proceedings from the Fifth Industrial Energy Technology Conference Volume II, Houston, TX, April 17-20, 1983

ESL-IE-83-04-129

Refrigeration Cycle that acts

like a heat pump, removing heat from
the freezer and compressing it to a
sufficient pressure that it will
condense to provide the hea t needed
to melt the crystal after it has
been separated. A Heat Rejection
portion of this cycle 'pumps' the
ambient heat leaking into the system
and inefficiencies in the process
from the operating temperature up to
ambient conditions, where this heat
is rejected from the system.

The freeze crystallization process has a

great deal of inherent design flexibility.
Thus, it should not be treated like
evaporators, where a standard commercial
unit is purchased and installed with
minimal optimization.
Rather, it should
be thought of in terms of fractional
distillation and extraction trains, and
optimized for each application. The
freeze process will ultimately be a
'building block' technology, with standard
and custom components, assembled into a
complete process technology, optimized for
each general application area.
Unit
operations that make up the freeze
crystallization process are discussed
below.

- Also included in the process are

Heat Exchangers to recover the
'cold energy' from the process
streams, for cooling the fresh feed
material.

FREEZE SEPARATION TECHNOLOGY

The Unit Operations

A general operating mode is as follows.

Feed enters the process through heat
exchangers where the cold is recovered
from the product and concentrate streams
exiting the system. This feed then enters
the freezer or crystallizer where a
portion of it is converted to a solid, in
discreet, relatively small (100 to 500
microns) crystals. The crystals are
pumped as a slurry from the freezer to a
separator which removes the liquid from
the slurry, and usually washes the
crystals with a small portion of either
melted product or some suitable wash
material that will not dissolve the
crystal. Most of the liquid is recycled
to the freezer where more of the desired
constituent is recovered.
Excess
concentrate is bled from the system,

A general process schematic of the freeze

crystallization separation process is
shown in Figure 1. The major components
of the process include:
- A Freezer, or crystallizer, where
a portion of the liquid is changed
to the solid phase by removing heat.
- A Separator where the crystal
phase is separated from the
remaining liquid, and the crystals
are washed to remove adhering brine
from the surface. Leaching of the
crystal pack can also occur here if
there is a solid solution in the
crystals.

C.H.

r-v-$
PROOUCT~------~

r ~AIN

FEED HEAT
EXCHANGERS

-~--L-~-

(
I
COMPRESSOR
_ _ _ _ _ --.J~ _ - - l

RECYCLE LIQUID
FREEZER

PRODUCT
SLURRY

CRYSTAL
SEPARATOR
HASHER

CONCEN-f-_ _---J
TRATE

FIGURE 1

FREEZE CRYSTRLLIZRTION

PROCESS DIRGRRM

838
Proceedings from the Fifth Industrial Energy Technology Conference Volume II, Houston, TX, April 17-20, 1983

ESL-IE-83-04-129

through the feed exchanger, to prevent

excessive build-up of impurities. The
washed crystal is then melted, either
directly in contact with the refrigerant
(which condenses on the crystal giving up
its latent heat to melt the crystal), or
through a heat exchange surface.
Part of
the melted product can be recycled to
reslurry the washed crystal, as necessary.
The net product flow is pumped through the
feed exchanger and out of ~he system. The
refrigeration equipment removes heat from
the freezer and transfers it to the
melter, with any excess heat being removed
from the system through the heat rejection
compresser.

with melted product for transport to a

melt heat exchanger. The crystals are
washed in this device from the top, with
the wash material combining with the
liquid and flowing out the screens.

SCRAPER
MECHANISM

HASH
FLOW

MELT l

CRYST~L

The Freezer removes sensible heat to

cool the feed down to the freezing point,
and then latent heat to convert liquid to
solid. Heat is removed in one of three
ways:

DRAIN
SCREENS

1) Indirectly, through a heat transfer

surface with refrigerant separated
from the process liquid.
2) By direct contact of a secondary
refrigerant with the process
liquid.
SLURRY

3) By evaporating one of the

components of the liquid, in effect
using it as a secondary
refrigerant.

FIGURE 2

WASH COLUMN SCHEMATIC

The direct contact freezers have no

practical or theoretical size limitation.
Conventional indirect contact freezers
have used scraped surface heat exchangers,
which have practical size limits.
Alternative technologies, using falling
film and less expensive scraping
mechanisms, are being developed and will
improve the the cost effectiveness of the
indirect process.

The Heat Exchangers used in a freeze

separation process for energy recovery
from the cold process streams are usually
of the plate type, selected to achieve
closer approach temperatures. They are
used principally to cool the feed to the
plant, but are also used in absorption
refrigeration systems.
Phase Equilibria

The Refrigeration System is a function

of the freezer and the difference in
temperature between the crystal forming in
the freezer and melting in the melter.
The refrigeration cycle can use either
conventional mechanical compression of the
refrigerant or a thermal compression
cycle. Another alternative is an
absorption refrigeration cycle, giving the
process the opportunity to use waste heat
and cooling water in place of the higher
quality forms of energy.

Freeze processes are, like fractional

distillation, sUbject to the dictates of
thermodynamic equilibria. The principal
difference is that, in vapor phase
processes multiple vaporizations are
needed to meet reflux requirements.
In
solid phase separations the effect is to
create a larger difference in temperature
between crystal formation (in the impure
solutions) and melting (in pure
component).

The Separator can be either a

centrifugal device, a filter, a screen, or
a vessel called a wash column.
A typical
wash column is pictured in Figure 2.
Slurry is pumped in the bottom, with the
liquid flowing out at the screens and the
crystal forming a porous plug that is
propelled up the column. The crystals are
scraped from the top and either dumped
into a direct contact melter or slurried

A simple binary solid-liquid phase

equilibria diagram is shown in Figure 3.
Points T(Ml) and T(M2) represent the
melting temperatures of pure Component 1
and 2, respectively. The point T(E) is
the eutectic temperature, or composition
and temperature at which both Components 1
and 2 crystallize simultaneously.
In a
eutectic the components normally form two
discreet, pure crystals.

839
Proceedings from the Fifth Industrial Energy Technology Conference Volume II, Houston, TX, April 17-20, 1983

ESL-IE-83-04-129

have to calculated from binary component

data. We have found that portraying the
more complex equilibria by the method
shown in Figure 4 is a useful
visualization of what happens in these
freeze processes. Here, crystallizing
temperature is shown as a function of the
percent recovery of the first component
that crystallizes.
Eutectic points are
shown on the diagram, and as depicted,
usually result in a change in the slope of
the curve.

The curve between the eutectic point and

the pure component melt temperatures is
the solid-liquid equilibria line for
various compositions. At a starting
composition X and at temperature T(i),
nothing happens as the solution is cooled
until it reaches temperature T(Ci), the
initial crystallization temperature. At
this point pure Component I crystals start
to form, and the composition of the
remaining liquid then becomes richer with
Component 2.
As heat is removed from the
solution more Component I crystal is
formed, but the crystallization
temperature also decreases. Eventually
the composition is changed sufficiently
that the remaining brine achieves the
eutectic composition and then Component 2
begins to crystallize. Further heat
removal produces stoichiometric quantities
of each crystal.

TC

I
I
I

, X~T~
I
I
I
I

~1 TEMP

907.

75%

507.

257.

OX

% RECOVERY
~~

FIGURE 4
OPERATING SCHEMATIC
07. 1
1007. 2

COMPOSITION

DESIGN VARIABLES

1007. 1
07. 2

A number of options are available to the

process engineer to design an efficient
freeze separation process. Much is common
with other engineering practices, such as
insulation thickness and type, pipe
pressure drops, pump efficiencies, and
heat exchanger surface area.
In addition,
many other factors are considered for the
design of the freeze process:

FIGURE 3
BINARY SLE PHASE DIAGRAM
The eutectic might represent an upper
limit to recovery of one component from
the material.
But usually the solid
phases can be further separated based on
size, density, or other properties. Thus,
the only limit in recovery from the
process is imposed by other factors, such
as a build up of trace materials which
have to bled from the system.

- Integration of freezing with the

rest of the process.
- Phase equilibria alterations.
- Crystallizer design and staging.
- The refrigeration cycle.

In a mUlti-component system, the phase

equilibria diagram is not as simple as the
one shown in Figure 3. Triangular
diagrams can be used for tertiary
solutions, but most systems cannot be
portrayed accurately by even this.
Usually phase equilibria in real systems

- Melter design.
Washing/leaching processing.

MO

Proceedings from the Fifth Industrial Energy Technology Conference Volume II, Houston, TX, April 17-20, 1983

ESL-IE-83-04-129

Here, as in virtually all applications,

there is an advantage to integrating the
freeze separation process as early in the
main production process as possible. Th
alternative streams for processing by
freeze crystallization are shown in Figure
6.
As is shown, there is relatively
little difference in the energy required
for freeze refining any of the proc8ss
streams.
However, the further back into
the conventional refining process the
freeze process is placed, the more energy
reduction is effected by replacing the
components in the conventional refining
train.

Process Integration
The importance of selecting the right part
of the process in which to place the
freeze separation process is illustrated
by BTX separations. This application
involves the fractionation of the benzene
toluene and xylene found in both petroleu~
fractions and in the by-product stream
from olefins plants.
BTX's can comprise
from 25 to 75% of the streams from crude
distillations, from reforming, and from
olefin pyrolysis furnaces.
The other
components are principally parafins and
cycloparafins, as well as some heavier
aromatics.

Phase Equilibria

The parafi~s and aromatics have very close

bOlllng pOlnts, so fractional distillation
is not practical.
Extraction with
tetramethylene sulfone or tetraethylene
glycol (TeEG) is the usual method used to
separate the aromatics from the parafins.
The aromatics are then fractionated in a
series of columns as shown in Figure 5.

Another set of design varibles that can be

used to minimize energy consumption in
freeze separation processing are the solid
liquid equilibria that govern the
temperatures and concentrations at which
the various solid (crystal) phases form.
The temperature and concentration at which
a product begins to crystallize from
solution can be altered by either changing'
the solution it is in (eg., through a
preliminary solvent extraction step), or
by using a refrigerant or other material
which alters the phase equilibria of the
original solution.

Included in Figure 5 is the energy

consumed in each of the refining steps.
Note that half of the energy is used in
separating the aromatics from the
paraffins. The other half is used to
separate the aromatics into the benzene,
toluene, and (mixed) xylene fractions.

PRRRFFINS

RRFFINRTE
BENZENE
250 BTU
B

~__-4~125

BTU
BTX

BENZENE
COLUMN

EXTRRCT
STRIPPER
375-400 F

FIGURE 5
BTX FRACTIONATION
BY DISTILLATION

XYLENE

TOLUENE
COLUMN

C9

RROMRTICS

~l

Proceedings from the Fifth Industrial Energy Technology Conference Volume II, Houston, TX, April 17-20, 1983

ESL-IE-83-04-129

Refrigerants can also be selected to alter

the freezing temperature of a solution.
In organic solutions the refrigerant is
chosen to increase the activity
coefficient of the crystallizing material,
which in turn increases its relative
crystallizing temperature.
In water
solutions the ice crystallizing
temperature can be raised by as much as 30
degrees Centigrade by refrigerants that
form hydrates with the water. This
hydrate is a crystalline structure called
a clathrate, and is formed of water and
the refrigerant.

(CONVENTIONAL REFINING)

240

CRUDE BTX [25 WTY.

DE-PARIFFINED
EXTRACT [60 WTY.
TETRAETHYLENE GLYCOL)
EUTECTIC POINT

230

220

210

FIGURE 6

8TX FREEZE REFINING

x:

W
t

200

The first of these is illustrated in

Figure 7 by the same BTX application
discussed above. As the various BTX
solutions are cooled, benzene is the first
component to reach its solubility limit
and begin to crystallize. Xylene monomers
and then toluene follow in the
de-paraffined BTX solution, while some of
the paraffins may begin to crystallize
before the toluene in the crude BTX. The
initial crystallizing temperature is a
function of the other components in the
solution. The paraffins depress the
initial crystallizing temperature, but the
extractant (TeEG in the example shown)
actually increases the crystallizing
temperature even though the fraction of
benzene in the solution is substantially
lower.
Note that the TeEG also decreases
the solubility of the xylenes in the
solution.
Thus, for a given operating
temperature, the effect of a suitable
phase alteration material is to increase
the amount of product recovered and
decrease the energy consumption.

190

.B

.6

.4

180

.2

FRACTION BTX RECOVERY

,

1.

.8

I f '

.6 .4

.2

FRACTION BENZENE RECOVERY

FIGURE 7

8TX SOLID-LIQUID EQUILIBRIA

DIf\.GRAM

The hydrate phase diagram is shown in

Figure 8. The salient features of the
diagram are:
- A critical temperature, Tc, above
which the hydrate crystal will melt,
regardless of pressure.
- A critical pressure, Pc, which
corresponds to the maximum
temperature with hydrate crystal
formation.
Below this critical
pressure the maximum temperature at
which hydrate crystals form
decreases, corresponding to line AB.

The power requirements shown in Figure 6

are for recovery to an operatin~
temperature of 200 degrees Kelvin. The
difference in energy consumption between
Figure 6 and Table 1 reflects full
recovery of the BTX's. With the TeEG
absorbent studied here, the absorbent
crystallizes and increases the energy
required, although the consumption is
still less than for conventional
fractional distillation.

- A normal fusion temperature, Tf,

where water normally forms ice
crystals.

842
Proceedings from the Fifth Industrial Energy Technology Conference Volume II, Houston, TX, April 17-20, 1983

ESL-IE-83-04-129

VAPOR REF
+ HIITER

VIIPOR REF
+HYDRIITE

W
IX

n.

An example of hydrate use is sugar

refining.
In the production of sugar from
cane and beets, a thin juice is produced
which is concentrated, purified, and then
crystallized.
Freezing and reverse
osmosis(RO) are currently being
investigated for water removal.
To date
it has been found that RO can only
concentrate to 30% sugar, and non-hydrate
freeze processes have been limited to
about 45% sugar before the viscosity is
too high.

HYDRATE
AGENT

W
IX
:J
(I)
(I)

Since most food industry separation

requirements are for water removal, which
is now usually done in multiple effect
evaporators (MEE's), this is an ideal area
of application for hydrate freeze
separation processes.

/
/

c
/ I

LIQUID REF /
+HYDRATE
/

LIQUID REF
+HATER

1/

/S' /

S-/

IS

IQUID I

REF +ICE I

Tf

Tc

A hydrate process that increases the

crystallizing temperature by 30 degrees F'
will allow an increase in sugar
concentration to over 60% at the same
viscosity.
This condition will be very
near to the eutectic crystallizing
temperature, where sugar will also
crystallize from the solution as hydrate
crystals are formed.
The energy reductio~
shown in Table 1 presumes either RO or
freeze pre-concentration, followed by
hydrate freeze crystallization.

TEMPERATURE

FIGURE 8
HYDRATE PHASE
EQUILIBRIA DIAGRAM
- Freezing point depression lines,
A'B' and A' '8", which show the
effects of impurity levels on the
crystallizing temperature of both
the hydrate and ice.

Staging
Through the use of process staging, energ~
consumption can be reduced significantly.
In large facilities, where multiple
equipment trains would be used for
flexibility and reliability, the cost
penalties are minimal.

- The vapor pressure line CAD, of the

hydrating agent, which also is the
refrigerant in the freeze process.
Refrigerant selection to increase the
crystallizing temperature of the
components in the solution has two primary
advantages:

A good example of the effect of staging on

energy consumption is provided in the case
of acrylic acid manufacture. This
commodity chemical is produced in plants
of typically over 100 million pound per
year capacity.
The reaction products are
absorbed into water, producing a 20%
solution.
In conventional refining the
acrylic acid is extracted from the water
and then refined.

1) There is less difference between

the crystal formation temperature
(in the impure solution) and the
melting and/or heat rejection
temperatures.
2) The higher operating temperature
increases crystal growth rates and
decreases the viscosity of the
solution.

The acrylic acid freeze refining process

is governed by the solid-liquid equilibria
of Figure 9.
In a freeze refining process
the water solution would be concentrated
to the eutectic (42% acid at -19 degrees
F), and then acrylic acid and water would
be crystallized together.
Freeze refining
has an additional advantage of an improved
yield, since the dimer formation of the
present vacuum distillation refining
methods would not occur. Table 2 shows
the effect of staging on energy
consumption, with an equal freezing point
lowering in each stage.

The effect of the lower temperature

difference is to decrease overall energy
consumption by up to 10%. The advantage
of the lower viscosity is in greater
production in the separators, with less
product loss, which improves the economics
of the process.
In some applications the viscosity
achieved at low temperatures and high
concentration can actually limit ultimate
concentration by freezing.
This is
especially prevalent in the food industry.

843

Proceedings from the Fifth Industrial Energy Technology Conference Volume II, Houston, TX, April 17-20, 1983

ESL-IE-83-04-129

The pairing of crystallizer design and

refrigeration cycle are determined by the
method by which heat is removed from the
process sOlution.
There are essentially
two ways to remove heat:

20

15

1) Indirectly, through a heat transfer

surface.

10

2) Directly, by boiling a refrigerant

that is in direct contact with the

process solution.

~
~

Indirect heat transfer allows the choice

of the optimal refrigerant for the
temperature range being covered, as well
as providing optimal conditions for the
compressor.
The predominant factor is,
however, the increased temperature
difference needed for transfer of heat
through the exchanger. With expensive,
scraped surface exchangers, the economical
choice is for very high temperature
differences (often over 30 degrees F),
which can double the energy consumption of
the freeze process.

-5

-10

-15

-20

20

30

40

WT /.

50

70

SO

~ATER

80

FIGURE 9
ACRYLIC ACID - WATER SLE

In a direct contact processes, the

refrigerant either can be an immiscible
second phase that is thoroughly mixed with
the process fluid, or it can be one of the
constituents in the process fluid itself.
Water, for instance, has been used in the
most successful desalting pilot plants in
the past, acting at its triple point.
Here water is boiled at about 3.5 mm Hg
absolute pressure.
The heat removed
produces ice at a ratio of about 7 pounds
of ice formed per pound of water boiled.

TABLE 2

STAGING EFFECTS ON ENERGY CONSUMPTION

Design
Condition

Energy
kW

1 Stage

1100

2 Stage

770

30

3 Stage

670

40

Reduction
%

In a direct contact process,

are either:

the vapors

- Compressed by mechanical

compression;

Basis: 100 Million pound per year

20% Acrylic Acid in water

- Compressed by thermal compression;

or
- Absorbed into a suitable material,
which is then regenerated.
The method is selected based on the
conditions of the refrigerant.
For
instance, the thermal compression and
absorption processes are usually used only
for those refrigerants that act at low
partial pressures.

C ystallizer/Refrigeration Cycle
The crystallizer and the refrigeration
cycle are often dictated by the process
necds of the application, rather than by
energy considerations.
Still, they have
an impact on energy efficiency of the
process.

M4
Proceedings from the Fifth Industrial Energy Technology Conference Volume II, Houston, TX, April 17-20, 1983

ESL-IE-83-04-129

103"F

130" F

P=3 .4Bmm Hg
T=BO" F - - - l - - + (
COOLING
HATER
T=90" F --J---\--o

VAPOR

----

PLATE
HEAT
EXCHANGER
ABSORBER
100"F

LOH QUALITY
STEAM
T=130"F

12S" F

REFRIGERANT
p=3.SSmm Hg
T=26"F

MELTER
CONDEN
SER
P =S .00 P =4 .80
mm Hg
mm Hg
T=32"F
CONDENSATE

NOTE: T & P CONDITIONS ARE

TYPICAL FOR AQUEOUS
SYSTEM.

FIGURE 10
ABSORPTION REFRIGERATION CYCLE
An absorption refrigeration cycle can
operate with energy supplied from a waste
heat source.
The cycle is shown in Figure
10.
In the absorber, the vapor is
condensed in the absorbent and the
condensing latent heat load is removed by
cooling water.
In the generator. the
absorbent that has previously absorbed the
vapor is heated. and that absorbed vapor
is evaporated back out of the solution.
That regenerated vapor then must be
condensed onto either melting crystals or
into a heat sump such as cooling water.
The temperature difference required
between the waste heat and the cooling
water is a function of the process. but
can be as little as 20 degrees F in water
systems.
Melting
The final design variable that can
materially affect energy consumption in a
freeze process is the method of melting
the crystallized product.
Melting is done
to recover the 'cold'. or the energy used
in crystallizing the material.
In a heat
pump cycle. as is used in freezing
processes. the energy used in the
compressor is a function of the
temperature difference between the
evaporator and condenser. or freezer and
melter.

Melting can be done either by indirect

heating in a heat exchanger (usually shell
and tube using a slurry of the crystal and
melted product). or by direct condensation
of refrigerant vapors onto the crystals.
The method choice is usually dictated by
the refrigerant cycle and/or the
application.
Direct melting can be done with less than
a I degree F driving force and heat fluxes
of over 50.000 BTU per square foot per
hour per degree F.
Indirect melting
requires usually at least a 5 degree F
driving force. with the heat fluxes
determined from conventional heat transfer
coefficient calculations.
CONCLUSIONS
Freeze crystallization has many inherent
design variables for optimizing energy
consumption for an application.
Most
equipment options can be scaled up to
large sizes with very favorable
economies-of-scale.
The thermodynamic
advantages of the process for separation
applications. as compared to other phase
change options, indicate that freeze
crystallization should be considered for.
and ultimately used in many commercial
applications.

Proceedings from the Fifth Industrial Energy Technology Conference Volume II, Houston, TX, April 17-20, 1983