Semipermeable composite membrane

Abstract: In a semipermeable composite membrane comprising a microporous substrate and an ultra-thin membrane with which the substrate is coated the ultra-thin membrane is com­ posed of a cross-linked aromatic polyamide and the cross-­ linked aromatic polyamide contains a tri- or higher functional aryl residue having at least two -NH groups. The semiperme­ able composite membrane has a high solute rejection, high and stable water flux and durability, and is thereby applicable to various fields.

Description: This invention relates to a semipermeable membrane for separating ingredients of liquid mixture by selective permeation, and more specifically, it relates to a semipermeable composite membrane for the desalination of sea water, brackish water and selectively removing or recovering pollutant or useful materials from waste water causing public pollutions, for example, from dyeing processes or from electrodepositing process, and which is thereby capable of contributing to the completeness of treatment of such waste water under a closed system. Asymmetric membranes prepared from cellulose acetate are known as the semipermeable membranes utilized industrially, for example, so-called "Loeb" type of those membranes as disclosed in U.S.P. Nos. 3133132 and 3133137. However, these membranes are poor in the resistivity to hydrolysis, bacterial attack and chemicals. Particularly, if an attempt is made to improve their permeability, their pressure resistance and durability are sacrificed, and accordingly they have not yet been put into practical use for a wide range of applications although employed in a restricted field. Extensive studies have been made for investigating a new material free from the drawbacks of the asymmetric cellulose acetate membranes mainly in U.S.A. and Japan, and materials which have partially overcome the foregoing drawbacks have been obtained, such as aromatic polyamide, polyamide hydrazide (U.S.P. No. 3567632), polyamide acid (Japanese Patent Publication No. 55-37282. U.S.P. No. 3878109), cross-linked polyamide acid (Japanese patent Publication No.58-3769), polyimidazopyrrolone, polysulfonamide, polybenzimidazole, polybenzimidazolone and polyarylene oxide. However, none of them is superior to the cellulose acetate membrane with respect to the selective separation characteristic or permeability. On the other hand, composite membranes comprising an ultra-thin membrane which is substantially responsible for membrane performance and a microporous substrate for supporting the ultra-thin membrane have been developed as a different type of semipermeable membrane from, the "Loeb" type. In such composite membrane, it is possible to select the optimum materials for each of the ultra-thin membrane and microporous substrate according to the purposes, and this can increase the degree of freedom for membrane fabrications. Another advantage of those composite membranes is said to be that they can be stored in the dry state, unlike the "Loeb" type membranes which must be stored always in a wet condition. These composite membranes are classified into two types, that is, those comprising an ultrathin membrane and a microporous substrate coated with the ultrathin membrane directly and those comprising an ultrathin membrane, microporous substrate and a gel layer intermediately between them. Examples of the former are described in US-A-3744642, US-A-3926798, EP-B-0015149, US-A-4557949, US-A-4366062, JP-A-57-140607 and JP-A-58-24303, and examples of the latter are described in JP-A-49-133282 (US-A-4039440), JP-A-55-49524, US-A- 3951815), JP-A-55-38164 (US-A- 4005012) PB Report No. 80-182090. US-A-4387024 and US-A-4559139. EP-B-0015149 referred to above describes a composite membrane comprising a microporous substrate coated with an ultrathin membrane composed of a polyamide formed by in-situ reaction of (a) an aromatic amine-reactive reactant comprising a polyfunctional acyl halide and (b) an aromatic polyamine. The polyfunctional acyl halide has at least three acyl groups and the polyamine has a primary amine functionality which is no more than the carboxylic acid equivalent functionality of the polyfunctional halide. The specifically exemplified polyamines are all derived from diamines. In JP-A-57-140607 on the other hand, where the membrane is again formed by the reaction of a polyfunctional acyl halide and an aromatic polyamine, the polyamine comprises a benzene ring or non-fused binuclear aromatic ring having a plurality of amine groups and also one or two carboxyl groups or salts thereof. Those prior semipermeable composite membranes mentioned above, however, can not satisfy all of the desired properties required for the membranes, such as high solute rejection against both organic and inorganic materials dissolved in, water, high water flux rate, durability such as heat resistance, chemical resistance, pressure resistance, chlorine resistance and hydrogen peroxide resistance. Reverse osmosis is generaily expected to be applied in various fields, such as, desalination represented by the conversion of sea water or brackish water into potable water, concentration or recovery of valuable materials, production of ultrapure water and separation of organic liquid mixtures. Accordingly, the desired specific properties required for the reverse osmosis membrane would vary multifariously depending on its use and application. The important properties among them are selective permeability (solute rejection: Rej (%), water flux: Flux (m³/m².day)), durability (m-value relating to the change of flux with the lapse of time), pressure resistance, heat resistance, oxidation resistance, workable pH range, resistance to microorganisms durability for chemicals and solvent storage stability, etc. The m-value mentioned above is represented by the formula log(Qt₂/Qt₁)/log(t₂/t₁) where t₁ is an initial time and t₂ is a time after a predetermined period and Qt₁ and Qt₂ represent the flux at the time t₁ and the time t₂, respectively. However, no asymmetric nor semipermeable composite membrane fulfilling all of these requirements has been developed at present. For example, the prior composite reverse osmosis membrane having an ultrathin membrane of cross-linked polyamide is said to show significant reduction of the flux with the lapse of operation period. While the desirable m-value for practical use of the reverse osmosis membrane is usually around -0.02, which corresponds to about 20 % reduction of the flux during the operation of three years, any reverse osmosis membrane which has the m-value far from the above can not be considered useful from the viewpoint of efficiency and economy, even though its initial characteristics and properties are excellent and acceptable. While on the other hand, the practical level of the solute rejection against organic material is usually required to be higher than 90 %, representatively, against neutral, basic and acidic molecules such as isopropyl alcohol, ethylenediamine and acetic acid, no reverse osmosis membrane capable of fulfilling this requirement has been developed. In addition, although some of the prior reverse osmosis membranes made of polyamide or cross-linked polyamide had been considered as chlorine resistant, their water flux is, in fact, usually reduced by about 20 to 30 % or more after they are brought into contact with chlorine (refer to Journal of Applied Polymer Science, Vol. 29, 3369 (1984)), and the loss of the rejection and increase in the flux rate occur in an unrecoverable manner, possibly due to the decomposition of polyamide upon contact with chlorine for a long period of operation or at high chlorine concentration. A practically attractive reverse osmosis membrane should have a salt rejection of 99 % or higher and water flux of 0.8 m³/m².day or greater under the condition of an applied pressure of 56 kg/cm² and a saline water feed of 35,000 ppm in the case of sea water desalination, or a salt rejection of 99 % or higher and water flux of 0.7 to 1.3 m³/m².day or greater under the conditions of an applied pressure of 15 to 30 kg/cm² and a saline water feed of 1500 ppm in the case of brackish water desalination, in addition to a small reduction of water flux with the lapse of operation period, an improved rejection against organic materials and an oxidation resistance. The reverse osmosis membranes having been developed so far can only partially satisfy these requirements, and accordingly are subjected to various restrictions when put into practical use. The object of the invention is to provide a semipermeable composite membrane of which the ultra-thin membrane is made of specific cross-linked aromatic polyamide, having superior hydrophilicity, and high cross-linking density to improve especially the solute rejection against both inorganic and organic materials and water flux as well as the mechanical durability of the ultra-thin membrane. In accordance with the present invention we provide a reverse osmosis membrane comprising a microporous substrate coated with an ultra-thin membrane composed of a cross-linked aromatic polyamide having a degree of cross-linking sufficiently high to provide a salt rejection of 98.9% or higher and a water flux of 0.69 m³/m².day or greater under he conditions of an applied pressure of 56 kg/cm² (5492 kpa) and 25° C in the case of sea water (saline concentration of 3.5%) desalination, or a salt rejection of 99% or higher and a water flow of 0.7 to 1.3m³/m².day or greater under the condition of an applied pressure of 15 to 30 kg/cm² (1471 to 2943 Pa) and 25° C in the case of brackish water (saline concentration of 1500ppm) desalination. The cross-linked polyamide is prepared by interfacial polycondensation of a monomeric aromatic acid halide component and a monomeric aromatic amine component containing 1,3,5-triaminobenzene and/or tetraaminobenzanilide, which aromatic amine component may comprise 25 mol% of the 1,3,5-triaminobenzene and/or tetraaminobenzanilide. The composite membrane may be modified by being brought into contact with a chlorine-containing solution. The ultra-thin membrane of the invention is composed of the cross-linked aromatic polyamide obtainable by the interfacial polycondensation, and the thickness thereof can optionally be selected within the range of 10 to 1,000 nm depending on the intended purpose. The microporous substrate of the membrane of the present invention is exemplified by a polysulfone microporous substrate reinforced with fabric mainly composed of a polyester and/or aromatic polyamide The microporous substrate does not have substantial separation capacity, but serves to provide the strength to the ultra-thin membrane which has the substantial separation capacity. The substrate preferably has a structure with uniform micro pores or those micro pores gradually enlarged from one surface to the other surface, with the size of the micro pores on one surface being smaller than about 100 nm. While the microporous support may be selected from various commercially available materials such as milipore filter (VSWP) or Toyo Filter Paper (UK10), it can usually be prepared according to the method described in "Office of Saline Water Research and Development Progress Report" No. 359 (1968). Homopolymers or the blended polymers of , such as, polysulfone, cellulose acetate, cellulose nitrate and polyvinyl chloride may be usually employed as the material. As one embodiment for preparing the microporous substrate, a microporous support having micro pores with a diameter of not greater than dozens nm on a main part of the surface can be obtained by casting a solution of polysulfone in dimethyl formamide (DMF) to a predetermined thickness over a closely woven polyester fabric or non-woven fabric and then dipping in an aqueous solution containing 0.5 % by weight of sodium dodecylsulfate and 2 % by weight of DMF. In addition to the aromatic amines referred to above as essential components of the monomeric amine component for reaction with the aromatic acid halide component, other aromatic amines, which may be additionally used in combination therewith, may be represented by the formulae (III) and (IV); wherein R₁-R₁₀ represent a reactive amino group or other substituent. The number of the amino groups in the compound of formula (III) is at least 2, and preferably 2 to 6, more preferably 2 or 3 for the convenience of handling. Other substituents than the amino group in the compound of the formula (III) may be any of substituents that do not hinder the formation of the cross-linked polyamide bridge, for instance. -H, -OCH₃, -CH₃, -C₂H₅, -C₃H₇, -SO₃H, -COOH, -NHCH₃, -OH, -F, -Cl, -Br, and -I. Hydrophilic substituents such as -H, -OCH₃, -COOH, -SO₃H and -OH are preferable for increase of water permeability. The number of the reactive amino groups in the compound of the formula (IV) is at least 2, and preferably 2 to 10 for the oxidation resistance of the semipermeable membrane, more preferably 2 to 7, and most preferably from 2 to 4 for the availability of the starting compound and the convenience of handling. Other substituents than the amino group in the compound of the formula (IV) may be any of substituents that do not hinder the formation of the cross-linked polyamide bridge, for instance. -H, -OCH₃, -CH₃, -C₂H₅ -C₃H₇, -SO₃H, -COOH, NHCH₃, -OH, -COCH₃, -F, -Cl, -Br and -I. Hydrophilic substituents such as -H, -OCH₃, -SO₃H, -COOH and -OH are preferable for increase of water permeability. The symbol X in the formula (IV) means a single bond between two aromatic rings, or alternatively may be any of the divalent groups capable of bonding two aromatic rings, for instance. -NHCO-, -SO₂-, -S-, -COO-, and -O-, preferably oxygen-containing groups such as -NHCO-, -SO₂-, -COO- and -O-for the interaction with water, and more preferably -O- and -NHCO- for the affinity with water. While the position of each substituent is not particularly restricted, those positions undergoing less steric hindrance are preferable for the separation capacity. In view of the selectivity, permeability, durability and the like of the semipermeable composite membrane according to the present invention, the aromatic amine preferably contains not less than 5 % by weight of at least one of aromatic amines represented by the following formulae: and most preferably contains not less than 5 % by weight of the aromatic amine of the formula for the overall point of view on the separation capacity, chlorine resistance, hydrogen peroxide resistance and change of flux rate with the lapse of time, The aromatic acid halide, the other reagent for preparing the cross-linked aromatic polyamide according to the invention, may be represented by the formulae (V) and (VI): wherein R₁₁-R₂₀ represent a reactive acyl halide group or other substituent. The number of the acyl halide groups in the compound of the formula (V) is at least 2, and preferably 2 to 6, more preferably 2 or 3 for the convenience of handling. Other substituents than the acyl halide group in the compound of the formula (V) may be any of substituents that do not hinder the formation of the cross-linked polyamide, for instance, -H, -OCH₃, -CH₃, -C₂H₅, -C₃H₇, -COCH₃, -F, -Cl, -Br and -I. Hydrophilic substituents such as -H and -OCH₃ are preferable for the increase of water permeability The number of the acyl halide groups in the compound of the formula (VI) is at least 2, and preferably 2 to 7 for the oxidation resistance of the semipermeable membrane, and more preferably from 2 to 4 for the availability of the starting compound and the convenience of handling. Other substituents than the acyl halide group in the compound of the formula (VI) may be any of substituents that do not hinder the formation of the cross-linked polyamide, for instance, -H, -OCH₃, -CH₃, -C₂H₅, -C₃H₇, COCH₃, -F, -Cl, -Br and -I. Hydrophilic substituents such as -H and -OCH₃ are preferable for the increase of water permeability The symbol Y in the formula (VI) means a single bond between two aromatic rings, or alternatively may be any of the divalent groups capable of bonding two aromatic rings, for example, -NHCO-, -SO₂-, -S-, -COO-, -C(CH₃)₂- and -O-, preferably oxygen-containing groups such as -NHCO-, -SO₂-, -COO- and -O- for the interaction with water, and more preferably -O- and -NHCO- for the affinity with water. While the position of each substituent in the formula (V) or (VI) is not particularly restricted, those positions undergoing less steric hindrance are preferable for the separation capacity. Preferable examples of the acid halide used in the process of the invention include By the term "average functionality" of the aromatic amine in the present invention is meant the total number of the amino groups divided by the number of molecules in the aromatic amines comprising one or more of aromatic amines having two or higher functionality. On the other hand, by the term "average functionality" of the aromatic acid halide in the present invention is meant the total number of the acyl halide groups divided by the number of molecules in the aromatic acid halide comprising one or more of aromatic acid halides having two or higher functionality. The average functionality of the aromatic amine thus defined may be 2.05 or more, and particularly preferable between 2.05 and 3.00 for enhancing the membrane performance and stability of the semipermeable composite membrane. The average functionality of the aromatic acid halide may be 2.00 or more, and preferably from 2.00 to 3.00 for the membrane performance. The employable organic solvent for the present invention may be any one of those which are immiscible with water, can dissolve the acid halide, does not destroy the microporous substrate, and can form the cross-linked aromatic polyamide by the interfacial polycondensation. Preferable examples of the solvent include hydrocarbons, cyclohexane and trifluorotrichloroethane, more preferably at least one of n-hexane and trifluorotrichloroethane for the reaction rate and volatility of solvent, and most preferably trifluorotrichloroethane for further considering the safety with respect to inflammability. The present invention is further illustrated by referring to specific examples described hereinafter, but in no way limited by them. The following examples show the characteristics of composite reverse osmosis membranes prepared from at least one of 1,3,5-triaminobenzene, 3,3',5,5'-tetraaminobenzanilide and 2,3',4,5'-tetraaminobenzanilide as the amine moiety and at least one of trimesic chloride and terephthalic chloride as the acid chloride moiety. As the selective separation capacity, the sodium chloride rejection is determined by the measurement of electroconductivity, and the rejection against organic compounds is determined by the analysis by the total organic carbon. As the permeation characteristic, the water flux per unit area and per unit time is determined. Example 1 : Preparation of 1,3,5-triaminobenzene 5-nitro-m-phenylenediamine (100.0 g) was dissolved in acetone (100 ml) and insolubles were filtered off by means of suction, 15.0 g of activated carbon was added into the solution: after stirring for 5 minutes it was removed by suction filtration. The solution was concentrated till crystals were slightly deposited, and 200 ml of water was added. The precipitated solids were filtered by means of suction, and dried under a reduced pressure to obtain 68.5 g of purified 5-nitro-m-phenylenediamine. The purified 5-nitro-m-phenylenediamine (55.0 g), platinum/carbon (5 %) (1.06 g) and dioxane (580 ml) were placed in a tightly closed vessel and stirred at the rate of 851 rpm under a hydrogen pressure of 1 to 4 kg/cm² (98 to 392 kPa) at 80 °C. Hydrogen absorption was ceased within 25 minutes, and the mixture was stirred further for one hour at 80 °C followed by being left to cool. After filtering off the catalyst, the mixture was concentrated to 250 ml, then added with n-hexane (250 ml), and the white precipitate produced filtered off. This white solid was washed with n-hexane and dried to obtain 1,3,5-triaminobenzene (39 g). The yield was 88 %. Example 2 : Preparation of 3,3',5,5'-tetraaminobenzanilide While maintaining the inside of the reaction vessel in nitrogen atmosphere, 3,5-dinitroaniline (36.9 g) was dissolved in dehydrated tetrahydrofuran, to which triethylamine (26.4 g) was added. A solution of 3,5-dinitrobenzoyl chloride (51.0 g) in dehydrated tetrahydrofuran was added dropwise, then the reaction mixture was stirred at room temperature for 4 hours and further subjected to reflux for 4 hours. After filtering off the precipitates, the tetrahydrofuran in the reaction mixture was distilled off under reduced pressure followed by addition of methanol, and the precipitated powder was filtered and dried to obtain 52.7 g of white powder of 3,3',5,5'-tetranitrobenzanilide. The product of 3,3',5,5'-tetranitrobenzanilide (50.00 g) thus obtained, platinum/carbon (5 %) (5.00 g) and dioxane (500 ml) were placed in a pressurized vessel and allowed to react under the hydrogen pressure of 2 to 4 kg/cm² (196 to 392 kPa) at 80° C for 3 hours. After cooling the catalyst was removed by filtration and dioxane was distilled off under the reduced pressure to obtain yellow powder of 3,3',5,5'-tetraaminobenzanilide (34 g). Example 3 : Preparation of 2',3,4',5-tetraaminobenzanilide 2,4-dinitroaniline (18.05 g), triethylamine (12.97 g) and benzene (750 ml) were placed in a reaction vessel and stirred under the nitrogen atmosphere. To the reaction mixture, 3,5-dinitrobenzoyl chloride (25.00 g) was added and refluxed under heating for 6 hours. The reaction mixture was filtered in hot state and the filtrate was cooled to deposit crystals of 2',3,4',5-tetranitrobenzanilide which was collected by filtration. The product of 2',3,4',5-tetranitrobenzanilide (3.00 g) thus obtained, platinum/carbon (5 %) (0.18 g) and dioxane (85 ml) were placed in a pressurized vessel and allowed to react under the hydrogen pressure of 1 to 3 kg/cm² (98 to 294 kPa) at 80°C for 10 hours. After cooling, the catalyst was removed by filtration and dioxane was distilled off under reduced pressure to obtain brown powder of 2',3,4',5-tetraaminobenzanilide. Example 4 : Preparation of fiber-reinforced polysulfone substrate A polyester woven fabric of taffeta (30 cm x 20 cm. 160 µm in thickness, woven by multifilament of 150 deniers (17 tex), warp density of 90/inch (35.4/cm) and woof density of 67/inch (26.4/cm) was fixed on a glass plate, over which 15 wt% solution of polysulfone (Udel P-3500, manufactured by Union Carbide Co., Ltd.) in dimethylformamide (DMF) was cast in a thickness of 200 µm at room temperature (20° C). Then it was immediately immersed into purified water and left for 5 minutes to obtain a fiber-reinforced polysulfone substrate, hereinafter referred to as FR-PS. The water permeation coefficient of FR-PS (210 to 215 µm in thickness) was 0.005 to 0.01 g/cm².sec.atm. (0.005 to 0.01 g.cm.s.bar) under the pressure or 1 kg/cm² (98kPa) and at the temperature of 25° C. Example 5 The FR-PS obtained in Example 4 was immersed in hot water at 90° C for 2 minutes, and then cooled in water at room temperature. The FR-PS was then immersed in aqueous solution containing 0.55 % by weight of 1,3,5-triaminobenzene and 1.45 % by weight of m-phenylenediamine (molar ratio = 25 : 75) for 2 minutes. After removing the excess amount of the aqueous solution from the surface of the FR-PS, the surface was coated with a solution containing 0.5 % by weight of trimesoyl chloride, 0.5 % by weight of terephthaloyl chloride and 0.015 % by weight of dimethylformamide in 1,1,2-trichloro-1,2,2-trifluoroethane so that the surface of the FR-PS was completely covered with the solution for 1 minute. After draining off the excess amount of the solution in a vertical position, the membrane was immersed in an aqueous solution containing 0.2 % by weight of sodium carbonate for 5 minutes followed by washing with water. The reverse osmosis performance of the semipermeable composite membrane thus obtained was evaluated under the following conditions. Pressure: 15 kg/cm² (1471 kPa) Temperature: 25° C Feed: 1500 ppm NaCl As a result, the salt rejection was 99.65 % and the water flux was 0.90 m³/m².day. The thickness of the ultra-thin aromatic polyamide membrane was found to be from 30 to 800 nm with the average thickness of about 150 nm. Examples 6, 7, 8 and Comparative Example 1 Membranes were prepared by repeating the same procedures as those of Example 5 excepting that amine and acid chloride listed in Table 1 below wire used for the synthesis of the ultra-thin membrane according to the invention. The membrane performance of each membrane are shown in Table 1. Example 9 and Comparative Example 2 The m-value representing the change of water flux of the semipermeable composite membrane obtained in Example 5 was measured (the m-value being formulated as log(Qt₂/Qt₁)/log(t₂/t₁) wherein t₁ is the initial time, t₂ is a time after a predetermined period, and Qt₁ and Qt₂ are the flux rate at the times t₁ and t₂, respectively). As a result, the m-value at 1,000 hours was -0.011. In the same way, the membrane of Comparative Example 1 had the m-value of -0.04. Example 10 The membrane performance of the semipermeable composite membrane of Example 5 were measured after running of 100 hours under the same conditions as those of Example 5 excepting that chlorine was added to the feed water at the level of residual chlorine content of 10 ppm during the operation and pH was adjusted to 7.5. The salt rejection was 99.05 % and the water flux was 0.83 m³/m².day. After interrupting the addition of chlorine, by cleaning with trisodium phosphate at 500 ppm and then with phosphoric acid at 1,000 ppm, the salt rejection was recovered to 99.65% and the water flux to 1.08 m³/m².day. Comparative Example 3 A composite membrane was prepared by the same procedures as those of Example 5 excepting that m-phenylenediamine as the starting amine and trimesoyl chloride as the starting acid chloride were used. As a result of the evaluation of the membrane thus obtained, the salt rejection was 98.5 % and the water flux was 0.8 m³/m².day. Example 11 The membrane performance of the membrane obtained in Example 5 against isopropyl alcohol was measured at the following conditions. Pressure: 15 kg/cm² (1471 kPa) Temperature. 25° C Feed: 1000 ppm solute The rejection was 96.6 %. Comparative Example 4 The membrane performance of the membrane obtained in Comparative Example 3 was measured under the same conditions as those of Example 11. The rejection was 87.7 %. Example 12 The membrane performance of the membrane obtained in Example 5 against ethylenediamine was measured under the same conditions as those of Example 11. The rejection was 95.5 %. Comparative Examples 5 The membrane performance of the membrane of Comparative Example 3 was measured against ethylenediamine under the same conditions as those of Example 11. The rejection was 93.3 %. Example 13 The membrane performance of the membrane of Example 5 was measured against acetic acid under the same conditions as those of Example 11. The rejection was 50.0 %. Comparative Example 6 The membrane performance of the membrane obtained in Comparative Example 3 was measured against acetic acid under the same conditions as those of Example 11. The rejection was 43.9 %. Example 14 The FR-PS obtained in Example 4 was immersed in hot water at 90° C for 5 minutes, and then cooled in water a, a room temperature. Then, the FR-PS was immersed in an aqueous solution containing 1.00 % by weight of 1,3,5-triaminobenzene and 1.00 % by weight of m-phenylenediamine (molar ratio = 47 : 53) for 2 minutes. After removing the excess amount of the aqueous solution from the surface of the FR-PS, it was coated with a solution of 0.05 % by weight of trimesoyl chloride and 0.05 % by weight of terephthaloyl chloride (molar ratio = 43 : 57) in 1,1,2-trichloro-1,2,2-trifluoroethane so that the surface was completely covered for one minute. After draining off the excess amount of the solution in a vertical position, the surface of the membrane was coated with 1,1,2-trichloro-1,2,2-trifluoroethane so that the surface was completely covered for 30 seconds. Then, after draining the membrane in a vertical position, the membrane was dried at room temperature. The membrane performance of the composite membrane thus obtained was measured using 3.5 % synthetic sea water with an osmotic pressure of 25 kg/cm² under the conditions of 56 kg/cm² and 25° C. As a result, the membrane performance was found to be 99.0 % of rejection and 0.85 m³/m².day of water flux. Examples 15-17 Fresh FR-PS obtained in Example 4 was immersed for 2 minutes in on aqueous solution containing 2 % by weight in total of 2,3',4,5'-tetraaminobenzanilide and m-phenylenediamine in a molar ratio shown in Table 2 below. After removing the excess aqueous solution, the surface of the membrane was coated with a solution of 0.063 % by weight in total of trimesoyl chloride and terephthaloyl chloride in a molar ratio shown in Table 2 in trifluorotrichloroethane so that the surface was completely covered for about 30 seconds followed by draining. The membrane performance of the composite membrane thus produced was measured under the following conditions. Pressure: 56 kg/cm² (5492 kPa) Temperature: 25° C Feed: 3.5 % NaCl The results are shown in Table 2. Examples 18 - 21 Fresh FR-PS obtained in Examine 4 was immersed for 2 minutes in an aqueous solution containing 2 % by weight in total of 3,3',5,5'-tetraaminobenzanilide and m-phenylenediamine in a molar ratio as shown in Table 3 below. After removing the excess aqueous solution ,the surface was coated with a solution of 0.063 % by weight in total of trimesoyl chloride and terephthaloyl chloride in a molar ratio shown in Table 3 in trifluorotrichloroethane so that the surface was completely covered for about 30 seconds followed by draining. The membrane performance was measured under the same procedure as Examples 15 - 17. The results are shown in Table 3. Example 22 A semipermeable composite membrane was prepared under the same conditions as those of Example 5 except that the molar ratio of the acid chlorides was 4 : 6, the content of dimethylformamide was 0.008 % by weight and the membrane was not immersed in the aqueous solution of sodium carbonate. Then, the membrane performance was measured under the following conditions. Pressure: 30 kg/cm² (2943 kPa) Temperature: 25°C Feed: 1500 ppm NaCl As a result, the salt rejection was 99.7 % and the water flux was 1.40 m³/m².day. Example 23 A composite membrane was prepared under the same conditions as those of Example 14 except that a FR-PS reinforced with poly(methaphenylene-isopthalamide) fibers was used and the surface was not washed with 1,1,2-trichloro-1,2,2-trifluoroethane after the cross-linking reaction. The membrane performance was measured under the same procedure as Example 14. As a result, the salt rejection was 98.9% and the water flux was 0.69 m³/m².day. After immersion of the membrane in an aqueous 1N-NaOH solution at 25° C for 7 days, the membrane performance under the same conditions as described above showed 98.9% of the salt rejection and 0.68 m³/m².day of the water flux. Example 24 The membrane characteristics of the semipermeable composite membrane of Example 5 were measured under the same conditions as those of Example 5 after immersing the membrane in an aqueous solution containing residual chlorine concentration of 1,000 ppm and of pH 10.3 under the room temperature for 18 hours. The salt rejection was 98,2% and the water flux was 2.70 m³/m².day. Example 25 The membrane characteristics of the semipermeable composite membrane of Example 5 were measured under the same conditions as those of Example 5 after immersing the membrane in an aqueous solution of 2% hydrogen peroxide at the room temperature for 12 hours. The salt rejection was 99.57% arid the water flux was 0.95 m³/m².day. Example 26 The FR-PS obtained in Example 4 was immersed in an aqueous solution of 2 % by weight of 1,3,5-triaminobenzene for 2 minutes. After removing the excess aqueous solution from the surface of the FR-PS, the surface was coated with a solution of 0.025 % by weight of terephthaloyl chloride dissolved in 1,1,2-trichloro-1,2,2-trifluoroethane so that the surface was completely covered for one minute. Then, in vertical position to drain off the excess solution, the surface was coated with 1,1,2-trichloro-1,2,2-trifluoroethane so that the surface was completely covered for 30 seconds and then in vertical position to drain off and dried under the room temperature. The resultant composite membrane was subjected to a reverse osmosis test using a liquid filtrate containing 0.5 % by weight of the paint ingredient derived from the ultrafiltration of a cationic electrodepositing paint, under the conditions of 30 kg/cm² (2943 kPa) of pressure and 25° C of temperature. The rejection against the paint ingredient was 99.7 % and the water flux was 0.42 m³/m².day. Example 27 The composite membrane produced in Example 5 was cut into an appropriate size and immersed in methylene chloride to separate an ultra-thin membrane layer, which was then filtered off by means of suction using a glass filter. The thus obtained sample of the ultra-thin layer (29 mg) was hydrolyzed with 12 ml of 6N hydrochloric acid solution at 180° C . After removing the insolubles, the hydrolysate was dried to be solidified. The weight of the solid was measured to be 25 mg. The solid was dissolved in a mixture of 2 ml of methyl alcohol and 10 ml of ethyl ether, to which diazomethane was bubbled to esterify by methylation. After distilling off the solvent under reduced pressure, 2 ml of methyl acetate and 0.5 ml of trifluoroacetic acid anhydride were added and left for five minutes. After further distilling off the solvent under reduced pressure, the residue was dissolved in 1 ml of methanol to examine its composition by the GC-MS method. As a result, molecular ion peaks and fragment ion peaks corresponding to the trifluoroacetylated product of 1,3,5-triaminobenzene and m-phenylenediamine and methyl esters of trimesic acid and terephthalic acid were detected by mass spectroscopy. According to the gas chromatographic analysis using internal standard method, the weight, ratio of 1,3,5-triaminobenzene to m-phenylenediamine was about 0.5 : 1.5 and the weight ratio of trimesic acid to terephthalic acid was about 0.5 : 0.5. As described in the forgoing examples, it can be understood the semipermeable composite membrane according to the present invention has a high solute rejection and high water flux, and is excellent in the m-value for maintaining the stable water flux and oxidation resistance such as chlorine resistance and hydrogen peroxide resistance which are important factors in view of the practical use and further applicable within a broad pH range. It has, in addition, been confirmed that the composite semipermeable membrane of this invention may be subjected to a wide variety of applications, for instance, from low pressure to high pressure operation, production of ultra-pure water, desalination of sea water, separation of inorganic salts and organic materials and, further, recovery of electrodepositing paints depending on the variation of composition thereof and the method of the preparation thereof.

Claims: A reverse osmosis membrane comprising a microporous substrate and an ultra-thin membrane with which the substrate is coated, characterised in that said ultra-thin membrane is composed of a cross-linked aromatic polyamide having a degree of cross-linking sufficiently high to provide a salt rejection of 98,9% or higher and a water flux of 0,69m³/m².day or greater under the conditions of applied pressure of 56 kg/cm² (5492 kPa) and 25° C the case of sea water (saline concentration 3.5%) desalination, or a salt rejection of 99% or higher and a water flux of 0.7 to 1.3m³/m².day or greats under the conditions of an applied pressure of 15 to 30 kg/cm² (1471 to 2943 kPa) and 25°C in the case of brackish water (saline concentration of 1500ppm) desalination, which is prepared by interfacial polycondensation of a monomeric aromatic acid halide component and a monomeric aromatic amine component containing 1,3,5-triaminobenzene and/or tetraaminobenzanilide. A reverse osmosis membrane according to claim 1, which is prepared by interfacial polycondensation of a monomeric aromatic amine component containing 1,3,5-triamine benzene and a monomeric aromatic acid halide component. A reverse osmosis membrane according to claim 1, which is prepared by interfacial polycondensation of a monomeric aromatic amine component containing tetraaminobenzanilide and a monomeric aromatic acid halide component. A reverse osmosis membrane according to claim 1 or claim 3 wherein the tetraaminobenzanilide is 2,3',4,5'-tetraaminobenzanilide or 3,3',5,5'-tetraaminobenzanilide. A reverse osmosis membrane according to any preceding claim wherein the monomeric aromatic amine component also contains m-phenylene diamine or p-phenylene diamine. A reverse osmosis membrane according to any preceding claim wherein the 1,3,5-triamino benzene and/or the tetraminobenzanilide constitutes at least 5% by weight of the monomeric aromatic amine component. A reverse osmosis membrane according to claim 6, wherein the 1,3,5-triaminobenzene and/or the tetraaminobenzanilide constitutes 25 mol percent of the monomeric aromatic amine component. A reverse osmosis membrane according to any preceding claim wherein the monomeric aromatic acid halide component is selected from trimesoyl chloride, isophthaloyl chloride and terephthaloyl chloride. A reverse osmosis membrane according to any preceding claim wherein the average functionality of the aromatic amine is from 2.05 to 3.0. A reverse osmosis membrane according to any preceding claim wherein the average functionality of the aromatic acid halide is from 2.0 to 3.0. A reverse osmosis membrane according to any preceding claim wherein the microporous substrate comprises polysulfone. A reverse osmosis membrane according to any preceding claim, wherein the microporous substrate is reinforced with fabric mainly composed of polyester and/for aromatic polyamide. A reverse osmosis membrane according to any preceding claim wherein the composite membrane is further modified by being brought into contact with a chlorine-containing solution.

Inventors: HIMESHIMA YOSHIO, KURIHARA MASARU, UEMURA TADAHIRO, HIMESHIMA, YOSHIO, KURIHARA, MASARU, UEMURA, TADAHIRO
Applicants: TORAY INDUSTRIES, TORAY INDUSTRIES, INC.
Application year: 1986
Main classification: B01D69
IPC codes: B01D71, B01D69