The Freeze Concentration Process and its

Applications
P. Englezos
Department of Chemical Engineering, Universdy of Brifsh Columbia,
Vancouver; British Columbia, CANADA V6T I24

In this paper, the freeze concentration separation process is described and the status of
its industrial applications is reviewed. The pilot plant and commercial applications in the
chemical and food processing industry for desalination and environmental protection,
and in the pulp and paper industry are summarized. The advantages of using this
process in the various industrial sectors as well as the lirnitalions are delineated. The
development of the clathrate hydrate process is also discussed. Finally, some anticipated
developments are described.

Introduction
The first paper on the application of the freezing process to desalinate sea water was
published in 1786 by Anton Maria Lorgna in Italy [l]. He described a method to
purify sea water and impure waters by freezing, melting of the ice, and successive
freezing of this water. However, his experimental work only became of practical
interest after the development of refrigerating machines. The difficulties in
establishing a simple apparatus to produce drinking water have been pointed out in
the early 1940s [2]. Sea water desalination was thought to present an excellent
opportunity to apply freeze concentration because thermodynamically it is more
favorable than evaporation. A sizable effort was devoted to understanding the
fundamentals of the process and the unit operations involved. Although the technical
feasibility of the technology was demonstrated it was not possible to go beyond the
pilot plant stage. Only one commercial desalination unit has so far appeared, this is
in Saudi Arabia [3]. The first commercial scale application of the freeze
concentration process was in the chemical and petroleum industry, it was installed in
the 1950s to purify p-xylene. Research and development efforts during the last 30
years resulted in over twenty commercial freeze concenaation systems in the US
food products industry. The main attraction of this technology is that volatile heat-
sensitive components required for taste, aroma and nutrition are not lost during the
freezing of the solutions. In spite of significant pilot plant development work it has
not yet been possible to utilize the technology for the concentration of the black
liquor in a Kraft pulp mill. This is partly because much of the energy advantage over
evaporation can not be realized with low oil and gas prices. However, the forest
products industry is currently (December 1992) seeing the first commercial
application in Chetwynd BC, Canada, where a freeze concentration system has been
installed to concentrate the effluents from a pulp mill.
In addition to the commercial applications in the food industry, one area where
commercialization of the process appears to be promising is the area of waste

3
P. Englezos

minimization through recycle and volume reduction (concentration). The urgent

need to preserve the quality of the environment and the advantages of the freeze
concentration process compared to evaporation and distillation, have renewed the
interest in freeze concentration. Freeze concentration presents new opportunities in a
wide variety of applications where there is a need to separate substances in the
crystalline form in a manner that allows for economic growth. Therefore, the
objective of this work is to describe the fundamentals of the freeze concentration
process, review the status of its application in various industries, and discuss some
anticipated future developments.

The Freeze Concentration Process

The term freeze concentration is often used interchangeably with the term freeze
crystallization. Freeze crystallization refers to any process that removes heat from a
mixture during which a component crystallizes. Freeze concentration is a particular
type of freeze crystallization in which the crystallized substance is physically
removed, leaving behind a more concentrated liquid. This work will be concerned
with the concentration of aqueous solutions. Water, the solvent, is the substance that
crystallizes and is separated from the concentrated solution (mother liquor),
however, the solution need not be aqueous. Organic-based solutions can also be
frozen to facilitate recovery of chemicals. The main aspect of freeze concentration is
that crystallization of an aqueous solution produces crystals that do not contain any
of the solutes present in the original solution. At the freezing temperature, a small
amount of crystals is formed. As the process continues the original solution becomes
more concentrated and this lowers its freezing point. Lower temperatures are then
required to increase the conversion. Terwillinger and Dizio [4] reported results for
the salt redistribution process during the freezing of aqueous sodium chloride
solutions. They found that the redistribution process is controlled by (a) the liquid-
phase interface concentration: and @) the thermal driving force imposed to initiate
and maintain freezing. The liquid-phase interface concentration was found to be a
function of the bulk concentration and the thermal driving force.

Basic Process: An important characteristic of the freeze concentration process is that

it can be carried out in several ways. Because of the equipment and refrigerant
alternatives, several freeze-concentration process systems can be conceived.
However, there is a general process schematic which illustrates the basic unit
operations involved as shown in Figure 1. This is based on a fundamental process
operation for desalination IS]. The original solution must first be cooled to a point
close to its freezing point before it is fed into the crystallizer. This is accomplished
through a feed heat exchanger. Ice crystals formed in the crystallizer together with
the concentrate are pumped into the separator. In most of the cases, this is a wash
column, i.e. a cylindrical vessel with screens. The cold concentrateis removed and a
portion is recycled to the crystallizer to increase the overall conversion. The ice from
the separator is passed into the melter where it melts due to contact with a hot
refrigerant stream. Liquid refrigerant is recycled to the crystallizer. The product
water is removed after exchanging heat with the feed in the heat exchanger. The
process inefficiencies and heat leakages into the system necessitate the use of a heat

4
 The Freeze ConcentrationProcess and its ApplicatiorrS

Figure I . Schematic of the basicfreeze concentrationprocess based on desalination.

removal system. In addition to the basic components shown in Figure 1 and the
associated instrumentation and control systems for efficient operation, there are
several auxiliary systems [5]. These include venting systems, feed deaerators and
refrigerant strippers. Hahn [5J discusses the basic flow diagram for a freeze
desalination process, the functions and design of the major and ancillary process
equipment,and the instrumentationand control equipment.

Advantages: The major advantage of freeze concentration is related to possible

energy savings. These occur because the latent heat of fusion for water is
approximately seven times less than the latent heat of vaporization (6.008 J/mol vs
40.66 J/mol). Therefore, freeze concentration is preferred over evaporation and
distillation because it requires less energy. However, multiple effect evaporators can
substantiaIly reduce this energy advantage of the freeze process. The freeze
concentration process has lower capital costs and requires less maintenance because
it operates at low temperatures where corrosion is not significant. Other advantages
include the insensitivity to fouling and the ability to handle acidic and alkaline
solutions. Finally, it is particularly suitable for the concentration of heat-sensitive
food products, and wastewaters containing volatile air-polluting substances.

Unit Operations
The most important unit operations are the crystallization stage and the
crystalkoncentrate separation. Successful operation of these two unit operations is
required in order to make the overall separation process economicallyattractive.

Crystallization
Ice crystal formation takes place in the crystallizer and proceeds in two steps:
nucleation and growth. The crystallizer can operate in several ways: (a) with the aid

5
P. Englaos

of a refrigerant that acts as a heat-transfermedium; (b) with water as the refrigerant

at conditions near the triple point; and (c) as an indirect process where the
refrigerant is not mixed with the original solution. The ice crystals that are formed
are pure but coated with the solutes found in the concentrated solution. Therefore, it
is desirable to form large ice crystals because then the surface area available for the
solutes to adhere is minimized. The separation of the ice crystals from the
concentrated solution is the important step that determines the efficiency of the
separation and ultimately the economics of the process. This step is influenced by
the crystallization step. Correct control of the ice production stage can minimize the
total loss of entrapped material per unit weight of ice [6].Therefore, it is important
to understand the factors that determine the crystal size, the crystal size distribution,
and the crystal morphology in a particular freeze concentration application.
Significantprogress in understanding ice nucleation and growth was made as a result
of the need to design freeze concentration systems for sea water desalination [7-141
and fruit juice concentration [15-171.
Control of crystal size involves many factors that influence the nucleation and
growth of ice crystals. It is desired to avoid primary nucleation of the ice crystals.
Secondary nucleation is preferable. Under this mechanism, nucleation can occur at
low supersaturations. Secondary nuclei are formed when existing crystals collide
with the crystallizer walls or other crystals or the stirrer blades [IS]. Ripening is an
important process which slowly increases the mean crystal sizes. It is used to
produce substantially larger ice crystals which can then be easily separated from
freeze concentrated solutions [ 191. Garside [20]has reviewed the published
information on the process of crystallizationfrom solution.

Separation and Purification of Ice Crystals

Separation and purification of ice crystals is a difficult but important operation. It
may determine the success of the commercialization of the freeze process in a
particular application. The difficulties associated with the separation of the ice
crystals from the concentrated solution have prevented the use of the energy-efficient
freeze concentration process for desalination.The low interfacial tension between ice
and brine probably causes the mother liquor to adhere to the crystal surface [21].A
wash column was identified as the appropriateequipment to carry out the separaiion
efficiently. The brine is displaced from the interstices between the ice crystals by
fresh water in gravity drainage, and from the surfaces of the ice crystals by diffusion.
The fundamentals of the washing process were studied experimentally and
theoretically in the late 1960s and early 1970s as part of the effort to develop a
commercial freeze concentration process for the desalination of sea water [22-251.
Additional work can be found in the proceedings of the desalination symposia[9-141.
Tleimat [211discusses in detail the wash column theory in his review of the freeze
concentration and the clathrate processes for the desalination of seawater. The
discussion is based mainly on the work by Schwartz and Probstein [22-231.It was
reported that the production rate of fresh water increases with an increase in the ice
crystal size, the ice plug length above the screens, the concentration of ice crystals
in the slurry, and the external mechanical restraining forces on the ice plug. It is also
generally known that the operation of the crystallizer influences the operation of the

6
 The Freeze Concentrdwn Process and its Applications

wash column. Therefore, when studying a particular application this relationship

should be explored.
Finally, removal of the refrigerant from the product water and the concentrate is
required when a refrigerant such as butane is mixed with the process stream to
facilitate the freezing of the solution by evaporation. Bajolle et al. [26] investigated
the use of a packed column but this separation increases the complexity and cost of
the process and can only be justified in large plants.

Freeze-ConcentrationTechnology Systems
Freeze concentration systems are divided into direct and indirect processes [3,5,27-
301. Heist [29, 301 described extensively the various systems and the refrigeration
cycles that can be employed. Hahn [5] presented a detailed description of the
equipment required and the instrumentation. The choice of a particular system
depends upon the type of solution to be concentrated. One might have to select from
more than two options and therefore, an economic analysis of the freeze
concentration system integrated into a particular application should be performed.

Indirect systems
In indirect systems, the solution to be concentrated constitutes the hot stream in a
heat exchanger. This stream does not come into direct contact with the cold stream
which is the refrigerant of a closed refrigeration cycle. Scruped-surface heat
exchangers are generally used. Freeze concentration of food products is carried out
in indirect freezing systems to avoid contaminating the solution with the refrigerant.
This type of heat exchanger is very expensive and development of non-scrapped
surface equipment is underway. The indirect systems are ideal for the food industry
because all volatile substances remain in the concentrate. Furthermore, the
economics of small plants are more favorable. The refrigeration cycle could be a
mechanical or absorption-type system.

Direct systems
For direct freeze concenmtion systems, a heat exchange surface is not required as
the refrigerant acts as the heat-transfer medium. There are two types of direct
systems: (a) triple point (vacuum freezing); and (b) secondary refrigerant.

(a)Direct contact, triple point (vacuumfreezing)

This process operates near the triple point of water. The water itself acts as the
refrigerant because as it vaporizes it removes heat and allows crystallization of the
solution.The refrigeration cycle can be based on vapor compression or absorption.
The major advantages are: (a) high heat-transfer rates with the corresponding low
energy requirements; and (b) the simplicity of the operation. The major disadvantage
is the large volumetric flow of water vapor that needs to be handled. The treatment
of the low-pressure vapor produced in the vacuum freezing step presented the
technical difficulties that decreased the likelihood of commercializing the process.
Recently, Cheng et al. [31] described the results of bench-scale experiments for a
vacuum freezing process that circumvents the vapor handling problems encountered
by previous vacuum freezing processes. Economic comparisons of their process with

7
P. EngreZos

distillation and reverse osmosis indicated substantial savings. The vacuum process
can also be defined according to the method by which the vapors are removed.

(b) Secondary refrigerant

In this process, a refrigerant which must be almost insoluble in water is added into
the solution in order to act as a heat-transfer medium by evaporation. Freons and
butane have been considered as possibilities. The process causes contamination of
the solution and therefore, requires additional separations in order to remove the
refrigerant from the product water and the concentrate. This complicates the
operation of the process and increases the capital and operating costs. Obviously, it
is not a preferable option in the food industry where the concentrate is the desired
product. Emulsification is an additional problem that has been identified. The
process is considered for applications where large volumes are to be treated and the
contamination issue is not important. Because most of the refrigerants have
significant ozone depletion potential it is expected that they will be eliminated from
the list of substances to be used in a freeze system. The flammability of the
refrigerant is an additional problem. Recent developments in the direct contact
process that uses butane as the secondary refrigerant have been reviewed by
Wiegandt et al. [32]. The secondary refrigerant systems can be further classified
according to the refrigerant used and the way in which it is mixed with the process
fluid. Methods to achieve intimate contact between the refrigerant and the solution
have been discussed by Ziering et al. [a].

The Clathrate Hydrate Concentration Process

Clathrate hydrates are formed at suitable temperature and pressure conditions, e.g.
propane and water at 278.3 K and 0.545 MPa, by the physical combination of water
molecules with a large number of molecules which can be trapped within a network
of hydrogen-bonded water molecules. The gas hydrate crystals are non-
stoichiomeuic compounds and contain only water and the clathrate-forming
substance. Since they can be formed at temperatures above the normal freezing point
of water, there is an energy advantage in replacing the crystallization step of a freeze
system by clathrate hydrate formation [33]. This is accomplished by injecting the
clathrate-fonningsubstance in the solution to be concentrated. The clathrate-forming
substance can also act as a refrigerant to remove the heat evolved by the
crystallization. Removal of the clathrate crystals from the concentrated solution can
be achieved by mechanical separation, after which the crystals can be decomposed
by reducing the pressure and /or elevating the temperature. The vaporized hydrate
former is recovered and recycled, although this may increase the cost of the
installation considerably. Tleirnat [21] describes the basic clathrate process for
seawater desalination and cites its advantages.
The clathrate process can be considered as a variant of the direct freeze-
concentration process because most of the refrigerants used in the direct secondary-
refrigerant process form hydrares. However, in this work, it is treated in a separate
section. In our opinion, the clathrate process offers a great opportunity to improve
the operation and the economics of the freeze concentration process because of
lower capital and operating costs. In the clathrate process, it is desired to find a

8
 The Freeze ConcentrationProcess and its Applications

clathrate-forming substance that forms hydrates close to the ambient temperature,

and at a pressure close to atmospheric. Vlahakis et al. [7] described the properties of
a suitable clathrate-forming agent for the desalination of sea water. Some of the
clathrate-forming substances form crystals which are highly porous and act l i e a
sponge, thus making the crystal/concentrate separation more difficult. It is also
desired to avoid the formation of fluffy, bulky crystal masses which will occlude
large volumes of the mother liquor. The hydrate process has been examined for sea
water desalination, wastewater concentration, and concentration of food products. In
spite of considerable research and pilot plant development efforts, the process has
not become a commercial success. However, the clathrate process is now becoming
more attractive for waste minimization and in the food products industry. These
developments are discussed in the next section.

Industrial Applications of the Freeze Concentration Process

Successful commercial applications of the freeze concentration process have been
established in the petroleum industry and in the food products industry. New
opportunities have arisen in wastewater treatment, chemical processing, the pulp and
paper industry, and for desalination. The status and the future prospects of these
applications will now be presented.

Chemical and Petroleum Industry

The first commercial scale application of the freeze concentration process was in the
chemical and petroleum industry. Two-thirds of the high-purity p-xylene produced in
USA, and used in the production of polyester, is obtained by freeze concentration
from a mixture of petrochemicals. Indirect scruped-su?$xe heat exhungers are used
in this application. Distillation and evaporation have been the dominant separation
processes used in the chemical process industries and the oil and gas industry.
However, freeze concentration is beginning to be adopted because it can result in
improved efficiency and throughput [3]. The Electric Power Research Institute
(EPRI)in the United States together with Heist Engineering considered replacing all
the evaporators in a chlor-alkali plant by freeze concentration systems. They
concluded that returns on investment ranging from 27.5 to 40% could be realized
[34]. Another application seriously considered by EPFU G in removing hazardous
organic wastes from petrochemical plant discharges.

Pulp and Paper Industry

The concentration stage plays a key role in the pulp and paper industry.
Concentration of the Kraft black liquor from 15 to 65% solids is accomplished by
evaporation. The black liquor is a liquid stream produced in the pulping process and
the subsequent separation of the pulp. It is burned in the recovery furnace to recover
the pulping chemicals and steam. There has been an effort to introduce freeze
concentration technology in order to concentrate the black liquor initially from 15 to
25% solids. The vacuum freezinghapor-absorptionprocess was selected as the most
appropriate method, but in spite of considerable laboratory and pilot plant
development work it did not materialize into commercial application [35-381.
Although the process is feasible, its economics are not favorable especially with low

9
P. Englaos

energy prices. The freeze concentration process is highly unlikely to replace

evaporation at present fossil fuel prices (December, 1992). Only a sizable economic
benefit will convince the industry to adopt a new technology. However, a more
optimistic view is presented by EPRI particularly with respect to the clathrate
process [3,341.

Desalination
A significant amount of work was carried out in the 1960s and 1970s. This work is
reported in a series of symposia and conferences [9-141, in a collection of patents
[39], and in two review papers by Barduhn [4041]. Initially, the freezing process
appeared to be very promising. Much work was performed to understand the
fundamentals of the process and the unit operations involved. Although the technical
feasibility of the technology was demonstrated it was not possible to go beyond the
pilot plant stage. The difficulty of separating the ice particles from the slurries
prevented the method from being competitive. Commercial desalination units which
are not based on freeze concentration were found to be more economical and
technically easier.
Recently, some new developments have been reported. Maguire [42] described a
new process which yields relatively large ice crystals, uniform in size and shape,
thus greatly facilitating separation from the concentrated solution. The vacuum-
freezing multiple-phase transformation process described by Cheng et al. [31] is a
vacuum direct process. It was found to offer significant economic advantages over
distillation and reverse osmosis because of an innovative design [43]. Another
development reported recently was a commercialplant that began operation in Saudi
Arabia [34]. Finally, a zero-discharge direct-contact freezing/solar evaporator
desalination plant was also proposed and evaluated for installation in the Middle
East [MI. Its purpose was to separate salts and minerals from the rejected blow-
down of sea water desalination plants.
The hydrate process was also examined for sea water desalination [45, 461.
However, it was not possible to develop the process beyond the pilot plant stage
because of two problems. First, it was difficult to produce crystals of sufficient
quality (size and shape) at a sufficient rate. Second, it was difficult to desorb the
clathrate hydrate-forming substance fiom the concentrateand the product water. The
majority of the work on the clarhrate process for desalination was published in the
desalination symposia and conferences [9-141.

Food Processing Industry and Biotechnology

The food industry is the sector where freeze concentration has been the most
successful. Steam-driven evaporation is the competing process. Scruped-surface heat
exchangers have been used to produce ice in a variety of solutions. The first
commercial application was installed in 1959 to concentrate vinegar solutions [47].
Fellows [48] discusses the application of freeze concentration in the food industry. It
was reported that freeze concentration is particularly suitable to remove water from
food because the low temperatures used in the process cause a high retention of
volatile aroma compounds. However, the process has high refrigeration costs, high
capital costs for equipment required to handle frozen solids, high operating costs and

10
 The Freeze ConcentrationProcess and its Applications

low production rates compared to evaporation. The degree of concentration achieved

is higher than in membrane processes but lower than concentration by evaporation.
Due to these limitations, freeze concentration is only used for high value juices or
extracts. Douglas [34] presented an optimistic view of future developments in this
area as they are anticipated by the Electric Power Research Institute. Freeze
concentration could be used to concentrate milk and exploit the by-products. The
most important of these by-products is whey, the watery liquid that remains when
cheese is curdled. Freeze concentration could be used to produce pharmaceutical
grade lactose (which crystallizes eutectically out of solution), and whey protein
concentrate (which forms when the remaining condensed liquid is passed through a
spray dryer) [%I. This concentrate has a high protein content which could be used as
a dietary supplement for humans and livestock.
Glew [49] was awarded the first patent for the concentration of fruit juices.
Huang et al. [SO] performed gas hydrate formation experiments in apple, orange and
tomato juice solutions. A basket-type centrifuge was used to separate the crystals.
The purity of the crystals was further improved by washing. The concentration
process was found to diminish the quality of the substrates. Warezak [51] also
investigated the clathrate process experimentally. He found that liquid ethylene oxide
(totally miscible with water) was an excellent hydrate former. Recently, a freeze
concenrration process based on clathrate formation has been studied and was found
to be very attractive for use in the beet sugar industry 1521.
Freeze concentration could be very important in bioprocessing. The products
from fermentation are produced in dilute solutions and concentration is an important
step in their separation.

Waste Minimization
Minimization of wastes through recycle and volume reduction (concentration) is an
area of increasing importance due to more stringent environmental regulations.
Freeze concentration and the clathrate process are expected to have a major impact in
this area. The ability to recover and recycle much of the water contained in
wastewaters will facilitate the realization of "zero-discharge'' plant operation.
Barduhn and Manudhane [53] discuss the eutectic freezing process for treating
wastewaters from cooling tower and boiler blowdown. and the brine effluent from
inland desalination plants. The process separates aqueous solutions of inorganic salts
into solid salt and fresh water. Concentration of the wastewaters from cooling tower
blowdown and recycle of the water is the most economical method in the absence of
a geological formation that would favor a low-cost evaporation pond [30].Heist [30]
also studied two other applications and found that freeze concentration can be a
viable alternative. One was concerned with wastewaters from the production of
terephthalic acid, and the other was the concentration of an acid solution in the
metals industry.
According to Douglas [34], new opportunities for the process include the
concentration of deep-mine reject water, recovery of process chemicals from
ammunition plant wastes, treatment of wastewaters from a metal-plating facility, and
by-product recovery from organic chemical and pharmaceutical waste streams. Heist
[54] discusses hazardous-wastesapplications of freeze crystallization. He reported a
P. Englezos

cost of $0.025to 0.15 per gallon of purified water including equipment amortization.
Chowdhury [43]discusses the application of freeze crystallization in the chemical
process industries. He listed seven industrial applications mainly in the treatment of
hazardous wastes. Recently, HPD Inc (Napperville, Illinois) announced the first
commercial utilization of freeze concentration for pulp-mill effluent concentration
[55, 561.It is an indirect freezing system used to concentrate the effluent from
Louisiana Pacific Corp's bleached-thermo-mechanical-pulp (BCTMP) mill at
Chetwynd, B.C., Canada. However, skepticism has been expressed regarding
application of the freeze crystallization method to concentrate CTMP effluents, and
in another mill evaporation was selected and found to perform really well [57, 581.
The presence of resins in the effluent is expected to cause problems in the separation
of the ice from the concentrated solution. However, development work still
continues in this area [59]. Gaarder and Englezos [a]are currently investigating a
clathrate hydrate-based process for the concentration of mechanical pulp-mill
effluents.

Discussion
The main problems that have prevented commercialization of freeze concentration
technology are: (a) the separation of ice crystals from the adhering mother liquor; (b)
the separation of refrigerant from product water; (c) the handling of large volumetric
water-vapor flows; (d) emulsification; and (e) explosions when butane is used as a
refrigerant. There is now a renewed interest in freeze concentration, due to: (i) the
inherent advantages of the process; (ii) new engineering developments that alleviate
most of these problems; and (iii) new applications. The advantages of the freeze
concentration process are: (a) it has reduced energy requirements; (b) it is not
sensitive to scale formation and corrosion; (c) it has the ability to handle acidic and
basic solutions; (d) it does not destroy heat-sensitive taste and aroma compounds;
and (e) it keeps volatile air-polluting wastewater substances in the concentrate. The
clathrate process may result in additional energy savings and, in our opinion. it may
make freeze concentration operations technically easier because it has additional
degrees of freedom. New engineering developments include the vacuum freezing
multiple-phase transformation process of Cheng et al. [31, 431,and the secondary
refrigerant process of Maguire [42].Both of these processes have been patented in
the US. New opportunities both in the food industry and for waste minimization
have stimulated interest in freeze concentration [34,43,48,541. In these two
industrial sectors, the clathrate process appears to have more potential for
commercial development.

Conclusions
The material presented in this paper is not an exhaustive presentation of what is
currently known about freeze concentration technology. What has been attempted is
the following: (a) to describe the process and its characteristics; (b) to summarize the
status of its applications in various indusmal sectors; and (c) to consider the new
opportunities. The clathrate process was also emphasized because it has the
potential to substantially improve the process operation and its economics.

12
 The Freeze ConcentrationProcess and its Applicatiom

Acknowledgement
The author acknowledges financial assistance provided by the Natural Sciences and
Engineering Research Council of Canada (NSERC).

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Received: 20 May 1992;Accepted after revision: 3 February 1993.

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