PRIMARY REFRIGERANT EUTECTIC FREEZING (PREUF) PROCESS AND APPARATUSES FOR USE THEREIN

Abstract: The primary refrigerant eutectic freezing (PREUF) process is designed to separate mixtures containing at least one volatile component and two or more crystal-forming components (1). Heat is removed from a eutectic mixture at near its eutectic temperature by inducing vaporization of a portion of the volatile component(s) at a pressure below the vapor pressure of the eutectic mixture at its eutectic temperature (2). The vapor is liquefied by a two-step process (a) mixed condensation/desublimation and (b) desublimate-melting (3). Co-crystallization of different components in the same zone of the freezer (4) or selective crystallization of different components in different sub-zones of the freezer (5) are possible with several different flow schematics possible (6). Separation of crystals of different components formed in co-crystallization in the same liquid pool followed by separation of individual component crystals from adhering liquids give purified products (7). Separation of crystals of different components is not required where selective crystallization is effective (8).

Description: DESCRIPTION OF THE INVENTION: Primary Refrigerant Eutectic Freezing (PREUF) Process and Apparatuses for Use Therein BACKGROUND (i). Technical Field Various methods have been used to separate mixtures in chemi- cal and other industries. These are distillation, freezing [or fractional solidification], crystallization, extraction, absorption and adsorption processes. A freezing process has several unique advantages such as (1) a broad field of application, (2) a high de- degree separation in a single step operation, (3) insensitivity to corrosion, (4) minimal pretreatment required, and (5) low energy input required. Among the possible freezing processes are freezing by heat exchange through a metallic surface, freezing by direct contact with a refrigerant foreign to the solution being processed and vacuum freezing in which the volatile componen (s) of the solution are vaporized to accomplish the required heat removal. (ϋ). Background Art Conventionally, the above freezing processes have been designed to separate a mixture into a purified solvent (the solid phase) and a concentrate with the maximum solute concentration attainable being that of the eutectic mixture. Professor A.J. Barduhn of the Univer- sity of Syracuse introduced the first eutectic freezing process, to crystallize the solute(s) as well as the solvent out of solution so that the solute as well as the solvent can be concentrated [to a high purity]. In the process, a refrigerant such as Freon 114 is brought in direct contact with a eutectic mixture to form two or more solid phases. Separation of the solid phases from each other and then from the mother liquor results in highly concentrated sol¬ vent and solute. Because the Freon refrigerant is foreign to the solution being processed, it is referred to as a secondary refriger¬ ant, and the process will be referred to as the Secondary Refriger- ant Eutectic Freezing (SREUF) Process. The SREUF Process may be used in separating binary eutectic, ternary eutectic, quaternary eutectic and other multi-component eu¬ tectic mixtures. In processing a binary eutectic, two solid phases are formed; in processing a ternary eutectic, three solid phases are formed, etc. Using the simple system NaCl-ϊ ? - the essential feature is that at -21 degrees Celsius, both ice and NaCl^&pO crystals precipitate from solution as heat is removed. As long as heat removal occurs by direct contact heat transfer, the ice and salt crystals can be nu- cleated and grown as separate, distinct phases in a continuously stirred tank crystallizer. Due to the fact that the ice and salt crystals are not mechanically interlocked, as in the case of metal¬ lic eutectics, physical methods of separation are possible. One may thus maintain these two solid products in a slurry using a recycled brine stream (23.3% NaCl) and remove heat from them to produce addi¬ tional crystals. The slurry effluent can be separated into one stream containing brine plus ice and another of brine plus solid salt (sodium chloride di-hydrate NaCl 2f_2θ) since ice floats and the salt sinks. There is no brine product. Some of the important aspects of the SREUF Process were tested at Syracuse University and reported in the following references: Reference No. 1: Allen J. Barduhn, "Waste Water Renovation-Part 1. A Design Study of Freezing and Gas Hydrate Formation," A TR-4, Envi¬ ronmental Health Series, U.S. ϋept. HEW-?ublic Health Ser¬ vice, October 1963. Reference No. 2: Allen J. Barduhn and A. Manudhane: "Temperatures Required for Eutectic Freezing of Natural Waters" Published in De¬ salination, 28 (1979) 233-241. Because of their interest in treating inorganic industrial waste AVCO Corporation developed the SREUF Process successfully through a small test unit stage. This work was reported in the following references: Reference No. 3: G.L. Stepakoff, D. Siegelman, R. Johnson and W. Gibson, Fourth Int. Symp. on Fresh Water From the Sea, Heidelberg, 3 (1973) 421-33. Reference No. 4: Final Report on Eutectic Freezing Process Investigations. Office of Saline Water Contract 14-30-2945, prepared by AVCO Systems Division, March 20, 1973. They found that the ice and salt crystals which are formed in the concentrated eutectic solution were rather small (125 microns and 40 microns respectively) and presumed that ice-brine separation would be difficult in a conventional wash column. They devised and successfully operated a modified separation column, called a floata- tion column, in which all the operations of ice separation, washing and melting occur. Although the SREUF Process has been tested on bench scale, lar¬ ger scale testing of the process has not been accomplished. Fluor Engineers and Constructors, Incorporated submitted a bid to the Office of Water Research and Technology, U. S. Department of Interi¬ or, for a 10,000 GPD SREUF pilot plant in August 1975 as reported in PB-250455. Parts of the plant are now located in Roswell, New Mex- 4 ico, but there is no record of its operation. The disadvantages of the SREUF Process are: 1. The recovery is low. 2. The crystal sizes are small. 3. There is a need to recover refrigerant from the product streams. 4. There is loss of refrigerant. The PREUF Process introduced herein does not bring a secondary refrigerant into direct contact with a eutectic mixture. Rather, the volatile component or components of the feed are vaporized to cool the mixture and thereby form two or more solid phases from the mixture. With this approach, the potential problems of the SREUF Process are avoided, indicating promise for a successful eutectic freezing process. If the PREUF Process is successful, the limita- tions of conventional freezing processes will be overcome, allowing for a complete separation of solute and solvent. (iii). Disclosure of the Invention The Primary Refrigerant Eutectic Freezing (PREUF) Process is an improved eutectic freezing process in which the required heat remov- al is accomplished by vaporizing a portion of the volatile compo¬ nent(s) of the mixture at a pressure slightly lower than the eutec¬ tic pressure, which is defined as the vapor pressure of the eutectic mixture at the eutectic temperature. The PREUF Process has the fol¬ lowing advantages over the conventional Secondary Refrigerant Eutec- tic Freezing (SREUF) Process: 1. The degree of supercooling can be precisely controlled by a fine adjustment of the system pressure, which is accomp¬ lished by controlling the condenser temperature. 2. It is easier to control nucleation rates of the components and suppress undesirable nucleation by a proper seeding, a precisely controlled degree of supercooling, and suppress¬ ing thermal, pressure and mechanical shocks. 3. It is possible to grow larger crystals by a proper seeding, a fine adjustment of the degree of supercooling and by sup¬ pressing undesirable nucleation. Therefore, the slush formed can be separated into two or more streams, each con¬ taining mostly a mass of the solid of one component and a mass of mother liquor. 4. Selective Crystallization using separate crystallization zones in each of which crystallization of one component takes place predominantly by a proper seeding and suppres¬ sion of undesirable nucleation. JO 5. Since no secondary refrigerant is used, there is less ther¬ mal shock and less pressure shock caused by vaporization of the secondary refrigerant and there is no refrigerant loss problem. Just as in the SREUF Process, the PREUF Process can be used for l ζ separating binary eutectic mixtures, ternary eutectic mixtures and eutectic mixtures of a larger number of components. (iv). Brief Description of Drawings Figure 1 illustrates a solid-liquid phase diagram of a binary system of A and B components indicating the presence of a binary 20 eutectic mixture with its eutectic temperature and eutectic composi¬ tion. Figure 2 illustrates a solid-liquid phase diagram of a ter¬ nary system of A, B and C-components and shows the presence of three binary eutectic mixtures and one ternary eutectic mixture. Figures 3-a, 3-b and 3-c respectively illustrate the P-T projection, the P-C 25 projection and the T-C projection of the P-T-C space model of a bi¬ nary system containing A and B components. They show the presence of the quadruple point or 4-phase point (Q-point) at whhich A-en- riched solid (denoted as A-solid), B-enriched solid (denoted as B-solid), liquid and vapor phases co-exist. 30 Figure 4 illustrates the operations of the PREUF Process using the Co-Crystallization Mode in which both components, A and B, of the eutectic mixture are crystallized out of solution in the same region as the temperature is lowered below the eutectic temperature shown in Figure 5. The reduction in temperature and the heat remov- 35 al required for crystallization is provided by the vaporization of a portion of feed upon reduction in pressure to below the 4-phase pressure. The slurry produced by this operation contains solid A, Sή, solid B, Sg, and mother liquor, L. If there is a significant difference in the densities of S« and Sg, the slurry can be separa¬ ted into two streams, one containing S« and a part of the mother liquor, L- | , and another containing So and the other part of the mother liquor, L2« Then S* is separated from L-| to form one product and So is separated from L2 to form the other product. L-| and 2 are recycled back to the freezer. Figure 6 illustrates the operations of the PREUF Process using the Parallel Crystallization Mode in which A-crystals and B-crystals are grown in separate freezers: A-crystals in the A-freezer and B— crystals in the B-freezer. In the A-freezer, a suply of A-crystals are maintained as seed crystals for the growth of A-crystals with the growth of B-crystals suppressed. Similarly, in the B-freezer, only B-crystals are maintained as seeds for the growth of B-crystals and the formation of A-crystals is suppressed. Figure 7-a shows the extension of the A-L equilibrium line below the eutectic tempera¬ ture. T« represents the temperature maintained in the A-freezer. As A-crystals are formed and grow, the concentration of B in the mother liquor wil be increased from Xg towards the equilibrium con¬ centration X*. Thus, L-( will have a B concentration greater than that of the eutectic mixture. Similarly, Figure 7-b shows the ex¬ tension of the B-L equilibrium line below the eutectic temperature to the temperature, Tg, maintained in the B-freezer. As B-crystals are formed and grow in the B-freezer, the concentration of A in the mother liquor will increase from Xg to X". Thus, L2 will have an A concentration greater than that of the eutectic mixture. The solid, Sβ, formed in the A-freezer is separated from Li to form one pro¬ duct, and the solid, Sg, formed in the B-freezer is separated from L2 to form the second product. Figure 7-c illustrates the mixing of L- | and 2 to form a eutectic mixture. As in the Co-Crystallization Mode, refrigeration for Parallel Crystallization is provided by vaporization of a portion of the feed at a pressure below the 4-phase pressure in both the A-freezer and the B-freezer. The Successive Crystallization Method is the third mode of con¬ ducting the PREUF Process. When it is used in separating a binary mixture, it may also be called the Alternate Crystallization Method. Figure 8 illustrates the Alternate Crystallization Method. The pro¬ cessing zone has an A-crystallizer and a B-crystallizer with a mass of A-crystals and a mass of B—crystals respectively maintained in the two crystallizers. By maintaining a low degree of supercooling and preventing pressure and mechanical shocks, nucleations of B—com¬ ponent and A-component are suppressed in A-crystallizer and B-crys¬ tallizer respectively. By growing A-crystals while suppressing the formation and growth of B-crystals, a mother liquor L* which is en¬ riched in B is formed; by growing B—crystals while suppressing the formation and growth of A-crystals, a mother liquor Lg which is en¬ riched in A is formed. L* and Lg are then introduced into B-crys¬ tallizer and A-crystallizer respectively. Portions of the feed may be added to L« and Lg and introduced to the B-crystallizer and the A-crystallizer respectively. This mode of operation may be extended to separate ternary eutectic or higher eutectics. Again, cooling and heat removal are accomplished by vaporization of a portion of the volatile components. Figures 9-a and 9-b illustrate these operations on the phase diagram. Figures 10, 11, 12 and 13 respectively show constant pressure solid-liquid phase diagrams of sucrose-water, sodium chloride-water, acetic acid-water and caprolactum-water systems. Figure 11 shows that sodium chloride and water form an incongruently melting binary compound, a di-hydrate NaCl ♦ 2H2O. Figure 13 shows that caprolac- tum and water also form an incongruently melting binary compound and shows a metastable region. These figures show the eutectic tempera¬ tures of these systems. The eutectic pressure of a binary system of A and B is the sum of the vapor pressures of solid A and solid B. Since sucrose, sodium chloride and caprolactum have low volatilities compared with water, the eutectic pressures of the systems of Fi¬ gures 10, 11 and 13 are essentially equal to the vapor pressures of ice at their respective eutectic temperatures. In the case of the acetic acid and water system, the eutectic pressure is the sum of the vapor pressures of solid acetic acid and ice. Figures 14-a and 14-b show vapor pressures of ice at various temperatures. As has been described, the figures may be used to find the eutectic vapor pressures of aqueous systems. Figure 15 shows phase diagrams of the binary m-xylene - p-xy- lene system under various pressures and show three phase (solid- liquid-vapor) lines under the pressures. As the pressure decreases, the three phase line becomes longer and the three phase temperature approaches the eutectic temperature. Figure 16 shows similar phase diagrams for the binary o— ylene - p-xylene system. Figure 17-a shows a possible equipment set-up for the Co-Crys¬ tallization operation (Mode 1 operation). The vacuum freezing ves¬ sel contains vertical plates which provide surface area for vapori- zation and freezing. The liquid feed is combined with crystals at the bottom of the tank to provide seeds for crystal growth and then pumped to the top of the vessel for distribution down the plates. The slurry thickens as it flows down the plates and is taken to a separator column in which A and B—crystals are separated. Figure 17-b shows an alternative arrangement of the plates at a tilted angle. Figure 17-c shows a third possible plate arrangement with rotating trays and a scraper at each plate to scrape the crystals from the tray. Low pressure vapors are discharged from these vessels, Figure 18-a shows a possible arrangement for the Parallel Crys¬ tallization operation (Mode 2 operation). As in the example for Mode 1 operations, vertical plates can be used to provide surface area for evaporation and crystallization. The feed going to the A- freezer is a near eutectic mixture combined with a portion of the A product from the A-freezer which provides seed A-crystals. Similar¬ ly, the feed going to the B-freezer is a near eutectic mixture com¬ bined with a portion of the B product from the B-freezer. Figure 18-b shows that horizontal plates with scrapers for slurry removal can also be used for Parallel Crystallization. A tilted plate arrangement (not shown in the figure) may also be used. Figure 19-a shows a possible arrangement for performing the Successive or Alternate Crystallization operations (Mode 3 opera¬ tion). In the system illustrated, there are two sets of rotating crystallizer plates, A-plates and B—plates, provided with filter plates, that are placed alternately. A mass of A-crystals and a mass of B-crystals are placed on each A-plate and each B-plate re¬ spectively. A new eutectic mixture is added on the top plate and liquid flows successively through the lower plates. Formation and growth of A-crystals take place on A-plates and formation and growth of B-crystals take place on B—plates. A-crystals and B-crystals are scraped off each A-plate and B-plate respectively. Figure 19-b illustrates another system for conducting the Suc¬ cessive or Alternate Crystallization operations. In this system, A- plates and B—plates are placed in separate compartments respective¬ ly, denoted as the A-compartment and the B-compartment. A mass of A-crystals is placed on each A-plate and a mass of B-crystals is placed on each B-plate. A mass of A-crystals and a mother liquor, LΛ, enriched with B is discharged from the A-compartment; a mass of B-crystals and a mother liquor, Lg, enriched with A is discharged from the B-compartment. After separating from A-crystals, a major portion of the mother liquor L« is introduced onto B-plates; after separating from B-crystals, a major portion of the mother liquor Lg is introduced onto A-plates. Feed may be added to LA and/or Lg be¬ fore they are introduced onto B-plates and A-plates respectively. (v). Best Modes For Carrying Out The Invention (vl). Detailed Process Description The PREUF Process cari be used in separating a multi-component mixture by forming masses of crystals of two or more components either in a common crystallization region or separate crystalliza¬ tion regions. There are a normal process and a modified process. In a normal process, the number of components that are crystallized out is the same as the number of major components in the feed mix- ture. Thus, in the normal process of separating a ternary mixture of A, B and C, a mass of A-crystals, a mass of B-crystals and a mass of C-crystals are formed either in a common region or separate re¬ gions. However, in a modified process, the number of components that is crystallized out is less than the number of major components in the feed mixture. Thus, in a modified PREUF Process for separa- rating a ternary mixture of A, B and C, masses of crystals of two components, A and B, B and C, or A and C, may be formed in a common crystallization region or separate crystallization regions. Similar statements can be made in separating mixtures containing four or more components. It is noted that in dealing with a multi-component mixture that contains a number of minor components, the minor compo¬ nents may be allowed to accumulate in the mother liquor and be purged from the system. Thus, the minor components do not have to be included in counting the number of components. Furthermore, it is noted that a ternary mixture of A, B and C may be treated as a pseudo-binary mixture of A and (B + C) when there is no need to separate masses of crystals of B and C. Similar statements may be applied to a mixture containing four or more components. Figure 1 illustrates the solid-liquid phase diagram of a binary system, A and B, under a given pressure. It shows the eutectic tem- perature 1-3-2 at which an A-enriched solid phase 1 [denoted simply as A-solid], a B-enriched solid phase 2 [denoted simply as B-solid] and a liquid phase [denoted as the eutectic mixture] co-exist, the melting point 4 of pure A, and the melting point 5 of pure B. It also shows an A + L region 1-3-4, a B + L region 2-3-5 and an A + B region 6-1—2-7. Since the solubility of B in A-enriched solid and the solubility of A in B-enriched solid are extremely low in most systems, lines 6-1-4 and 7-2-5 almost coincide with the vertical A-line and B-li_ιe respectively. When a eutectic mixture e repre¬ sented by 3 is cooled under a near equilibrium condition, A-solid 1 and B-solid 2 are formed in the ratio of 3-2 and 3-1, while the remaining mother liquor remains at the composition of e. However, by a selective seeding of A and suppressing of nucleation of B, A-crystals can be formed predominantly and the remaining mother liquor becomes enriched in B. In a similar way, B-crystals can also be formed predominantly. Figure 2 illustrates the solid-liquid phase diagram of a ter¬ nary system containing A, B and C. It shows melting points 8, 9, 10 of components A, B and C, binary eutectic points e 11, e 12 and e 13 of A and B, B and C, and A and C respectively and a ternary eu- tectic point E, 14. A normal PREUF Process is applied to a mixture near E to form masses of A, B and C-crystals in a single crystalli¬ zation region or two or three separate crystallization regions. A modified PREUF Process is applied to a mixture near a point along e E, 11-14, say d, to form masses of crystals of two components, say A and B. In the modified process, the mother liquor composition changes along line 11-14 rather than staying at a constant composi- " tion. The operating temperature and pressure then depend on the mother liquor composition. Figures 3-a, 3-b and 3-c respectively illustrate the P-T pro- jection, the P-C projection and the T-C projection of the three-di¬ mensional P-T-C model of a binary system, A and B. Figure 3-a shows the triple points of A 15 and B 19, denoted as Og and Ou, vaporiza- tions lines of A 15-16 and B 19-20, melting lines of A 15-17 and B 19-21, sublimation lines of A 15-18 and B 19-22. It also shows the quadruple point 23, denoted as the Q point, three phase A-|-L*-V« line 15-23, three phase B-j-Lg-Vg line 19-23, three phase A2~B2- ^ line 23-24 and three phase A3-B3-V11gline 23—25. A-J-LA-V» lines 15-26, 15-28 and 15-29, B^-Lg-Vg lines 19-27, 19-28 and 19-29, A2-E--_A ι gli-es 26-30, 27-31 and 28-32, and lines 26-33, 27-34 and 29-35 are shown in the P-C projection and T-C projection shown in Figures 3-b and 3-c. In many systems, A-| , A2 and A3 lines are almost the same as the pure A-line and B1 , B2 and B3 lines are almost the same as the pure B-line. When the PREUF Process is applied to the eutectic mixture of A and B described by these figures, the eutectic freezing operation is conducted under a pressure that is just slightly lower than the pressure at the quadruple point. Since the eutectic temperature and eutectic composition of the binary A-B system are substantially un¬ affected by a small change in the applied pressure, the quadruple point pressure may also be taken as equal to the vapor pressure of the eutectic mixture at the eutectic temperature evaluated at the ambient pressure. This pressure is also equal to the sum of vapor pressures of pure A-solid and pure B—solid at the three phase equil¬ ibrium temperature of A-solid, B-solid and the liquid. The key difference between the PREUF Process and the SREUF Pro¬ cess is in the way cooling needed in the formation of masses of crystals is accomplished. In the PREUF Process, a portion of the feed liquid and recycle liquid are vaporized to remove the latent heat released in the crystallization operation; in the SREUF Pro¬ cess, the necessary cooling is accomplished by vaporizing a secon¬ dary refrigerant. There are the following three modes of operation of the PREUF Process: (a) Mode 1 Co-Crystallization (b) Mode 2 Parallel Crystallization (c) Mode 3 Successive Crystallization In the case of separating a binary mixture, Mode 3 may also be called the Alternate Crystallization Mode. Figure 4 illustrates how a binary mixture containing A and B can be separated using the Co-Crystallization Mode. A binary mix- ture F, near the eutectic composition and recycle liquids L- | and 2 to be described are mixed and fed into a co-crystallizer 36, wherein a part of the mixed liquor is vaporized to form a low pressure vapor V and a first slush, denoted also as a first condensed mass, con¬ taining masses of A-crystals and B—crystals. The slush containing A-solid (Sa), B-solid (S«) and liquid is separated into a slush con¬ taining S« and L- | and a second slush containing Sn and L2 in a sepa¬ rator 37 such as a cyclone separator. S. and S R are separated from these slushes and the mother liquors L^ and L« so obtained are re¬ cycled. The low pressure vapor V is condensed into masses of A-solid and B—solid and are melted and recovered. An effective way of handling the low pressure vapor has been described by Chen-Yen Cheng and Sing-Wang Cheng in U.S. Patent No. 4,505,728 and its ex¬ tension to be filed. Figure 5 shows that when the eutectic mixture 38 is cooled to a temperature T«g below the eutectic temperature 39-38-40 and equilibrium is attained, it 41 separates into a mass of A-solid and a mass of B-solid in the ratio of 38-40 and 38-39. How¬ ever, by controlling the cooling and thus the degree of solidifica¬ tion, one can obtain a solid-liquid mixture containing a mass of A-solid, a mass of B-solid and some mother liquor. Figure 6 shows how a binary mixture of A and B can be separated by the Parallel Crystallization Mode of operation. In the process, a mass of feed F and a recycle stream Lg to be described are mixed to form a mixed feed. A portion of the mixed feed F« is introduced in the A-crystallizer 42 and the rest F« is introduced into the B- crystallizer 43. In the A-crystallizer, there is a mass of A-solid but no B-solid. The liquid mixture in the A-crystallizer is flash vaporized to form a first vapor . and cause crystallization and growth of A-crystals, while nucleation of B-crystals is suppresed. The required cooling is accomplished by vaporizing a portion of the volatile component(s) from the mixture. Nucleation of B-crystals is suppressed by maintaining a low degree of super-cooling and by avoiding thermal, mechanical and pressure shocks. The operating condition is illustrated by Figure 7-a. It shows a freezing point curve for A 44-45 and a freezing curve for B 44-46. When a mixture near the eutectic point 44 is introduced into the A-crystallizer 42 maintained at temperature T» , a mass of A-crystals (S»)is formed and the mother liquor L- j 47 is enriched in B-component. The solid-li¬ quid mixture is then separated to form a mass of A-solid and a mother liquor L- j . In a similar way, the mixed liquid introduced into the B—crystallizer maintained at temperature T« becomes a solid-liquid mixture (S« + L_), which is separated to form a mass of B-solid S Q and mother liquor 2. As shown in Figure 7-b, the mother liquor L2, represented by point 48, is enriched in A-component. As illustrated in Figure 7-c, these two mother liquors, L- j and 2 » are mixed to form a liquid L3 49 that is of a near eutectic composition. This liquid becomes the recycle liquid described. Figure 8 shows how a binary mixture of A and B can be separated using the Successive Crystallization Mode. This mode of operation as applied to a binary mixture may be called the Alternate Crystal¬ lization Mode. Referring to the figure, feed is introduced into the A-crystallizer or the B-crystallizer or both. In the A-crystallizer 50, a mass of A-solid is formed while the formation of B-solid is suppressed. The required cooling is accomplished by vaporizing a mass of volatile components V from the mixture. The mother liquor L« 52 leaving the A-crystallizer is enriched with B-component; it is introduced into the B-crystallizer. Similarly, in the B-crystalli¬ zer 51, a mass of B-solid is formed while the formation of A-solid is suppressed. As shown in Figure 9-b, the mother liquor Lg 53 leaving the B-crystallizer is enriched with A-component. It is introduced as feed into the A-crystallizer. Figure 10 shows the solid-liquid phase diagram of the sucrose- water system. The eutectic composition is sucrose 63.4% by weight, the eutectic temperature is -13.9 degrees Celsius and the eutectic pressure is 0.9-1.36 torr. Sucrose solutions such as cane juice and beet juice may be concentrated to a near eutectic composition by a vacuum freezing process and the solution is then separated by the PREUF Process. Figure 11 shows the solid-liquid phase diagram of the NaCl-H-O system. There is a region in which a binary compound (NaCl-2H 0) exists. The eutectic composition is 23.3% NaCl by weight, the eutectic temperature is -21.1 degrees Celsius and the eutectic pressure is approximately 0.7 torr. By using the PREUF Process, ice and solid sodium chloride di-hydrate can be separated. - Figure 12 shows the solid-liquid phase diagram of the acetic acid- water system. The eutectic composition is 60% acetic acid by weight, the eutectic temperature is -31 degrees Celsius and.the eu¬ tectic pressure is approximately 0.257 torr. It is noted that there are various kinds of waste waters that contain acetic acid. Such 0 waste waters can be first concentrated by a vacuum freezing opera¬ tion and solid acetic acid can then be separated from the concen¬ trate by the PREUF Process. Figure 13 shows the solid-liquid phase diagram of the caprolactum-water system. It shows a stable eutectic and an unstable eutectic. The stable eutectic composition is 52,4% 5 caprolactum by weight, the stable eutectic temperature is -13.7 de¬ grees Celsius and the eutectic vapor pressure is approximately 1,4 torr. There are two methods by which the eutectic pressure of a eu¬ tectic mixture can be determined. There are: Q a) Liquid Phase Approach: The eutectic pressure Pr can be found from the eutec¬ tic liquid composition and the eutectic temperature by the following relation: p E - ( VH x A' y A + < P BVB' V ( W C ^C where (P» ) , (Pg°) and (Pp") are vapor pressures of pure A-liquid, B-liquid and C-liquid at the eutectic tempera¬ ture, Xa, Xg and X/» are mole fractions of A, B and C in the liquid mixture and y«, y R and y« are activity coefficients of these components, 0 b) Solid Phase Approach: In the normal PREUF Process, the eutectic pressure can also be found by the following relation: P E = (P A ) S + (P B ) S + (P C ) S where A, B and C represent crystallizing components and (P» ) Q , (Pg )e and (Pp )c are respectively vapor pressures of pure A-solid, B—solid and C-solid at the temperature at at which A, B, and C-solid co-exist with the equilibrium liquid. In an aqueous mixture containing only low vola¬ tility solutes, the eutectic pressure is simply equal to vapor pressure of ice at the eutectic temperature. Figures 14-a and 14-b show the vapor pressure of ice in the ranges of 0 degrees Celsius to -30 degrees Celsius and -30 degrees Celsius to -60 degrees Celsius respectively. These figures may"be used to find the eutectic pressure for an aquous mixture containing non-volatile solutes. Figure 15 shows solid-liquid-vapor phase equilibria for the binary m-xylene and p—xylene system under various pressures. It also shows the quadruple state under which solid m-xylene, solid p-xylene, liquid and vapor co-exist. Figure 16 shows a similar phase diagram for the o-xylene and p-xylene system. Separation of solid m-xylene and solid p-xylene from an isometric mixture of p-xylene, m-xylene, o-xylene and ethyl benzene will be very i por- tant in the chemical industries. However, as described in connec¬ tion with Figure 3, it is important to note that this application belongs to the modified PREUF Process because two components are separated as solid masses from a mixture containing more than two major components. A ternary phase diagram or a quarternary phase diagram may be used. (v2). Apparatus Figures 17-a, 17-b and 17-c show three types of co—crystalli- zers that may be used in carrying out the PREUF Process according to the Co-Crystallization Mode. Figure 17-a shows a vertical plate crystallizer; Figure 17-b shows a sloped surface crystallizer; Fi¬ gure 17-c shows a rotating tray crystallizer. The vertical plate crystallizer assembly comprises a vacuum chamber 54 with vertical plates 55 on which slush flows downward and a crystal separator 56 A slush 57 containing A-solid (SΛ), 3-solid (Sg) and a eutectic ix- ture, is distributed through a distributor 58 and is applied on the vertical plates. By maintaining the pressure in the vessel slightly lower than the eutectic point pressure, a portion of the volatile components vaporize to cause crystallization of A and B-components. A low degree of supercooling is maintained and mechanical, thermal and pressure shocks are avoided in order to grow A-crystals and B-crystals to relatively large sizes. The low pressure vapor formed is condensed into solid states, melted and removed by a method modi¬ fied from the method described in U.S. Patent No. 4,505,728. The slush formed is separated into two slush streams, one containing A and Lj and the other containing B and L2« A and B are separated from these slush streams and the liquid streams Li and Lj are mixed to become L and are recycled. Figure 17-b shows a sloped surface co-crystallizer. The operations in this unit is similar to those of Figure 17-a. A slush feed 57 is added to these sloped surfaces 59 and allowed to flow downward along these surfaces. Vaporization and crystallization take place on the sloped surfaces. Figure 17-c shows a rotating tray co-crystallizer having rotating trays 60. A slush is added to these trays and vaporization and crystallization take place on these tray"s. Operations in this unit are also similar to those described. Separation of a binary mixture by the PREUF Process according to the Parallel Crystallization Mode can be made in the units illus¬ trated by Figures 18-a and 18-b. The unit in Figure 18-a comprises a vacuum crystallizer 61 that is separated into an A-crystallization sub-zone 62 and a B—crystallization subzone 63. A slush containing a mass of A-solid and a near eutectic mixture L- is applied over the vertical surface of the A-crystallizer, The chamber is maintained under a pressure that is slightly lower than the eutectic pressure to cause vaporization with the formation of A-crystals and a first vapor V . The slush A + L-| so formed is separated into A and L-j at the separator 64. L-j is enriched with respect to B. A similar operation in the B-crystallizer 63 and a separator 65 produce B and LT. A first vapor Vnis formed in the B—crystallizer. L j is en¬ riched with respect to A. L and L j and feed are mixed to form a mixed feed. A mass of A-crystals is added to a portion of the mixed liquid L and introduced into the A-crystallizer; a mass of B-crys¬ tals is added to the rest of the mixed liquid L 4 and introduced into the B— rystallizer. Figure 18-b shows a vacuum chamber that compri¬ ses an A-crystallizer 66 and a B-crystallizer 67. There are rota¬ ting trays in each of these crystallizers. Vaporization and forma¬ tion of A-solid take place in the A-crystallizer and vaporiization and formation of B-solid take place in the B-crystallizer. Other operations are similar to those of Figure 18-a. One may also use a sloped surface crystallizer similar to that shown in Figure 17-b. Figures 19-a and 19-b show units in which a mixture can be separated by the PREUF Process according to the Successive Crystal- lization approach. When masses of solids of two components are formed, this approach may also be called Alternate Crystallization approach. The unit shown in Figure 19-a has a vacuum chamber 68, a set of A-trays 69 and a set of B-trays 70. These trays are placed alternately. A-trays are seeded with A-crystals and B-trays are seeded with B-crystals. A mixed liquid 71 formed by mixing the feed and a recycled liquid to be described are added to the top tray. The liquid on each A-tray is partially vaporized to grow A-crystals and form a liquid L» which is enriched with B. The liquid leaving an A-tray is filtered to remove A-crystals and is added to the E— tray below. Similarly, the liquid on each B-tray is partially va¬ porized to grow B-crystals and form a liquid Lg which is enriched with A. The liquid leaving a B-tray is filtered to remove B-crys¬ tals and is added to the A-tray below. The liquid leaving the last tray becomes the recycle liquid. Feed and recycle liquid are mixed and added to the top tray. The unit illustrated by Figure 19-b has two crystallization sub-zones, i.e. an A-crystallization sub-zone 72 and a B-crystallization sub-zone 73. Rotating trays are provided on each zone. Vaporization and crystallization of A takes place on A— trays; vaporization and crystallization of B takes place on B-trays. The slush removed from the A-sub-zone contains A-solid and liquid LA which are separated in a separator 74 into a mass of A-solid and LA. LA is enriched in B and is introduced into B-crystallizer with addi¬ tional feed F . The slush removed from the B-sub-zone contains B- solid and liquid Lg, which are separa ted in a separator 75 into a mass of B-solid and Lg. Lg is enriched in A and is introduced into A-crystallizer with additional feed F2. (v3). Multiple-Component Systems In the previous discussion, binary systems were used to illus¬ trate the essentials of the PREUF Process. However, the three modes of the PREUF Process can also be applied to multiple component sys- terns having three or more components. For instance, let there be n major components in the system with m components that crystallize in the overall process. These components are referred to as crystalli¬ zing components. Let there be k crystallizing sub-zones with possi¬ ble values for k being 1, 2, 3, ... up to m. Let the number of com- o ponents crystallizing in the first crystallizing zone be C- j , the number of components crystallizing in the second crystallizing zone be C2 and so forth so that c 1 + c 2 + c 3 + + c k = m with k = 1, 2, 3, 4, ... m. Of course, when a component crystalli- 5 zes in more than one sub-zones, the above equation must be properly modified. It can be seen that there are many possible ways of crys¬ tallizing the m crystallizing components using the three modes of the PREUF Process. For treating a mixture with two crystallizing components (m = 0 2) denoted as A and B, one may use a common crystallization region (k = 1) or use two separate crystallization sub-zones (k = 2). Therefore, there are the following two possible sets of values for k and C 's: Case 1: k = 1, C-| = 2; 5 Case 2: k = 2, C| = 1, C = 1. In Case 1, the co-crystallization mode illustrated by Figures 4, 17-a, 17-b and 17-c is used. A mass of A-solid and a mass of B- solid are formed in a common crystallization region. Therefore, k = 1 and C = 2. In Case 2, two separate crystallization sub-zones are used: the first sub-zone is used to form a mass of solid of A-compo¬ nent and the second sub-zone is used to form a mass of solid of B—component. Therefore, k = 2, C-| = 1 and _2= 1. For treating a mixture with three crystallizing components (m = 3) denoted as A, B and C, one may use a common crystallization re- gion (k = 1), two separate crystallization sub-zones (k = 2), or three separate crystallization sub-zones (k = 3). Therefore, there are the following possible sets of values for k and C 's: Case 1 k = 1, Cj = 3; Case 2 k = 2, Cj = 1, C 2 = 2; Case 3 k - 3, Cj » 1, _2 - 1, C3 - 1. In Case 1, the Co-Crystallization Mode is used. Crystals of the three crystallizing components are formed in a common crystalliza¬ tion region. The slush formed contains a mass of A-crystals, a mass of 3—crystals, a mass of C-crystals and a mass of mother liquor. Masses of A-solid, B-solid and C-solid are then separated from this slush. In Case 2, there are two crystallization sub-zones. In one sub-zone, one component, say A-component, crystallizes and in the other sub-zone, the remaining two components, B and C, crystallize. The Parallel Crystallization Mode and the Successive Crystallization Mode have been explained by referring to the processing of a binary mixture. These modes of operation may be extended to the processing of a ternary mixture or a mixture with four or more components. In the following discussion, the crystallizing zone refers to the sum of all the crystallizers in the process, whereas the crystallizing sub-zone refers to a single crystallizer or a zone within the crys¬ tallizer. A way of separating a ternary mixture involving the Parallel Crystallization Mode in two crystallization sub-zones may be described by referring to Figure 6. In this case, the first crystallizer 42 is used to form a mass of A-solid and the second crystallizer 43 is used to form masses of B and C crystals. The operations are similar to those described earlier, except that masses of B and C crystals are formed in the second crystallizer 43. The crystallization of B and C in the second crystallizer is a Co- Crystallization operation and the relation between the crystalliza¬ tion operations in the first and second crystallizer is a parallel relation. Therefore, the overall process is a combination of a parallel crystallization in the two crystallizers and a co-crystal¬ lization in the second crystallizer. It is noted that the feed and the recycle liquid to be described are mixed to form a mixed feed. The mixed feed is divided into two streams and these two streams are sent to the first crystallizer and the second crystallizer in a parallel way. Mother liquors obtained from the two crystallizers are mixed and the mixture becomes the recycle liquid described. A way of separating a ternary mixture involving the Successive Crystallization Mode in two crystallization sub-zones may be de¬ scribed by referring to Figure 8. In this case, the first crystal¬ lizer 50 is used to form a mass of A-solid and the second crystalli- 5 zer 51 is used to form masses of B and C-crystals. The operations are similar to those described earlier for separation of binary mix¬ tures except masses of both B and C-crystals are formed in the second crystallizer 51. The crystallization of 3 and C in the second crystallizer is a co-crystallization operation and the rela- 10 between the crystallization operations in the two crystallizers is a successive or alternate relation. Therefore, the overall process is a combination of a successive crystallization in the two crystalli¬ zers and a co-crystallization in the second crystallizer. It is noted that in the successive arrangement, the mother liquor obtained 15 from the first crystallizer is fed into the second crystallizer and vice versa. In Case 3, there are three crystallization sub-zones. Masses of A-crystals, B-crystals and C-crystals are formed separately in the three sub-zones. The relations among the crystallization opera- 20 tions in the three sub-zones may be the Parallel Crystallization Mode, the Successive Crystallization Mode or a mixed mode that is a combination of the two modes. For treating a mixture with four crystallizing components (m = 4), denoted as A, B, C and D, one may use a common crystallization __ region (k = 1), two separate crystallization sub-zones (k = 2), three separate crystallization sub-zones (k = 3) or four separate crystallization sub-zones (k = 4). There are the following possible sets of values for k and Cj 's: Case 1: k = 1, C = 4; Case 2: k = 2 30 Case 2A: k = 2, Cj = 1, C- = 3; Case 2B: k = 2, Cj = 2, C 2 - 2; Case 3: k = 3, Cj = 1, C- = 1 and C3 = 2; and Case 4: k = 4, Cj = 1, C = 1, C3 = 1 and C4 = 1. 35 In Case 1, there is only a common crystallization region and all of the four crystallizing components are crystallized in the common crystallization region. Therefore, Cj = 4. In both 2A and 2B, there are two crystallization sub-zones. In Case 2A, a compo¬ nent is crystallized in the first crystallization sub-zone and the remaining three crystallizing components are crystallized in the second crystallization sub-zone. In Case 2B, two components are crystallized in the first crystallizing sub-zone and the remaining two components are crystallized in the second crystallization sub- zone. In Case 3, there are three crystallization sub-zones; the first and second crystallizing components are respectively crystal¬ lized in the first and second crystallization sub-zones and the re- maining two components are crystallized in the third crystallization sub-zone. In Case 4, there are four crystallization sub-zones and one component is crystallized in each sub-zone. When there are two or more crystallizers, the liquid streams may be fed to the crystal¬ lizers in a parallel manner or a successive manner, or even a combi- nation of the two. In the preceding paragraphs, possible ways of arranging crys¬ tallizers have been described by referring to processing of mixtures containing two, three and four crystallizing components. The de¬ scription given can be further extended to mixtures with five or more crystallizing components. The descriptions given are based on an assumption that a given crystallizing component is crystallized only in one crystallizer sub-zone. The PREUF Process may be so operated that a component is crystallized in two or more crystalli¬ zers. For example, in separating a mixture with three crystallizing components, denoted as A, B and C, in two separate crystallizers, it may be so seeded that A and C crystallize in the first crystallizer and B and C crystallize in the second crystallizer. Such an opera¬ tion has at least accomplished a separation of A and B components. The type of modification described is obvious to one skilled in the art« A general statement can be made about ways of arranging one or more crystallizers. The PREUF Process can be used to separate a mixture containing n major components. The process may be so con¬ ducted to crystallize m components, denoted as the crystallizing components, from a near eutectic mixture in a crystallization zone that comprises k crystallizing sub-zones (k crystallizers). The m—value is equal to or more than two and is equal to or less than n. The k-value is equal to or more than one and is equal to or less than . Assuming that a given component is crystallized only in one crystallization sub-zone, letting the sub-zones be named first, second, , i-th, and k-th sub- zones and the number of compo- nents that crystallize in the sub-zones be denoted respectively as Cj, CO, , Cj , , Ci,, then there exist the following relation: Of course when a component crystallizes in two or more sub-zones, the above equation has to be properly modified. It is important to note that an ideal operation has been assumed in the discussion presented. For example, in the discus¬ sions presented in reference to Figures 6 and 8, it is assumed that A does not crystallize in the B-crystallizer and B does not crystal¬ lize in the A-crystallizer. In an actual operation, formation of a small amount of A-crystals in the B-crystallizer and vice versa may be tolerated. It has been described that, in the PREUF Process, the cooling needed in a eutectic freezing operation is accomplished by vapori¬ zing a part of the volatile component(s) in the liquid mixture in each crystallization sub-zone as shown in Figures 4, 6, 8, 17a, 17b, 17c, 18a, 18b, 19a and 19b. This vapor is denoted as the first vapor from each crystallization sub-zone, such as the first vapor from the A sub-zone, the first vapor from the B sub-zone, etc. The first vapors from the sub-zones may be individually reduced to a liquid state or be first combined and then reduced to a liquid state and removed from the vacuum system as a liquid. In view of the low pressure and the extremely large specific volume, it is desirable that the liquefaction be accomplished without compressing the low pressure vapor. One may use an absorbing liquid to absorb a first vapor and remove the resulting solution, regenerate the solution and return the absorbing liquid. However, it is more convenient not to use an absorbing solution. A modification of the multiple phase transformation operations introduced by Chen-Yen Cheng and Sing-Wang Cheng in U.S. Patent No. 4,505,728 is a convenient way of liquefying the first vapors without compressing the first vapor or absorbing it in a solution. The modified multiple phase transformation opera¬ tions as applied to the PREUF Process are described in the following paragraph. In order to liquefy a first vapor containing two or more vola¬ tile components, say A, B and C, generated in a eutectic freezing zone by the modified multiple phase transformation operations, a vapor liquefaction zone is connected to the eutectic freezing zone through a first valve. The vapor liquefaction zone is further con¬ nected to a second vapor generation zone through a second valve and is provided with a liquid discharge valve. A heat exchanger cooled by a refrigerant and provided with a refrigerant valve is installed within the vapor liquefaction zone. Another heat exchanger heated with a heating medium is installed within the second vapor genera¬ tion zone to generate a pure vapor or a vapor mixture that is at a pressure higher than the pressure prevailing in the eutectic freez¬ ing zone. The first vapor generated in the eutectic freezing zone is liquefied by the following steps conducted cyclically: Step 1: Desublimation of the first vapor; Step 2: Pressure isolation of the vapor liquefaction zone; Step 3: Generation of a second vapor; Step 4: Interaction between the second vapor and the desubli- mate to simultaneously condense the second vapor and melt the desublimate and discharge of the resulting liquid from the liquefaction zone; and Step 5: Pressure Isolating the Vapor Liquefaction Zone. During Step 1, the first valve is open, the second valve is closed and a cooling medium is introduced into the heat exchanger in the liquefaction zone. The first vapor containing the volatile compo¬ nents A, B and C is desublimed (condensed into a solid state) form¬ ing masses of A-solid, B-solid and C-solid on the heat exchanger surface. Toward the end of Step 1, the flow of the cooling medium into the heat exchanger is stopped. A layer of desublimates of a certain thickness has been formed on the heat exchanger surface. At the beginning of Step 2, the first valve is closed. During Step 2, both the first and second valves are closed and the liquefaction zone is pressure isolated from both the eutectic freezing zone and the second vapor generation zone. Step 2 is a transition step and is needed to prevent a rush of second vapor through the liquefaction zone into the eutectic freezing zone. During Step 3, a second vapor is generated in the second vapor generation zone by vaporizing a liquid. This liquid may either be a pure or a mixed liquid. A con¬ venient liquid to be vaporized is a liquid mixture discharged in Step 4 to be described. The pressure of the second vapor has to be such that on interacting with the desubli ate, it can be condensed and dissolve the desublimate. At the beginning of Step 4, the second valve and the liquid discharge valve are open while the first valve is still closed and the cooling medium is still not introduced into the heat exchanger. During Step 4, the second vapor enters the liquefaction zone to be condensed on the desublimate and dissolves it. This operation is essentially adiabetic; the latent heat re¬ leased in the condensation of the second vapor is utilized as the latent heat needed in dissolving the desublimate. By the end of Step 4, the thickness of the desublimate has been reduced to a thin layer or has been completely removed. The liquid mixture formed is discharged from the liquefaction zone. A part of this liquid mix¬ ture is used in generating the second vapor. At the beginning of Step 5, the second valve is closed and a cooling medium is intro¬ duced into the heat exchanger to pressure isolate and cool the li¬ quefaction zone. Then Step 1 of the next cycle of operation is initiated. The pressure of the second vapor has to be higher than the equilibrium pressure of the system in which five phases, A-solid, B-solid, C-solid, a liquid and a vapor, co-exist. According to the Phase Rule, the degree of freedom is zero. Therefore, the equili- brium pressure is a unique value. In the above discussion, it has been assumed that the first vapor contains three volatile compo¬ nents. The operations are similar when the first vapor contains any number of volatile components. (vi). Industrial Applicability The Primary Refrigerant Eutectic Freezing (PREUF) Process is applicable to the concentration of industrial and waste solutions, agricultural return flows, mine waters and other brines or impaired quality waters for the purposes of water recovery or solvent recov¬ ery and waste disposal or recovery of valuable solutes. By crystal- lizing out the solute(s) as well as the solvent, the degree of con¬ centration is greatly increased so that the recovery yield of sol- vent is greatly extended beyond that possible by conventional freez¬ ing processes. Also, as the solute(s) are removed in a nearly solid state, waste disposal is greatly simplified. In the case where the solute is valuable, recovery in near solid form is a great asset.

Claims: What we claim are as follows: Claim 1; A process of separating a multi-component liquid mixture containing n major components by forming crystals of m components, denoted as m crystallizing components, in a crystallization zone, denoted as a first processing zone, having k crystallization sub- zones, the value of m being equal to or greater than 2 and equal to or less than n, the value of k being equal to or greater than 1 and equal to or less than m, comprising a first step of crystallizing the m components in the k crystallization sub-zones to form a first condensed mass and a second step of vaporizing a mass of the vola¬ tile component(s) from the liquid mixture to form a first vapor in each sub-zone under a first pressure that is lower than the eutectic pressure defined as the equilibrium pressure at which the m solid phases and the liquid mixture co-exist with a vapor phase containing the volatile component(s), wherein the said first step and the second step are conducted simultaneously so that at least a major fraction of the heat released in Step 1 operation is removed by the Step 2 operation in each sub-zone. Claim 2: A process of Claim 1, which further comprises a third step of transforming the first vapor into a second condensed mass con¬ taining the volatile component(s) in a second processing zone, at least a large fraction of each component in the second condensed mass being in a solid state. Claim 3: A process of Claim 2, which comprises a fourth step of bringing a second vapor containing the volatile component(s) and be¬ ing at a second pressure that is higher than the said first pressure in contact with the second condensed mass to thereby condense the second vapor and melt the second condensed mass to thereby form a third condensed mass, at least a major fraction of which is in the liquid state, and a fifth step of discharging the third condensed mass from the second processing zone. Claim 4: A process of either one of Claims 1 through 3, wherein there is only one crystallization sub-zone in the crystallization zone, denoted as the first processing zone, and the first condensed mass contains crystals of the m crystallizing components and a mother liquor. Claim 5: A process of Claim 4, which further comprises a sixth step of separating the first condensed mass into two or more separated condensed masses, each containing crystals of selected crystallizing components in an enriched state. Claim 6: A process of Claim 5, wherein each separated condensed mass contains mostly a mass of crystals of one crystallizing compo- nent and a mother liquor. Claim 7: A process of either one of Claims 1 through 3, wherein there are at least two crystallization sub-zones and portions of the feed mixture are introduced into at least two of the crystallization sub-zones. Claim 8: A process of Claim 3, wherein portions of the mother li¬ quors recovered from at least two crystallization sub-zones are mixed and become a recycled liquid, portions of the recycled liquid being introduced into at least two of the crystallization sub-zones. Claim 9: A process of either one of Claims 1 through 3, wherein there are at least two crystallization sub-zones and the first con¬ densed mass discharged from a crystallization sub-zone contains a mass of crystals of a selected group, that is a part of the crystal¬ lizing components, and a mother liquor and at least a part of the mother liquor produced in a crystallization sub-zone, say the i-th sub-zone, is introduced into another crystallization sub-zone, say the j-th sub-zone, to be processed in the j-th sub-zone.

Inventors: CHENG CHEN-YEN, CHENG WU-CHEH, CHENG WU-CHING, CHENG, CHEN-YEN, CHENG, WU-CHEH, CHENG, WU-CHING
Applicants: CHENG CHEN YEN, CHENG WU CHEH, CHENG WU CHING, CHENG, CHEN-YEN, CHENG, WU-CHEH, CHENG, WU-CHING
Application year: 1987
Main classification: F25J5
IPC codes: B01D9, C02F1