Pervaporation method of selectively separating water from an organic material aqueous solution through aromatic imide polymer asymmetric membrane

Abstract: A pervaporation separation method of water from an organic material aqueous solution at a high separating efficiency is effected by using a specific asymmetric separating membrane comprising a heat-resistant, solvent-soluble aromatic imide polymer prepared by the polymerization and imidization of an aromatic tetra­ carboxylic acid component comprising, as a principal ingredient, at least one biphenyl tetracarboxylic acid compound with an aromatic diamine component comprising a principal member selected from: and an additional member selected from another aromatic diamine compounds having 2 to 5 benzene ring structures and different from the diamine compounds (I) and (II).

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a pervaporation method of selectively separating water from an organic material aqueous solution through an aromatic imide polymer asymmetric membrane. More particularly, the present invention relates to a pervaporation method of selectively separating water from an organic material aqueous solution through an aromatic imide polymer asymmetric membrane at a high selectivity and at a high permeation rate, to concentrate or collect the organic material. 2. Description of the Related Art It is known that water can be separated from an aqueous solution of an organic material by a distillation method. In the distillation method, however, some of the organic materials form an azeotropic mixture, or have boiling points close to water, or are chemically modified at the distillation temperature, and therefore, it is very difficult to selectively separate water from the organic materials. To avoid the above difficulty, a method of separating water from an organic material by using a separating membrane has been attempted. In this method wherein a membrane is used to separate or concentrate an organic material aqueous solution, an aqueous solution of organic material is brought into contact with a face of a membrane, to allow a specific liquid to selectively permeate through the membrane due to a differential osmotic pressure. This method is referred to as a reverse osmosis method. Usually, in the reverse osmosis method for an organic material aqueous solution, a higher pressure than the osmotic pressure of the aqueous solution must be applied to the aqueous solution, and therefore, the reverse osmosis method can not be applied to a concentrated organic material aqueous solution which exhibits a high osmotic pressure, and accordingly, the reverse osmosis method can be applied only to organic material aqueous solutions having a limited concentration of the organic material. Recently, as a new type of separating method in which a separating membrane is used, a pervaporation method has been developed for an organic material solution and is now under serious consideration in this field. In the pervaporation method, an organic material aqueous solution in the state of a liquid is brought into direct contact with a feed side face of a separating membrane capable of selectively allowing a specific component, for example, water, to permeate therethrough, and the opposite delivery side face of the membrane is exposed to a vacuum or a reduced pressure. The specific component, for example, water, is allowed to selectively permeate through the membrane and is collected in the state of a vapor at the opposite delivery side of the membrane. This method is useful for selectively separating or concentrating an individual organic material from an aqueous solution thereof compound mixture. Also, it is known that aromatic imide polymers exhibit a higher heat resistance and chemical resistance than those of conventional polyamides, cellulose and cellulose acetate, and thus the utilization of the aromatic imide polymer as a material for forming a separating membrane is now under serious consideration. Accordingly, attempts have been made to utilize an asymmetric membrane consisting of a conventional aromatic imide polymer for separating water in the vapor state from an aqueous solution of an organic material. Nevertheless, when used for the pervaporation method of separating water from an organic material aqueous solution, the conventional aromatic imide polymer separating membranes are disadvantageous in that: (1) when the contact of the aromatic imide polymer membrane with the organic material aqueous solution or water is kept at a high temperature for a long time, the separating performance and mechanical strength of the membrane are significantly decreased, because the aromatic imide polymer in the membrane is decomposed by a hydrolysis thereof; (2) due to the above-mentioned decomposition of the polymer, the aromatic imide polymer membrane exhibits a decreased durability, and thus does not always provide a satisfactory separation of water from the organic material aqueous solution; and (3) the selective separation of water from the organic material aqueous solution and the permeating rate of water through the conventional aromatic imide polymer membrane are not satisfactory in the pervaporation separating method. Accordingly, there is a strong demand for a new type of aromatic imide polymer asymmetric membrane useful for the pervaporation method of selectively separating water from an organic material aqueous solution. SUMMARY OF THE INVENTION An object of the present invention is to provide a pervaporation method of selectively separating water from an organic material aqueous solution, at a high selectivity and with a high efficiency. Another object of the present invention is to provide a pervaporation method of selectively separating water from an organic aqueous solution, through a specific aromatic imide polymer asymmetric membrane having a high durability and thus able to be continuously employed for a long time in industrial use. The above-mentioned objects can be attained by the pervaporation method of the present invention of selectively separating water from an organic aqueous solution, which comprises the steps of: bringing an aqueous solution of an organic material into contact under a pressure of from the ambient atmospheric pressure to 5.88 MPaG (60 kg/cm²G), with one face of an asymmetric membrane in the form of a hollow filament and comprising at least one type or heat-resistant, solvent soluble aromatic imide polymer comprising: 30 to 90 molar% of recurring unit of the formula (I) : and 10 - 70 molar% of at least one type of recurring units selected from those of the formulae (II) , (III) and (IV) : exposing the opposite face of the aromatic imide polymer asymmetric membrane to an atmosphere under a reduced pressure of 26.7 kPa (200 Torr)or less, to cause water in the aqueous solution to selectively permeate through the asymmetric membrane and the permeated water to be vaporized in the reduced pressure atmosphere; and collecting the permeated and vaporized water. EP-A-0 321 569 discloses a pervaporation method of removing water from a liquid mixture by using a separating membrane. The separating membrane of EP-A-0 321 569 comprises a compolyimide having constitutional repeating units of the formula: wherein R represents a group for 10 to 30 mol% of the repeating units and group for 90 to 70 mol% of the repeating unit, or a copolyamide-imide comprising from 90 to 10 mol% of the constitutional repeating unit of the formula : and 10 to 90 mol% of the constitutional repeating unit of the formula: The copolyimide or the copolyamide-imide polymer of EP-A-0 321 569 has no biphenyl tetracarboxylic acid residue of the formula: Also, the copolyamide or copolyamide-imide polymer of EP-A-0 321 569 has no diphenylether group-containing structure of the formula: The specific aromatic imide polymer separating of the present invention can eliminate all the disadvantages (1) to (3), as mentioned on page 3, lines 8 to 24, of the specification, from the separating membrane for the pervaporation method of separating water from an aqueous organic material solution. EP-A-0 321 569 does not disclose how to eliminate the disadvantages (1), (2) and (3), especially, a poor resistance to hydrolysis decomposition at a high temperature, from the conventional aromatic imide polymer separating membrane. In contrast, in the present invention, the aromatic imide polymer comprises 30 to 90 molar% of recurring unit of the formula (I): and 10 - 70 molar% of at least one type of recurring units selected from those of the formulae (II), (III) and (IV): This type of the aromatic imide polymer is useful for preparing an asymmetric separating membrane having a superior water-resistance and ethyl alcohol-resistance. Therefore, even after the membrane is treated with hot water, for example, at a temperature of 150°C for 20 hours, or with a water-ethyl alcohol mixture, for example at a temperature of 150°C for 20 hours, the treated membrane can exhibit a high retention of the water-permeating property and tensile strength thereof. The heat-resistant, solvent soluble aromatic imide polymer usable for the present invention can be prepared by polymerising and imidizing the specific aromatic tetracarboxylic acid component and the specific aromatic diamine components in molar amounts substantially equal to each other in an organic solvent preferably comprising at least one phenolic compound, in a manner such that the solution is heated at a relatively high temperature of about 150°C to 250°C or at a relatively low temperature of about 10°C to 100°C in the presence of an imidization agent, for example, acetic anhydride, pyridine, or a mixture thereof. The organic solvent for the polymerization and imidization process comprises at least one member compound, for example, phenol, 2-chlorophenol, 4-chlorophenol, 4-bromophenol, cresol, N,N-dimethylacetamide and dimethylsulfoxide. The resultant aromatic imide polymer is also soluble in the above-mentioned organic solvent. The aromatic imide polymer is converted to an asymmetric separating membrane which may be in the form of a hollow filament or a film. The asymmetric separating membrane usable for the present invention can be prepared by disolving the aromatic imide polymer in a solvent comprising at least one phenolic compound to provide a dope solution; shaping the dope solution into a hollow filament-formed stream or a film-formed layer; bringing the shaped dope solution into contact with a coagulating bath to provide a solidified membrane; washing the solidified membrane with an organic solvent not capable of dissolving the solidified membrane; drying the washed membrane; and aging the dried membrane at a temperature of 150°C to 420°C. The organic solvent for asymmetric membrane-preparing process comprises at least one compounds selected from those usable as a solvent for the above-mentioned aromatic imide polymer-preparing process. Preferably, in the dope solution, the aromatic imide polymer is in a concentration of 5 to 30% by weight. The dope solution is shaped in a hollow filamentary stream thereof by extruding through a spinning nozzle for hollow filaments or in a flat filmy layer by extruding through a slit for film, or by spreading on a film-forming surface, for example, a horizontal surface of a film-forming plate or a peripheral surface of a rotating film-forming drum. The resultant shaped dope solution is brought into contact with a coagulating liquid to provide a solidified membrane. The coagulating liquid is compatible with the solvent in the dope solution but cannot dissolve therein the aromatic imide polymer in the dope solution. The coagulated aromatic imide polymer asymmetric membrane is washed with an organic solvent not capable of dissolving the solidified membrane. The washing organic solvent comprises at least one member selected from, for example, lower aliphatic alcohols having 1 to 6 carbon atoms, for example, methyl alcohol, ethyl alcohol, propyl alcohols and butyl alcohols and aliphatic and cycloaliphatic hydrocarbons having 1 to 8 carbon atoms, for example, n-hexane, n-heptane, n-octane and cyclohexane. Then, the washed membrane is dried and aged at a temperature of 150°C to 420°C, preferably 180°C to 400°C, more preferably 180 to 350°C, for 1 second to 5 hours. The method of producing a polymeric asymmetric membrane is disclosed, for example, in Japanese Unexamined Patent Publication Nos. 56-21602 and 56-157435. The asymmetric separating membrane prepared by the above-mentioned process and usable for the method of the present inventions comprises a core porous layer preferably having a thickness of about 10 µm to 2000 µm and at least one dense layer formed at at least one side of the porous layer and preferably having a thickness of about 0.001 µm to 5 µm. The selective water separating property of the asymmetric membrane is mainly controlled by the density and thickness of the dense layer thereof. In the method of the present invention, the asymmetric aromatic imide polymer membrane is used for the pervaporation separation of water from an aqueous solution of an organic material. In this method, the aromatic imide polymer asymmetric membrane preferably has a water-permeation rate of 0.2 kg/m²·hr or more, more preferably about 0.4 to 5.0 kg/m²·hr. Also, the aromatic imide polymer asymmetric membrane preferably has a ratio [QH₂O]/[QC₂H₅OH] of water-permeation rate [QH₂O] to ethyl alcohol-permeating rate [QC₂H₅OH], of 20 or more, for example, 25 to 1000, more preferably 100 or more, still more preferably, 120 or more, particularly 130 to 1000. In the pervaporation method of the present invention, an aqueous solution of an organic material preferably in a concentration of 50% by weight or more is brought into direct contact with one surface of the aromatic imide polymer asymmetric membrane; the opposite face of the aromatic imide polymer asymmetric membrane is exposed to an atmosphere under a reduced pressure, to cause water in the organic material aqueous solution to selectively penetrate and permeate through the asymmetric membrane; and the permeated water is collected in the state.of a vapor in the reduced pressure atmosphere. Practically, the pervaporation method of the present invention is carried out in the following steps. (a) An organic material aqueous solution is fed to a feed side of a separating membrane module containing a number of aromatic imide polymer asymmetric membranes (in the form of a hollow filament or a flat film) so that the fed aqueous solution comes into direct contact with one face of each membrane. (b) A delivery side opposite to the feed side of the separating membrane module is exposed to a reduced pressure by connecting the delivery side to a pressure-reducing or vacuum pump placed outside of the separating membrane module, if necessary, a sweeping(carrier) gas, for example, helium, nitrogen, and argon gases and air, is made to flow through the delivery side of the module, to promote the penetration of water. (c) Finally, the permeated water in the state of a vapor is collected from the delivery side of the module, and if necessary condensed by cooling, and the remaining non-permeated portion of the aqueous solution is recovered from the feed side of the module. Usually, the organic material aqueous solution is fed into the separating membrane module preferably at a temperature of from about 25°C to 120°C, more preferably from 50°C to 100°C. In the method of the present invention, the pressure at the delivery side of the separating membrane module is lower than that at the feed side. Usually, the pressure at the feed side of the separating membrane module is preferably from atmospheric pressure to 5.88 MPa (60 kg/cm²), more preferably from atmospheric pressure to 2.94 MPa (30 kg/cm²). Also, the pressure at the delivery side of the separating membrane module is lower than the atmospheric pressure, and is preferably about 26.7 kPa (200 Torr)or less, more preferably 13.3 kPa (100 Torr)or less. If necessary, a sweeping gas is made to flow through the delivery side of the module, to promote the permeation of water. The pervaporation method of the present invention can be applied to aqueous solutions of various types of organic materials. Namely, the pervaporation method of the present invention is specifically useful for separating organic materials which cannot be separated from water by a usual distillation method, or which have boiling points very close to water, and thus are very difficult to separate from water by the usual distillation method. The organic materials adequate to which the pervaporation method of the present invention is applied, comprise at least one member selected from, for example, aliphatic alcohols, for example, methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol and ethylene glycol; cycloaliphatic alcohols, for example, cyclohexanol; aromatic alcohols, for example, benzyl alcohol; aliphatic carboxylic acids, for example, formic acid acetic acid, propionic acid and butyric acid; aliphatic carboxylic acid esters, for example, butyl acetate, ethyl acetate and methyl malonate; aliphatic ketones, for example, acetone, and methylethyl ketone; cyclic ethers, for example, tetrahydrofuran and dioxane; aliphatic nitriles, for example, acetonitrile and acrylnitrile; and aliphatic aldehydes, for example, formaldehyde and acetaldehyde. In the pervaporation method of the present invention, the organic material aqueous solution is not limited to those having a specific level concentration and can be concentrated or divided into water and the organic material. There is no restriction on the structure, type, and size of the separating membrane module to be subjected to the pervaporation method of the present invention, but preferably the separating membrane module is a plate and frame type module, spiral type module or hollow filament type module. EXAMPLES The present invention will be further illustrated by way of specific examples, which are merely representative and do not restrict the scope of the present invention in any way. In the examples, the permeating rate Q and separating coefficient α were determined in the following manner. When an organic material aqueous solution was subjected to a pervaporation method, a fraction was permeated through a separating membrane, liquefied by cooling, and then collected, and the weight of the liquefied fraction was measured. Then an internal standard liquid consisting of dehydrated n-propyl alcohol was added to the liquefied fraction, and the whole was subjected to a TCD-gas chromatography to determine the proportions in weight of water to the organic material. The permeating rate Q of the liquefied fraction through a separating membrane and the separating coefficient α of the separating membrane for water and the organic materials were determined in accordance with the equations: Q = A/B α = C₂/C₁ wherein A represents an amount (in kg) of a liquefied fraction permeated through the membrane per hour and B represents a permeation area (in m²) of the membrane through which the liquefied fraction permeates, C₁ represents a proportion in weight of water to the organic materials in the aqueous solution to be fed and separated, and C₂ represents a proportion in weight of water permeated through the membrane to the organic materials permeated through the membrane. In the Examples, the compounds are represented by the following abbreviations. BAPP: 2,2-bis[4-(4-aminophenoxy)phenyl]propane 4,4'-DADE: 4,4'-diaminodiphenyl ether 3,4'-DADE: 3,4'-diaminodiphenyl ether DM: 4,4'-diaminodiphenylmethane TSN: o-tolidinesulfone DABA: 3,5-diaminobenzoic acid TPEQ: 1,4-bis(4-aminophenoxy) benzene TPER: 1,3-bis(4-aminophenoxy) benzene BAPB: 4,4'-bis(4-aminophenoxy) biphenyl PASN: bis(4-aminophenyl)sulfone BAPS: bis[4-(4-aminophenoxy)phenyl] sulfone Referential Examples 1 to 3 (i) Preparation of an aromatic imide polymer solution In each of Referential Examples 1 to3 , an aromatic imide polymer solution was prepared by polymerizing and imidizing the aromatic tetracarboxylic acid component having the composition as indicated in Table 1 and the aromatic diamine component having the composition as shown in Table 1, in substantially equal molar amounts, in an organic polar solvent consisting of p-chlorophenol (PCP) at a polymerization temperature of 180°C for the polymerization time as shown in Table 1. The resultant aromatic imide polymer solution had a polymer concentration and rotation viscosity at a temperature of 100°C, as indicated in Table 1. (ii) Preparation of aromatic imide polymer hollow filament yarn The aromatic imide polymer solution was subjected, as a spinning dope solution, to a hollow monofilament - spinning process by using a tule-in-orifice type spinneret and a coagulating liquid consisting of a mixture of 60 parts by weight of ethyl alcohol and 40 parts by weight of water, at a temperature of 5°C. The resultant hollow monofilament was taken up at a speed of 10 m/min, washed with ethyl alcohol and with an aliphatic hydrocarbon (n-hexane), dried at a temperature of 50°C, and aged under the temperature as indicated in Table 1 for 30 minutes. The resultant aromatic imide polymer hollow monofilament had an outside diameter of 620 µm, an inside diameter of 370 µm, and a thickness of 125 µm. The tensile strength and ultimate elongation of a specimen of the hollow-monofilament were measured, and the results are shown in Table 1. Separately, another specimen of the hollow monofilament was immersed in hot water or a mixture of water and ethyl alcohol in a mixing weight ratio of 4:6 at a temperature of 150°C for 20 hours, and the immersion treated specimen then subjected to measurements of the tensile strength and ultimate elongation thereof and the retention of the tensile strength and the ultimate elongation. The results are shown in Table 1. Referential Example 4 (i) Preparation of an aromatic imide polymer solution An aromatic imide polymer solution was prepared by polymerizing and imidizing the aromatic tetracarboxylic acid component consisting of 3,3'4,4'-biphenyl tetracarboxylic dianhydride and the aromatic diamine component 85 molar% of 1,4-bis(4-aminophenoxy benzene (TPEQ) and 15 molar% of 4,4'-diaminodiphenylether (4,4'DADE), in substantially equal molar amounts, in the organic polar solvent consisting of p-chlorophenol (PCP) at the polymerization temperature of 180°C and for the polymerization time of 20 hours. The resultant aromatic imide polymer solution had the polymer concentration of 17% by weight and the solution viscosity, which is a rotation viscosity (poise) at a temperature of 100°C, as shown in Table 2. (ii) Production of aromatic imide polymer hollow monofilament The aromatic imide polymer solution was subjected, as a spinning dope solution, to a hollow monofilament spinning process by using a tube-in-orifice type spinneret and a coagulating liquid consisting of a mixture of 60 parts by weight of ethyl alcohol with 40 parts by weight of water, at a temperature of 5°C, the resultant hollow monofilament was taken up at a speed of 10 m/min, washed with ethyl alcohol and with an aliphatic hydrocarbon (n-hexane), dried at a temperature of 50°C, and aged under the conditions as indicated in Table 2, for 30 minutes. The resultant individual aromatic imide polymer hollow monofilament (asymmetric membrane) had the outside diameter of 432 µm, the inside diameter of 266 µm and the thickness of 83 µm. The type of resultant hollow monofilament will be represented hereinafter by the number of the Referential Example in which the hollow monofilament was prepared. The resultant hollow monofilament was subjected to the tests as described in Referential Example 1. The results are shown in Table 2. Referential Examples 5 to 15 In each of Referential Examples 5 to 15 , the same procedures as those described in Referential Example 1 were carried out except that, in the preparation of the aromatic imide polymer solution, the aromatic diamine component had the composition as indicated in Table 2, and the polymerization time was as indicated in Table 2 and the resultant polymer solution had the concentration and rotation viscosity as indicated in Table 2, and in the preparation of the hollow monofilament, the dried hollow monofilament was aged at the temperature as shown in Table 2 The results of the tests are shown in Table 2. Comparative Examples 1 to 5 In each of Comparative Examples 1 to 5, 4 of the aged hollow monofilaments of the type shown in Table 3 were arranged in parallel to each other to form a hollow monofilament bundle. The bundle was folded to form a loop, and the open ends of the individual hollow monofilaments were sealed with an epoxy resin to provide a hollow monofilament bundle element. The hollow monofilament bundle element was placed in a container having an inlet for feeding an organic material aqueous solution, an outlet for recovering a nonpermeated fraction, and an outlet for collecting a permeated fraction, to provide a separating membrane module. An aqueous solution of 80% by weight of ethyl alcohol was fed into the separating membrane module at a temperature of 90°C so that the solution comes into contact with the outside peripheral surfaces of the hollow filaments. The hollow spaces of the individual hollow monofilaments were connected to a pressure-reducing or vacuum apparatus, and the pressure in the hollow spaces was reduced to 0.4 kPa (3 Torr)or less, to cause a specific fraction of the solution to be selectively permeated through the hollow filaments. The permeated fraction in the state of a vapor was cooled, and the resultant liquefied fraction was collected. The permeating rate Q of the permeated fraction through the hollow monofilaments and the separating coefficient α of the hollow monofilaments are shown in Table 3. In Comparative Example 3, the hollow monofilaments were further treated with hot water or a water-ethyl alcohol mixture (4:6) at a temperature of 150°C for 20 hours, dried at 60°C under a reduced pressure, and the resultant treated hollow monofilaments were subjected to the same separating property tests as mentioned above. The separating properties of the treated hollow monofilaments are also shown in Table 3. Examples 1 to 7 and Comparative Examples 6 to 10 In each of Examples 1 to 4 and Comparative Examples 6 to 10, the same procedures as mentioned in Example 1 were carried out, except that the hollow monofilament bundle element was prepared from the individual hollow monofilaments prepared in the Referential Example indicated in Table 4. The results of the separating test are shown in Table 4. The hollow monofilaments were treated in hot water at a temperature of 150°C for 20 hours, withdrawn from the treating hot water, and then dried at room temperature under a reduced pressure. The dried monofilaments were dissolved in a solvent consisting of a mixture of 4 parts by weight of p-chlorophenol (PCP) with 1 part by weight of o-chlorophenol (OCP). The logarithmic viscosity V₁ of the solution of the treated hollow monofilaments was measured at a temperature of 30°C. Separately, the logarithmic viscosity V₀ of a solution of the non-treated hollow monofilaments were determined in the same manner as mentioned above. The retention of the logarithmic viscosity of the hollow monofilaments was calculated in accordance with the following equation: The results are shown in Table 4. Further, in both of Examples 7 and 11 and Comparative Example 6, the hollow monofilaments were further treated with water or a water-ethyl alcohol mixture (4:6) at a temperature of 150°C for 20 hours. The treated hollow monofilaments were dried at a temperature of 60°C under a reduced pressure. The separating properties of the treated hollow monofilaments are shown in Table 4. As the examples clearly indicate, the pervaporation separating method of the present invention, in which a specific aromatic imide polymer asymmetric membrane is used as a separating membrane, effectively and selectively separates water from an organic material aqueous solution at a high permeating rate and at a high separating efficiency over a long time. The specific aromatic imide polymer asymmetric membrane has a superior resistance to heat, hot water and solvent, and thus exhibits a high durability in a separating process at a relatively high temperature, over a long time.

Claims: A pervaporation method of selectively separating water from an aqueous solution of an organic material, comprising the steps of: bringing an aqueous solution of an organic material into contact under a pressure of from the ambient atmospheric pressure to 5.88 MPaG (60 kg/cm²G), with one face of an asymmetric membrane in the form of a hollow filament and comprising at least one type of heat-resistant, solvent soluble aromatic imide polymer comprising: 30 to 90 molar% of recurring unit of the formula (I): and 10 - 70 molar% of at least one type of recurring units selected from those of the formulae (II) , (III) and (IV) : exposing the opposite face of the aromatic imide polymer asymmetric membrane to an atmosphere under a reduced pressure of 26.7 kPa (200 Torr)or less, to cause water in the aqueous solution to selectively permeate through the asymmetric membrane and the permeated water to be vaporized in the reduced pressure atmosphere; and collecting the permeated and vaporized water. A method as claimed in claim 1, wherein the aromatic imide polymer asymmetric membrane has a water-permeation rate of 0.2 kg/m².hr or more. A method as claimed in claim 1 or claim 2, wherein the aromatic imide polymer asymmetric membrane has a ratio of water-permeation rate to ethyl alcohol-permeation rate of 20 or more. A method as claimed in any one of the preceding claims, wherein the aromatic imide polymer asymmetric membrane is composed essentially of a dense layer having a thickness of 0.001 to 5 µm and a porous layer formed on the dense layer and having a thickness of 10 to 2000 µm. A method as claimed in any one of the preceding claims, wherein the aqueous solution of organic material has a temperature of from 25 º C to 120 º C. A method as claimed in any one of the preceding claims, wherein the organic material in the aqueous solution comprises at least one member selected from the group consisting of aliphatic alcohols, cycloaliphatic alcohols, aromatic alcohols, aliphatic carboxylic acids, cycloaliphatic carboxylic acids, aromatic carboxylic acids, and aliphatic carboxylic acid esters, ketones, cyclic ethers, nitriles and aldehydes.

Inventors: KUSUKI YOSHIHIRO C O UBE INDUS, NAKATANI MASAYUKI C O UBE INDU, SUMIYAMA YOSHIYUKI C O UBE IND, KUSUKI, YOSHIHIRO, C/O UBE INDUSTRIES LTD., NAKATANI, MASAYUKI, C/O UBE INDUSTRIES LTD., SUMIYAMA, YOSHIYUKI, C/O UBE INDUSTRIES LTD.
Applicants: UBE INDUSTRIES, UBE INDUSTRIES, LTD.
Application year: 1990
Main classification: B01D61
IPC codes: C08G73, B01D61, B01D71