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WO1993013853A1 - Procede de production d'une membrane semi-permeable - Google Patents

Procede de production d'une membrane semi-permeable Download PDF

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Publication number
WO1993013853A1
WO1993013853A1 PCT/JP1993/000047 JP9300047W WO9313853A1 WO 1993013853 A1 WO1993013853 A1 WO 1993013853A1 JP 9300047 W JP9300047 W JP 9300047W WO 9313853 A1 WO9313853 A1 WO 9313853A1
Authority
WO
WIPO (PCT)
Prior art keywords
solvent
semipermeable membrane
membrane
copolymer
butanol
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP1993/000047
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English (en)
Japanese (ja)
Inventor
Kiyoshi Ishii
Kouichi Masuda
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Daicel Corp
Original Assignee
Daicel Chemical Industries Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Daicel Chemical Industries Ltd filed Critical Daicel Chemical Industries Ltd
Priority to JP51043393A priority Critical patent/JP3235836B2/ja
Publication of WO1993013853A1 publication Critical patent/WO1993013853A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/40—Polymers of unsaturated acids or derivatives thereof, e.g. salts, amides, imides, nitriles, anhydrides, esters
    • B01D71/42—Polymers of nitriles, e.g. polyacrylonitrile
    • B01D71/421—Polyacrylonitrile

Definitions

  • the present invention relates to a method for producing a semipermeable membrane widely used for refining foods, pharmaceuticals, fermented products, and the like, and for treating industrial wastewater, domestic wastewater, and the like.
  • U.S. Pat. No. 3,950,257 discloses a semipermeable membrane (ultrafiltration membrane) using a copolymer of acrylonitrile and a non-electrolyte water-soluble monomer as a membrane material.
  • a semipermeable membrane (ultrafiltration membrane) using a copolymer of acrylonitrile and a non-electrolyte water-soluble monomer as a membrane material.
  • Is a food, pharmaceutical, and fermentation product because the membrane has a good balance of membrane performance, and the membrane is relatively resistant to soiling and has the property of easily removing soiling by washing. It is widely used in the fields of refining, etc., and treating industrial and domestic wastewater.
  • the membrane performance especially the permeation flux, has not yet sufficiently responded to the demands of users seeking continuous progress.
  • the present invention has been made to meet such a user's demand, and has as its object to provide a method for producing a semipermeable membrane having higher membrane performance.
  • the present inventors In producing a semipermeable membrane by the phase conversion method, the present inventors have focused on the type of solvent and the non-solvent added to the solvent, among many factors that affect the membrane performance. A systematic review was performed. As a result, they found that the use of specific solvents and non-solvents could improve the permeation flux without reducing the solute rejection of the semipermeable membrane, and completed the present invention. It is.
  • the present invention relates to a copolymer (a) of acrylonitrile and a non-electrolyte water-soluble monomer as a membrane material, wherein the acrylonitrile content is 8 0 mol% to 96.1 mol%, the copolymer (a), the solvent (b) of the copolymer (a) which is miscible with water, and the copolymer (a)
  • the non-solvent (c) is a monovalent compound having 3 to 4 carbon atoms.
  • An object of the present invention is to provide a method for producing an acrylonitrile-based semipermeable membrane characterized by using alcohol and / or a polyvalent alcohol having 4 to 14 carbon atoms. Even if it is a conventional membrane material, by applying the method of the present invention, the permeate flow rate can be reduced without decreasing the solute rejection rate of the membrane performance as compared with a conventionally obtained semipermeable membrane. A semipermeable membrane with a significantly larger bundle was obtained.
  • the copolymer (a) having an acrylonitrile content of more than 90 mol% to 96.1 mol% can be used.
  • the solvent (b) it is preferable to use dimethyl sulfoxide and zo or dimethylformamide.
  • the non-solvent (c) is selected from the group consisting of 1-butanol, 2-butanol, isobutyl alcohol and polyvalent alcohols having 7 to 14 carbon atoms. It is preferred to use at least one species selected from the group consisting of 1-butanol, 2-butanol, isobutyl alcohol and polyvalent alcohols having 7 to 11 carbon atoms. It is even more preferred to use one or more of the selected ones.
  • non-solvent (c) examples include 2-butanol, diethyl glycol, triethylene glycol, polyethylene glycol 200 and polyethylene. It is particularly preferable to use at least one member selected from the group consisting of renglycol, 300, and 2-butanol, triethylene glycol, and polyethylene glycol. It is most preferred to use one or more selected from the group consisting of call 200.
  • non-solvent (c) 1-propanol, 2-propanol, 2-butanol, triethylene glycol, and polyethylene glycol It is also possible to use at least one member selected from the group consisting of
  • the membrane material is a copolymer (a) composed of acrylonitrile and a non-electrolyte water-soluble monomer, and has an acrylonitrile content of 8%. Use from 0 mol% to 96.1 mol%.
  • the constituent monomers of this copolymer () are essentially acrylonitrile and a non-electrolyte water-soluble monomer.
  • the acrylonitrile content is a value based on the total amount of the monomers (100 mol%).
  • Non-electrolyte water-soluble monomer means that the monomer is non-electrolyte and water-soluble, When the monomer is polymerized alone, the resulting polymer becomes a water-soluble monomer.
  • Such materials include, for example, N-vinyl-12-oxazolidone, N-vinyl-12-pyrrolidone (hereinafter simply referred to as vinylpyrrolidone), and acrylic acid. , Acrylonitrile hologram, hydroxy methacrylate creature, hydroxy methacrylate create, etc.
  • the acrylonitrile content of the copolymer (a), which is a membrane material, is 80 to 96.1 mol%. As the content of water-soluble monomer in the copolymer (a) increases, the permeation flux of the resulting semipermeable membrane increases, but the mechanical strength and heat resistance of the membrane tend to decrease. Therefore, the acrylonitrile content should be 80 mol% or more. On the other hand, if the acrylonitrile content exceeds 96.1 mol%, the membrane performance of the resulting semipermeable membrane, particularly the permeation flux, is not preferred.
  • the acrylonitrile content is preferably increased within the above range, that is, more than 90 mol% to 96.1 mol%.
  • the upper limit of the acrylonitrile content in the copolymer of the membrane material is 90 mol. % (See U.S. Pat. No. 3,950,257).
  • the upper limit of acrylonitrile content in the copolymer of the film material can be extended to 96.1 mol%. .
  • the method for producing the copolymer used in the present invention is not particularly limited, but generally, a monomer mixture as a raw material is mixed in a suitable solvent with an oil-soluble radical polymerization initiator (for example, benzoyl peroxide).
  • an oil-soluble radical polymerization initiator for example, benzoyl peroxide
  • the copolymerization is carried out in the presence of azobisisobutylonitrile.
  • a commercially available acrylonitrile-based copolymer may be used as long as the acrylonitrile-based copolymer satisfies the limitation requirements of the present invention. .
  • a solvent which dissolves the copolymer (a) well and is miscible with water is used as the solvent (b) of the copolymer (a).
  • water-miscible ones are used as a coagulating liquid during film formation and as a cleaning liquid for the cleaning tank.
  • a solvent (b) examples include dimethyl sulfoxide, dimethylinoformamide, dimethyl acetate, dimethylinoles norefone, 2-pyrrolidone, and N-methyl 2-pyrrolide. Dimethyl sulfo, etc. Preference is given to xide and di- or dimethylformamide.
  • the non-solvent (c) of the copolymer (a) is one which does not dissolve the copolymer (a) but is miscible with both water and the solvent (b), and has one to three carbon atoms.
  • the use of a solvent that is miscible with both water and the solvent (b) is used to obtain a uniform cast solution, and as a coagulating solution during film formation and as a washing solution for the washing tank, and is economically safe. This is because it is desirable to use preferable water or aqueous solution.
  • monovalent alcohols having 3 to 4 carbon atoms and / or polyvalent alcohols having 4 to 14 carbon atoms makes it possible to use semi-permeable membranes obtained by conventional methods by using these. In comparison, a semipermeable membrane with almost the same or better solute rejection ratio and higher permeation flux is obtained.
  • o-Monovalent alcohol having 3 to 4 carbon atoms For example, 1-prono. Knol, 2-propanol, 1-butanol, 2-butanol (sec-butyl alcohol), i-butyl alcohol and tert_butyl alcohol.
  • polyvalent alcohols having 4 to 14 carbon atoms include diethyl glycol, triethylene glycol, dipropylene glycol, and polyether. Tile glycol 200 and Polyethylene glycol 300 and the like.
  • non-solvent (c) at least one selected from the group consisting of 1-butanol, 2-butanol, isobutyl alcohol and a polyvalent alcohol having 7 to 14 carbon atoms is used.
  • one or more selected from the group consisting of 1-butanol, 2 -butanol, isobutyl alcohol and polyvalent alcohols having 7 to 11 carbon atoms are more preferably used.
  • non-solvent (c) 1-propanol, 2-propanol, 2-butanol, triethylene glycol and polyethylene glycol 20 are used.
  • One or more members selected from the group consisting of 0 may be used.
  • an acrylonitrile-based semipermeable membrane is produced by a phase conversion method.
  • An example of the film forming process (an example relating to the production of a flat film) is as follows.
  • a solution consisting of a polymer compound, a solvent, and a non-solvent (also called an additive).
  • the conditions of each step are not particularly limited, but examples of the conditions are as follows. .
  • the concentration of the copolymer (a), which is a membrane material can be 10 to 35% by weight, but is preferably 16 to 27% by weight.
  • It is usually between 0.01 and 0.30 mm, preferably between 0.05 and 0.25 mm.
  • the present invention includes not only a method for producing a flat membrane by a phase conversion method but also a method for producing a tubular membrane or a hollow fiber membrane by a phase conversion method.
  • test piece oval shaped cm 2 After leaving sufficient wash residual solvent in the resulting film, cut out the effective membrane area 2 5 test piece oval shaped cm 2 from the membrane, mounted it circulating tester flux of pure water (abbreviated as PWP, unit: ⁇ ⁇ 2 ⁇ h ⁇ kgf ⁇ cm "2) in the effective pressure lkgf / cm 2, or, to substantially and bovine serum Arve Mi emissions (BSA concentration l OO ppm> buffer solution
  • PWP pure water
  • R ej solute rejection rate
  • PR permeation flux
  • Example 1 1-F ⁇ ° N ° 1 27 1 48 1 0 9 ⁇
  • Example 2 2 -Phthano 1 d 9 1 52 1 1 3
  • Example 3 Diethylene glycol 1 0 1 1 42 1 805 Reference example 1 Ethylene glycol 7 9 1 33 9 7 Reference example 2
  • Reference example 4 Propionic acid 80 1 34 9 8
  • Example 4 Provides Example 4 1—Pro No. 208 1 85 1 3 5 Example 5 1 One Pro No. 223 1 9 3 1 1 Example 6 1 One Pro No. 243 2 1 2 1 5 5 5 Example 7 2-Pronolone 182 1 83 1 3 3 Example 8 2-butanol 229 1 9 7 1 44 Example 9 Triethylene glycol 1 55 1 97 1 4 Example 10 0 Diethylene glycol 19 3 1 82 1 3 3 Reference Example 8 Tetra Hydro Full Free 1 3 9 1 55 1 1 3
  • Films were formed in the same manner as in Examples 4 to 10 except that the solvent was changed from DMSO to DMF, and the film performance was evaluated.
  • Table 5 shows the results.
  • the measurement results (permeation flux) of the membrane performance of the semi-permeable membrane of the example and the reference example were compared with the measurement results of the membrane performance of the semi-permeable membrane of the comparative example.
  • Table 6 shows the conversion to the permeation flux.
  • the degree of improvement of the permeation flux when permeating the BSA buffer solution was determined to be a non-solvent (additive).
  • DMF is one of the solvents for this copolymer (acrylonitrile-based copolymer) that, together with DMSO, can form a membrane with the highest permeation flux. This is clear from the results shown in Tables 5 and 6. When a semipermeable membrane was produced by the method of the present invention using DMF as a solvent, the solute rejection was generally somewhat lower than in Comparative Example 1.
  • the copolymers consist of acrylonitrile and vinyl vinyl acetate, with an acrylonitrile content of 85.7 mol%, 92.3 mol% or 98.3 mol%. 6.1 mol% of copolymer was used, and in each case the copolymer concentration was 17% by weight, the additive was 11 propanol, and the concentration was 12% by weight. Were formed in the same manner as in Examples 1 to 10, and the film performance was evaluated. Table 7 shows the results.
  • the semipermeable membrane obtained by the method of the present invention is small.
  • the effect of improving the membrane performance of the permeable membrane is obvious.
  • a polymer solution (cast solution) having the same composition as that used in Example 1 was continuously applied to the inner surface of a polyester nonwoven fabric cylinder having an inner diameter of 14.6 mm to a thickness of about 0.15 mm. After coating, it was immersed in water at about 25 ° C to form a continuously formed tubular membrane.c From this tubular membrane, a flat membrane with the same dimensions and the same shape as in Example 1 was cut out. The film was mounted on the same device as in Example 1, and the membrane performance was evaluated. As a comparative example, a film was formed in the same manner as in Example 21 except that a polymer solution (cast liquid) having the same composition as that used in Comparative Example 1 was used. The film performance was evaluated. Table 9 shows the results.
  • the semipermeable membrane obtained by the method of the present invention showed significantly better performance than the semipermeable membrane obtained by the conventional formulation.
  • the cast liquid is continuously extruded from a cylindrical orifice (between the inner tube and the outer tube) of a double-tube nozzle into a cylindrical shape, and water at approximately 40 ° C is discharged.
  • the hollow fiber membrane having an inner diameter of 0.52 mm and an outer diameter of 0.78 mm was spun.
  • water was continuously extruded from the central orifice as the core liquid.
  • the obtained hollow fiber membrane is cut to a length of 20 cm to form a sample, and an injection needle connected to a pipe for circulating a test solution is inserted into both ends thereof, and the sample and the injection needle are rapidly cured.
  • the membrane performance was measured by the internal pressure method after sealing with a flexible epoxy adhesive. Table 11 shows the results.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)

Abstract

Procédé de production d'une membrane semi-perméable trouvant une large utilisation dans la purification d'aliments, de produits pharmaceutiques, de produits de fermentation etc., et dans le traitement d'effluents industriels, d'effluents ménagers etc., lequel procédé permet d'obtenir une membrane semi-perméable présentant un rendement relativement élevé comparé aux membranes produites par des procédés classiques, et lequel peut repousser la limite supérieure de la teneur en acrylonitrile dans un copolymère d'acrylonitrile destiné à être utilisé comme matière de membrane jusqu'à 96,1 mol %. Ce procédé consiste à produire une membrane semi-perméable par conversion en phase à partir d'une solution de coulage comprenant un copolymère d'acrylonitrile avec un monomère non électrolytique hydrosoluble ayant une teneur en acrylonitrile comprise entre 80 et 96,1 mol % à titre de matière de membrane, un solvant hydromiscible ainsi qu'un non-solvant miscible à la fois dans l'eau et dans le solvant prévus à cet effet, ledit non-solvant étant un alcool monovalent C3 ou C4 et/ou un alcool polyvalent C4 à C14.
PCT/JP1993/000047 1992-01-16 1993-01-14 Procede de production d'une membrane semi-permeable Ceased WO1993013853A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP51043393A JP3235836B2 (ja) 1992-01-16 1993-01-14 半透膜の製造方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP540792 1992-01-16
JP4/5407 1992-01-16

Publications (1)

Publication Number Publication Date
WO1993013853A1 true WO1993013853A1 (fr) 1993-07-22

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PCT/JP1993/000047 Ceased WO1993013853A1 (fr) 1992-01-16 1993-01-14 Procede de production d'une membrane semi-permeable

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JP (1) JP3235836B2 (fr)
WO (1) WO1993013853A1 (fr)

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5651209A (en) * 1979-10-02 1981-05-08 Japan Exlan Co Ltd Manufacture of acrylonitrile-based hollow fiber semipermeable membrane
JPS5888010A (ja) * 1981-11-18 1983-05-26 Toyobo Co Ltd アクリルニトリル系分離膜の製造方法

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5651209A (en) * 1979-10-02 1981-05-08 Japan Exlan Co Ltd Manufacture of acrylonitrile-based hollow fiber semipermeable membrane
JPS5888010A (ja) * 1981-11-18 1983-05-26 Toyobo Co Ltd アクリルニトリル系分離膜の製造方法

Also Published As

Publication number Publication date
JP3235836B2 (ja) 2001-12-04

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