KR20150069422A - Cellulosic membrane for water treatment with good anti-fouling property and Method thereof - Google Patents
Cellulosic membrane for water treatment with good anti-fouling property and Method thereof Download PDFInfo
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- KR20150069422A KR20150069422A KR1020130155805A KR20130155805A KR20150069422A KR 20150069422 A KR20150069422 A KR 20150069422A KR 1020130155805 A KR1020130155805 A KR 1020130155805A KR 20130155805 A KR20130155805 A KR 20130155805A KR 20150069422 A KR20150069422 A KR 20150069422A
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- South Korea
- Prior art keywords
- solvent
- support layer
- forming
- coating layer
- cellulose
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- 238000000034 method Methods 0.000 title claims abstract description 52
- 239000012528 membrane Substances 0.000 title claims abstract description 44
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 230000003373 anti-fouling effect Effects 0.000 title 1
- 239000010410 layer Substances 0.000 claims abstract description 99
- 239000002904 solvent Substances 0.000 claims abstract description 76
- 239000011247 coating layer Substances 0.000 claims abstract description 65
- 229920000642 polymer Polymers 0.000 claims abstract description 46
- 238000005191 phase separation Methods 0.000 claims abstract description 40
- 229920002678 cellulose Polymers 0.000 claims abstract description 28
- 229920000609 methyl cellulose Polymers 0.000 claims abstract description 28
- 239000001923 methylcellulose Substances 0.000 claims abstract description 28
- 235000010981 methylcellulose Nutrition 0.000 claims abstract description 28
- 238000004519 manufacturing process Methods 0.000 claims abstract description 21
- 239000000203 mixture Substances 0.000 claims abstract description 19
- 239000000080 wetting agent Substances 0.000 claims abstract description 19
- 239000003085 diluting agent Substances 0.000 claims abstract description 18
- 239000001913 cellulose Substances 0.000 claims abstract description 17
- 238000000926 separation method Methods 0.000 claims abstract description 16
- 238000011109 contamination Methods 0.000 claims abstract description 4
- 239000012510 hollow fiber Substances 0.000 claims description 22
- 239000011148 porous material Substances 0.000 claims description 19
- 230000035699 permeability Effects 0.000 claims description 13
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- 239000011248 coating agent Substances 0.000 claims description 7
- 238000000576 coating method Methods 0.000 claims description 7
- 238000009987 spinning Methods 0.000 claims description 7
- 230000001112 coagulating effect Effects 0.000 claims description 5
- 229920002301 cellulose acetate Polymers 0.000 claims description 4
- 239000000654 additive Substances 0.000 claims description 3
- 230000000996 additive effect Effects 0.000 claims description 3
- 125000000896 monocarboxylic acid group Chemical group 0.000 claims description 3
- 229920008347 Cellulose acetate propionate Polymers 0.000 claims description 2
- DQEFEBPAPFSJLV-UHFFFAOYSA-N Cellulose propionate Chemical compound CCC(=O)OCC1OC(OC(=O)CC)C(OC(=O)CC)C(OC(=O)CC)C1OC1C(OC(=O)CC)C(OC(=O)CC)C(OC(=O)CC)C(COC(=O)CC)O1 DQEFEBPAPFSJLV-UHFFFAOYSA-N 0.000 claims description 2
- 229920002284 Cellulose triacetate Polymers 0.000 claims description 2
- 239000000020 Nitrocellulose Substances 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 claims description 2
- FJWGYAHXMCUOOM-QHOUIDNNSA-N [(2s,3r,4s,5r,6r)-2-[(2r,3r,4s,5r,6s)-4,5-dinitrooxy-2-(nitrooxymethyl)-6-[(2r,3r,4s,5r,6s)-4,5,6-trinitrooxy-2-(nitrooxymethyl)oxan-3-yl]oxyoxan-3-yl]oxy-3,5-dinitrooxy-6-(nitrooxymethyl)oxan-4-yl] nitrate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O)O[C@H]1[C@@H]([C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@@H](CO[N+]([O-])=O)O1)O[N+]([O-])=O)CO[N+](=O)[O-])[C@@H]1[C@@H](CO[N+]([O-])=O)O[C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O FJWGYAHXMCUOOM-QHOUIDNNSA-N 0.000 claims description 2
- 229920006217 cellulose acetate butyrate Polymers 0.000 claims description 2
- 229920006218 cellulose propionate Polymers 0.000 claims description 2
- 150000002334 glycols Chemical class 0.000 claims description 2
- 229920001220 nitrocellulos Polymers 0.000 claims description 2
- 150000007524 organic acids Chemical class 0.000 claims description 2
- 235000005985 organic acids Nutrition 0.000 claims description 2
- 239000002798 polar solvent Substances 0.000 claims description 2
- 150000005846 sugar alcohols Chemical class 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims 1
- 229910052698 phosphorus Inorganic materials 0.000 claims 1
- 239000011574 phosphorus Substances 0.000 claims 1
- 238000002145 thermally induced phase separation Methods 0.000 abstract description 5
- 229920003086 cellulose ether Polymers 0.000 abstract 1
- 230000004907 flux Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 53
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 12
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- 235000011187 glycerol Nutrition 0.000 description 6
- 230000006698 induction Effects 0.000 description 6
- 230000000704 physical effect Effects 0.000 description 5
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 229920001477 hydrophilic polymer Polymers 0.000 description 4
- 230000002209 hydrophobic effect Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 108091003079 Bovine Serum Albumin Proteins 0.000 description 3
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 125000002252 acyl group Chemical group 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 229940098773 bovine serum albumin Drugs 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- -1 ethyl ketone Chemical compound 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 230000005012 migration Effects 0.000 description 3
- 238000013508 migration Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 229920006125 amorphous polymer Polymers 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229920003174 cellulose-based polymer Polymers 0.000 description 2
- 238000005345 coagulation Methods 0.000 description 2
- 230000015271 coagulation Effects 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- FBSAITBEAPNWJG-UHFFFAOYSA-N dimethyl phthalate Natural products CC(=O)OC1=CC=CC=C1OC(C)=O FBSAITBEAPNWJG-UHFFFAOYSA-N 0.000 description 2
- 229960001826 dimethylphthalate Drugs 0.000 description 2
- 239000002019 doping agent Substances 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- TVXBFESIOXBWNM-UHFFFAOYSA-N Xylitol Natural products OCCC(O)C(O)C(O)CCO TVXBFESIOXBWNM-UHFFFAOYSA-N 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 150000003997 cyclic ketones Chemical class 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000010612 desalination reaction Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000003094 microcapsule Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920005597 polymer membrane Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 239000000811 xylitol Substances 0.000 description 1
- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 description 1
- 235000010447 xylitol Nutrition 0.000 description 1
- 229960002675 xylitol Drugs 0.000 description 1
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Classifications
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- 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
- B01D71/08—Polysaccharides
- B01D71/12—Cellulose derivatives
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D65/00—Accessories or auxiliary operations, in general, for separation processes or apparatus using semi-permeable membranes
- B01D65/08—Prevention of membrane fouling or of concentration polarisation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
- B01D67/0016—Coagulation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
- B01D67/0018—Thermally induced processes [TIPS]
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/08—Hollow fibre membranes
- B01D69/087—Details relating to the spinning process
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/10—Supported membranes; Membrane supports
- B01D69/107—Organic support material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
- B01D69/1213—Laminated layers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
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- B01D69/12—Composite membranes; Ultra-thin membranes
- B01D69/1216—Three or more layers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
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- B01D71/06—Organic material
- B01D71/08—Polysaccharides
- B01D71/12—Cellulose derivatives
- B01D71/14—Esters of organic acids
- B01D71/16—Cellulose acetate
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- 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
- B01D71/08—Polysaccharides
- B01D71/12—Cellulose derivatives
- B01D71/20—Esters of inorganic acids, e.g. cellulose nitrate
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/24—Mechanical properties, e.g. strength
Abstract
Description
본 발명은 지지층 및 지지층의 일면 또는 양면에 형성된 코팅층을 일체형으로 구비한 셀룰로스계 수처리 분리막 및 이의 제조방법에 관한 것이다.
The present invention relates to a cellulosic water treatment separator having a support layer and a coating layer integrally formed on one or both sides of a support layer, and a method for producing the same.
분리막은 수자원 확보 측면에서 매우 유용한 기술로 주목을 받고 있다. 특히, 다공성 분리막의 경우에는 기술적 발전이 많이 이루어졌으며 상용화에도 성공하여 많이 사용되고 있다.Membrane is attracting attention as a very useful technology in terms of securing water resources. Particularly, in the case of a porous separator, technical progress has been made, and commercialization has been successful.
대부분의 분리막 특히 중공사막의 경우, 물리적 특성 (인장강도)을 높이기 위하여 소수성 분리막을 사용하였으나, 막오염에 취약점이 있다. 현재 상용화된 중공사 분리막 중 가장 내오염성이 우수한 소재는 셀룰로스 아세테이트, 폴리에테르술폰, 폴리아크릴로니트릴 등이 있으며, 이 중에서도 가장 친수성이 우수한 셀룰로스 아세테이트가 가장 내오염성이 우수한 것으로 알려져 있다. Most membranes, especially hollow membranes, use hydrophobic membranes to increase their physical properties (tensile strength), but they are vulnerable to membrane contamination. Among the commercially available hollow fiber membranes, cellulose acetate, polyethersulfone, polyacrylonitrile, and the like are the most resistant to contamination. Of these, cellulose acetate having the highest hydrophilicity is known to have the highest stain resistance.
한편, 열유도 상분리법은 상온에서는 서로 섞이지 않는 고분자와 희석제를 가열하여 균일액으로 용융 혼합한 후 성형하고, 적당한 조건에 따라 냉각하여 상분리를 유도한 후 사용하였던 희석제를 추출함으로써, 다공성 구조를 얻는 방법이다. 열유도 상분리법은 분리막 제조시 고분자의 농도를 높일 수 있어서 비용매유도상분리법 보다 기계적 강도가 월등히 향상될 수 있다. 또한, 열유도 상분리법에 의하면 비용매유도 상분리법보다 구조조절이 용이하다.On the other hand, in the heat-induced phase separation method, the polymer and diluent which are not mixed with each other at room temperature are heated and melted and mixed with a homogeneous liquid, and the mixture is cooled under appropriate conditions to induce phase separation. Method. The thermally induced phase separation method can increase the concentration of the polymer in the preparation of the separator, and thus the mechanical strength can be significantly improved as compared with the non-solvent based phase separation method. According to the heat-induced phase separation method, it is easier to control the structure than the non-solvent-induced phase separation method.
비용매유도 상분리법은 고분자 용액이 비용매와 접촉에 의해 용매가 추출되며 상분리를 일으키는 공정으로서, 고분자 용액내의 용매와 비용매의 교환에 의한 고분자의 침전을 이용하는 것이다. 열유도 상분리법과 비교하여 제조공정이 간단하여 평판형 분리막 제조시 일반적으로 많이 이용하는 기술이다. 고분자를 적정 용매에 용해시켜 만든 고분자 용액을 성형한 후 이를 비용매가 들어있는 응고조에 침전시키면, 고분자 용액내의 용매가 추출되며 고분자는 매트릭스를 형성하고 용매는 제거되어 기공을 형성하게 된다.
The non-solvent-derived phase separation method is a process in which a polymer solution extracts a solvent by contacting with a non-solvent and causes phase separation, and uses a precipitation of a polymer by exchanging a solvent and a non-solvent in the polymer solution. Compared with the heat-induced phase separation method, the manufacturing process is simple, and thus it is a technique commonly used in the manufacture of a flat plate type separator. When a polymer solution prepared by dissolving a polymer in an appropriate solvent is formed and precipitated in a coagulation tank containing a non-solvent, the solvent in the polymer solution is extracted, the polymer forms a matrix, and the solvent is removed to form pores.
친수성 소재들은 결정성이 없어서 열유도상분리법을 이용하여 분리막 제조시 기공형성이 어려운 문제가 있다. 따라서, 친수성 소재들은 비용매유도 상분리법을 이용하여 제조되고 있다. 그러나, 비용매유도 상분리법을 이용하여 중공사막을 제조할 경우 물성이 약하고 투과율도 떨어지는 단점이 있다. Since hydrophilic materials have no crystallinity, there is a problem that pore formation is difficult in the production of a separator using a heat induction phase separation method. Thus, hydrophilic materials have been prepared using the non-solvent-derived phase separation method. However, when the hollow fiber membrane is manufactured using the non-solvent-derived phase separation method, the physical properties are poor and the transmittance is also low.
한편, 기계적인 내구성이 우수하면서도 기공제어가 용이한 분리막을 제조하기 위해, 열유도 상분리법과 비용매유도 상분리법을 결합한 새로운 방법들이 제시되고 있다. 이러한 결합법들은 모두 결정성을 갖는 소수성 분리막에 적용되고 있는데, 열유도 상분리법 이용시 큰 기공들이 형성되어 코팅층 코팅이 원활히 이루어지기 때문이다. 반면에, 무정형의 친수성 고분자들은 열유도 상분리법을 이용할 경우 기공 형성이 어려워서 코팅층 코팅이 어려워진다. On the other hand, new methods combining heat-induced phase separation and non-solvent-induced phase separation have been proposed to produce a separator having excellent mechanical durability and easy pore control. All of these bonding methods are applied to crystalline hydrophobic membranes because of the formation of large pores when the thermally induced phase separation method is used to smoothly coat the coating layer. On the other hand, amorphous hydrophilic polymers are difficult to form pores when using the heat-induced phase separation method, which makes coating layer coating difficult.
따라서, 분리막의 물성을 극대화하기 위하여 즉, 인장강도가 높으면서도 기공크기가 작은 특성을 갖는 중공사 분리막은 주로 소수성 분리막을 이용하여 이루어졌으며, 친수성 고분자를 이용한 고강도의 작은 기공을 가지면서도 투과유량이 높은 분리막은 아직까지 제조가 되지 않고 있다.
Therefore, in order to maximize the physical properties of the membrane, a hollow membrane having a high tensile strength and a small pore size is mainly made of a hydrophobic membrane, and has a high strength small pore using a hydrophilic polymer, High separation membranes have not yet been manufactured.
본 발명의 목적은 인장강도가 높으면서도 내오염성이 우수한 셀룰로스계 분리막 및 이의 제조방법을 제공하는 것이다.
An object of the present invention is to provide a cellulose-based separator having high tensile strength and excellent stain resistance and a method for producing the same.
본 발명의 제1 양태는 아세틸화된 메틸 셀룰로스 고분자; 희석제; 습윤제; 및 용매를 함유하는 지지층 형성용 도프용액;; 및 아세틸화된 메틸 셀룰로스 고분자; 셀룰로스 에스테르; 및 용매, 빈용매 또는 이의 혼합물을 함유하는 코팅층 형성용 도프용액;;을 구비한 셀룰로스계 수처리 분리막 제조용 키트를 제공한다.A first aspect of the present invention relates to a method for producing a microcapsule comprising an acetylated methyl cellulose polymer; diluent; Wetting agents; And a solvent; And acetylated methyl cellulose polymers; Cellulose esters; And a dope solution for forming a coating layer containing a solvent, a poor solvent or a mixture thereof; and a kit for preparing a cellulose water treatment separation membrane.
본 발명의 제2 양태는 지지층 및 지지층의 일면 또는 양면에 형성된 코팅층을 일체형으로 구비한 셀룰로스계 수처리 분리막 제조방법에 있어서, 아세틸화된 메틸 셀룰로스 고분자; 희석제; 습윤제; 및 용매를 함유하는 지지층 형성용 도프용액을 사용하여 열유도 상분리법으로 지지층을 형성시키는 제1단계; 및 아세틸화된 메틸 셀룰로스 고분자; 셀룰로스 에스테르; 및 용매, 빈용매 또는 이의 혼합물을 함유하는 코팅층 형성용 도프용액을 사용하여 비용매유도 상분리법으로 상기 지지층 상에 코팅층을 형성시키는 제2단계를 포함하는 것이 특징인 제조방법을 제공한다.In a second aspect of the present invention, there is provided a process for producing a cellulose-based water treatment separation membrane comprising a support layer and a coating layer integrally formed on one or both surfaces of a support layer, diluent; Wetting agents; A first step of forming a support layer by a heat induced phase separation method using a dope solution for forming a support layer containing a solvent; And acetylated methyl cellulose polymers; Cellulose esters; And a second step of forming a coating layer on the support layer by a non-solvent-derived phase separation method using a dope solution for forming a coating layer containing a solvent, a poor solvent or a mixture thereof.
본 발명의 제3 양태는 지지층 및 지지층의 일면 또는 양면에 형성된 코팅층을 일체형으로 구비한 셀룰로스계 수처리 분리막에 있어서, 지지층은 아세틸화된 메틸 셀룰로스 고분자; 희석제; 습윤제; 및 용매를 함유하는 지지층 형성용 도프용액을 이용하여 열유도 상분리법으로 형성된 것이고, 코팅층은 아세틸화된 메틸 셀룰로스 고분자; 셀룰로스 에스테르; 및 용매, 빈용매 또는 이의 혼합물을 함유하는 코팅층 형성용 도프용액을 이용하여 비용매유도 상분리법으로 형성되는 것으로, 지지층의 표면 기공들 내부에도 코팅되어 지지층과 일체형으로 연속적인 코팅층을 형성하는 것이 특징인 수처리 분리막을 제공한다.The third aspect of the present invention is a cellulosic water treatment separator comprising a support layer and a coating layer integrally formed on one or both surfaces of the support layer, wherein the support layer comprises an acetylated methyl cellulose polymer; diluent; Wetting agents; And a heat-induced phase separation method using a dope solution for forming a support layer containing a solvent, wherein the coating layer comprises an acetylated methyl cellulose polymer; Cellulose esters; And a non-solvent-derived phase separation method using a dope solution for forming a coating layer containing a solvent, a poor solvent or a mixture thereof, and is also coated inside the surface pores of the support layer to form a continuous coating layer integral with the support layer In water treatment separator.
본 발명에 따른 셀룰로스계 수처리 분리막 제조용 키트 및 제조방법은 평막에도 적용될 수 있으나, 바람직하게는 중공사막에 적용될 수 있다.
The kit for manufacturing a cellulose-based water treatment membrane according to the present invention and the manufacturing method thereof may be applied to a flat membrane, but may preferably be applied to a hollow fiber membrane.
이하, 본 발명을 자세히 설명한다.
Hereinafter, the present invention will be described in detail.
본 발명에 따른 셀룰로스계 수처리 분리막은 지지체층 및 상기 지지체층 상에 코팅된 활성층을 구비한다. 상기 활성층은 수처리가 이루어지는 층일 수 있다. 이하, 본 발명에서 코팅된 활성층과 코팅층은 혼용하여 사용되고 있다.
The cellulose-based water treatment separation membrane according to the present invention comprises a support layer and an active layer coated on the support layer. The active layer may be a layer in which water treatment is performed. Hereinafter, the coated active layer and the coating layer are used in combination in the present invention.
열유도 상분리법을 이용할 경우, 결정성 고분자 분리막은 강도가 높으면서도 기공이 커지는 현상이 있고, 무정형 고분자 분리막은 강도가 높으면서도 기공이 작아지는 현상이 발생한다. 무정형 고분자를 이용하여, 열유도 상분리법으로 지지층을 형성하고 비용매유도 상분리법으로 코팅을 할 경우 코팅이 이루어지지 않는 경향이 있는데, 이는 열유도 상분리법으로 지지층을 제조할 경우 기공이 너무 작아서 코팅이 이루어지지 않아 각 층이 독립적으로 되며 일체형이 이루어지지 않는다. When the heat-induced phase separation method is used, there is a phenomenon that the crystalline polymer membrane has a high porosity and a large porosity, and the amorphous polymer separator has a high strength and a small porosity. When the support layer is formed by the thermal induction phase separation method using the amorphous polymer and the coating is performed by the non-solvent induction phase separation method, the coating tends not to be performed because the pore is too small when the support layer is produced by the heat induction phase separation method So that each layer is independent and not integrated.
내오염성을 위해 무정형의 친수성 고분자들을 이용하여 분리막 제조시, 열유도 상분리법으로 지지층을 형성할 때 기공크기가 작아 비용매유도 상분리법으로 코팅층 형성이 어려워지는 문제점을 해결하기 위해, 본 발명은 지지층 형성용 도프용액에 습윤제, 바람직하게는 OH 또는 COOH가 2개 이상인 친수성 첨가제를 함유시키는 것이 특징이다. 습윤제 함유 지지층 형성용 도프용액으로 지지층 형성시, 지지층의 기공이 작더라도 코팅층 도프용액이 지지층 표면을 코팅할 수 있게 한다는 것을 발견하였으며, 본 발명은 이에 기초한 것이다. In order to solve the problem of forming a coating layer by the non-solvent-derived phase separation method due to the small pore size when the support layer is formed by the heat induction phase separation method in the production of the separator using amorphous hydrophilic polymers for the stain resistance, It is characterized in that a hydrophilic additive having two or more wetting agents, preferably OH or COOH, is contained in the forming dope solution. It has been found that, even when the support layer is formed of the support layer with the dope solution for forming the wetting agent-containing support layer, the coating layer doping solution can coat the surface of the support layer even if the pores of the support layer are small.
본 발명에 따라 지지층 및 지지층의 일면 또는 양면에 형성된 코팅층을 일체형으로 구비한 셀룰로스계 수처리 분리막은, 지지층은 아세틸화된 메틸 셀룰로스 고분자; 희석제; 습윤제; 및 용매를 함유하는 지지층 형성용 도프용액을 이용하여 열유도 상분리법으로 형성된 것이고, 코팅층은 아세틸화된 메틸 셀룰로스 고분자; 셀룰로스 에스테르; 및 용매, 빈용매 또는 이의 혼합물을 함유하는 코팅층 형성용 도프용액을 이용하여 비용매유도 상분리법으로 형성되는 것으로, 지지층의 표면 기공들 내부에도 코팅되어 지지층과 일체형으로 연속적인 코팅층을 형성한다.
According to the present invention, a cellulose-based water treatment separator comprising a support layer and a coating layer integrally formed on one or both surfaces of the support layer, wherein the support layer comprises an acetylated methyl cellulose polymer; diluent; Wetting agents; And a heat-induced phase separation method using a dope solution for forming a support layer containing a solvent, wherein the coating layer comprises an acetylated methyl cellulose polymer; Cellulose esters; And a non-solvent-derived phase separation method using a dope solution for forming a coating layer containing a solvent, a poor solvent or a mixture thereof, and is also coated inside the surface pores of the support layer to form a continuous coating layer integrally with the support layer.
본 발명에서 사용되는 셀룰로스계 고분자는 하기와 같은 화학식 1의 구조를 갖는 화합물일 수 있다.The cellulose-based polymer used in the present invention may be a compound having a structure represented by the following formula (1).
상기 식에서 R1, R2 및 R3는 각각 독립적으로 수소 또는 C1 -6 알킬 또는 아실(acyl)이고, n은 2 이상의 정수이다.Wherein R 1 , R 2 and R 3 are each independently hydrogen or C 1 -6 alkyl or acyl, and n is an integer of 2 or more.
바람직하게는, 상기 화학식 1에서 R1, R2 및 R3는 각각 독립적으로 수소, 메틸기, 또는 아세틸기일 수 있다.Preferably, R 1 , R 2 and R 3 in Formula 1 are each independently hydrogen, a methyl group, or an acetyl group.
R1, R2 및 R3가 모두 수소인 경우, 하기 화학식 2와 같은 셀룰로스 구조이다.When R 1 , R 2 and R 3 are all hydrogen, they are cellulose structures as shown in the following formula (2).
상기와 같은 셀룰로오스 중 -OH기의 치환 정도 및 치환기 종류에 따라서 그 구조가 달라진다.
The structure of the cellulose varies depending on the degree of substitution of the -OH group and the type of the substituent.
본 발명에서 사용되는 아세틸화된 메틸 셀룰로스 고분자의 분자량은 200,000 내지 1,000,000 Mw인 것이 바람직하다. 화학식 1에서 n은 150 내지 750의 정수인 것이 바람직하다. 200,000 이하이면 기계적 강도가 떨어지고 1,000,000 이상이면 점도가 너무 상승하여 중공사로의 성형이 어려운 문제점이 있다.The molecular weight of the acetylated methyl cellulose polymer used in the present invention is preferably 200,000 to 1,000,000 Mw. In the formula (1), n is preferably an integer of 150 to 750. If the weight average molecular weight is less than 200,000, the mechanical strength is lowered. If the molecular weight is 1,000,000 or more, the viscosity becomes too high and molding into a hollow fiber is difficult.
아세틸화된 메틸 셀룰로스 고분자는 셀룰로스 단위 유니트당, 즉 3개의 -OH기당 0.5 내지 2.5 개의 알킬기 및/또는 아실기를 갖는 것이 바람직하다. 보다 바람직하게는 1.0 내지 2.0 개의 알킬기 및/또는 아실기를 갖는 것이 바람직하다. 0.5 이하이면 수용성이 있어서 중공사 성형이 어렵고 2.5 이상이면 소수성이 높아져서 막오염이 많이 일어나는 문제점이 있다.
The acetylated methylcellulose polymer preferably has from 0.5 to 2.5 alkyl and / or acyl groups per cellulose unit, i. E. Three-OH groups. More preferably 1.0 to 2.0 alkyl groups and / or acyl groups. If it is 0.5 or less, it is water-soluble and it is difficult to form a hollow fiber. If it is 2.5 or more, the hydrophobicity is increased and the film is contaminated.
지지층 형성용 도프용액 중 아세틸화된 메틸 셀룰로스 고분자의 사용량은 15 내지 30 중량%인 것이 바람직하다. 15 중량% 미만이면 분리막의 강도가 약해지는 문제가 있고, 30 중량%를 초과하면 점도가 너무 증가하여 분리막의 제조가 어려울 수 있다.
The amount of the acetylated methyl cellulose polymer in the dopant solution for forming the support layer is preferably 15 to 30% by weight. If the amount is less than 15% by weight, the strength of the separation membrane may become weak. If the amount is more than 30% by weight, the viscosity of the separation membrane may be excessively increased.
코팅층 형성용 도프용액 중 아세틸화된 메틸 셀룰로스 고분자의 사용량은 5 내지 15 중량%인 것이 바람직하다. 5 중량% 미만이면 분리막의 강도가 약해지는 문제가 있고, 15 중량%를 초과하면 점도가 너무 증가하여 분리막의 제조가 어려울 수 있다.
The amount of the acetylated methyl cellulose polymer in the dope solution for forming the coating layer is preferably 5 to 15% by weight. If the amount is less than 5% by weight, the strength of the separation membrane may become weak. When the amount exceeds 15% by weight, the viscosity of the separation membrane may be excessively increased.
한편, 고분자를 용해시키는 용매는 용해 정도에 따라 용매, 빈용매 및 비용매로 구분할 수 있다.On the other hand, the solvent for dissolving the polymer can be divided into a solvent, a poor solvent and a non-solvent depending on the degree of dissolution.
“용매”는 약 60℃ 이하의 온도에서 5중량부 이상의 고분자를 녹일 수 있는 용매로, 아세틸화된 메틸 셀룰로스 고분자의 용매로 디메틸아세트아마이드, 디메틸포름아미드, 디메틸술폭사이드 같은 극성용매, 아세톤, 메틸에틸케톤 같은 케톤류, N-메틸피롤리돈(NMP), r-부티로락톤 같은 사이클로케톤류 등을 사용할 수 있다. The "solvent" is a solvent capable of dissolving at least 5 parts by weight of polymer at a temperature of about 60 ° C. or less. As the solvent of the acetylated methyl cellulose polymer, a polar solvent such as dimethylacetamide, dimethylformamide, dimethylsulfoxide, Ketones such as ethyl ketone, and cyclic ketones such as N-methylpyrrolidone (NMP) and r-butyrolactone.
“빈용매”는 고분자를 60℃ 이하의 저온에서는 5중량% 이상 용해시킬 수 없지만, 60℃ 이상 또는 고분자의 융점 이하의 고온 영역에서는 5중량% 이상 용해시킬 수 있는 용매로서, 아세틸화된 메틸 셀룰로스 고분자의 빈용매로 디에틸렌글리콜, 트리에틸렌글리콜 같은 에틸렌글리콜 류, 디메틸프탈레이트 같은 프탈레이트 류 등을 사용할 수 있다.The "poor solvent" can not dissolve the polymer at a low temperature of 60 ° C. or lower at 5 wt% or more, but as a solvent capable of dissolving at least 5 wt% in a high temperature region of 60 ° C. or higher or lower than the melting point of the polymer, acetylated methyl cellulose As a poor solvent for the polymer, ethylene glycol such as diethylene glycol and triethylene glycol, phthalates such as dimethyl phthalate, and the like can be used.
“비용매”는 고분자의 융점 또는 액체의 비점까지 고분자를 용해시키거나 팽윤시키지 못하는 용매로서, 아세틸화된 메틸 셀룰로스 고분자의 비용매로 물, 알콜, 에테르, 헥산 등이 있으며, 바람직하게는 물을 사용할 수 있다.The "non-solvent" is a solvent that does not dissolve or swell the polymer until the melting point of the polymer or the boiling point of the liquid. Water, alcohol, ether, and hexane may be used as the solvent for the acetylated methyl cellulose polymer, Can be used.
상기 비용매는 본 발명에서 응고욕으로 사용될 수 있다.
The non-solvent may be used as a coagulating bath in the present invention.
열유도 상분리법에서 사용되는 희석제는 상온에서는 고분자와 서로 섞이지 않으나 가열하면 균일액으로 용융 혼합가능한 액체이다. 본 발명에서 사용되는 아세틸화된 메틸 셀룰로스 고분자에 대한 희석제는 아세틸화된 메틸 셀룰로스 고분자에 대해 빈용매일 수 있으며, 이의 비제한적인 예로는 디에틸렌글리콜, 트리에틸렌글리콜 같은 에틸렌글리콜 류, 디메틸프탈레이트 같은 프탈레이트 류 등이 있다.The diluent used in the thermally induced phase separation method is a liquid which can not be mixed with the polymer at room temperature but can be melt-mixed as a homogeneous liquid when heated. The diluent for the acetylated methylcellulose polymer used in the present invention can be used as a diluent for the acetylated methylcellulose polymer, and examples thereof include ethylene glycol such as diethylene glycol and triethylene glycol, phthalate such as dimethyl phthalate And so on.
지지층 형성용 도프용액 중 희석제의 사용량은 40 내지 85 중량%인 것이 바람직하다. 40 중량% 미만이면 중공사 성형이 어려운 문제가 있고, 85 중량%를 초과하면 점도가 너무 감소하여 성형이 어려운 문제가 있다.
The amount of the diluent used in the support layer-forming dope solution is preferably 40 to 85% by weight. If the amount is less than 40% by weight, there is a problem that the hollow fiber is difficult to be molded, and when it exceeds 85% by weight, the viscosity is too small to form.
본 발명에서 지지층 형성용 도프용액은 습윤제를 함유하는 것이 특징이다.In the present invention, the dope solution for forming the support layer contains a wetting agent.
습윤제는 고-액 두 상이 접하는 경우, 표면장력을 변화시켜 두 상의 젖음의 특성을 크게 개선하기 위해 쓰이는 물질이다. 본 발명에 사용되는 습윤제는 바람직하게는 OH 또는 COOH가 2개 이상인 친수성 첨가제일 수 있으며, 이의 비제한적인 예로는 글리세린, 프로필렌글리콜 등의 글리콜류, 솔비톨, 자일리톨 등의 당알콜, 구연산, 숙신산, 옥살초산 등의 유기산이 있다. A wetting agent is a material used to significantly improve the properties of wetting of two phases by changing the surface tension when the solid-liquid phase is in contact. The wetting agent used in the present invention may preferably be a hydrophilic additive having two or more OH or COOH groups. Nonlimiting examples of the wetting agent include glycols such as glycerin and propylene glycol, sugar alcohols such as sorbitol and xylitol, citric acid, And organic acids such as acetic acid.
본 발명에서 지지층 형성용 도프용액 중 습윤제의 사용량은 5 내지 20 중량%인 것이 바람직하다. 5 중량% 미만이면 지지층과 코팅층의 접착력이 떨어지는 문제가 있고, 20 중량%를 초과하면 도프용액 제조가 어려운 문제가 있다.In the present invention, the amount of the wetting agent used in the dope solution for forming the support layer is preferably 5 to 20% by weight. If the amount is less than 5% by weight, there is a problem that the adhesive strength between the support layer and the coating layer is lowered, and when it exceeds 20% by weight, there is a problem in that it is difficult to prepare the dope solution.
본 발명의 일구체예에서는, 친수성이 높은 아세틸화된 메틸 셀룰로스 함유 분사액을 이용하여, 열유도 상분리법으로 지지층을, 비용매유도 상분리법으로 코팅층을 형성하되, 습윤제로 OH가 3개인 글리세린을 함유하는 열유도 상분리용 분사액을 사용하여, 기공크기가 작은 지지층 상에도 코팅층을 일체형으로 형성시킬 수 있었다(실시예 1 ~ 3).
In one embodiment of the present invention, a support layer is formed by a thermally induced phase separation method using a acetylated methylcellulose-containing injection liquid having high hydrophilicity, a coating layer is formed by a non-solvent-derived phase separation method, glycerin having three OHs as a wetting agent The coating layer could be integrally formed on the support layer having a small pore size by using the spray for heat-induced phase separation (Examples 1 to 3).
코팅층과 지지층이 동시에 방사되면서 화학적으로 결합시키기 위해, 본 발명에 따른 지지층 형성용 도프용액은 용매를 함유한다. 지지층 형성용 도프용액에 용매 없이 희석제만 사용하면, 지지체의 기공이 커질뿐아니라 지지층과 코팅층간의 일체도도 떨어진다(비교예 1-2 참조).To chemically bond the coating layer and the support layer simultaneously while spinning, the dope solution for forming the support layer according to the present invention contains a solvent. When only the diluent is used in the dope solution for forming the support layer, not only the pores of the support are increased but also the degree of integration between the support layer and the coating layer is low (see Comparative Example 1-2).
본 발명에서 지지층 형성용 도프용액 중 용매의 사용량은 10 내지 30 중량%인 것이 바람직하다. 10중량% 이하이면 접척력이 떨어지고 30중량% 이상이면 중공사 성형이 어려운 문제가 있다.
In the present invention, the amount of the solvent used in the dopant solution for forming the support layer is preferably 10 to 30% by weight. If it is 10% by weight or less, the contact force is decreased. If it is 30% by weight or more, there is a problem that hollow fiber molding is difficult.
또한, 본 발명에서 코팅층 형성용 도프용액은 셀룰로스 에스테르(cellulose esters)를 함유하는 것이 바람직하다. 셀룰로스 에스테르와 아세틸화된 메틸 셀룰로스를 동시에 사용함으로서 내구성이 향상된다. 셀룰로스 에스테르의 비제한적인 예로는 셀룰로스 아세테이트, 셀룰로스 트리아세테이트, 셀룰로스 프로피오네이트, 셀룰로스 아세테이트 부티레이트, 셀룰로스 아세테이트 프로피오네이트, 셀룰로스 나이트레이트, 셀룰로스 설페이트, 이의 혼합물 등이 있다.Further, in the present invention, the dope solution for forming the coating layer preferably contains cellulose esters. Durability is improved by using cellulose ester and acetylated methyl cellulose simultaneously. Non-limiting examples of cellulosic esters include cellulose acetate, cellulose triacetate, cellulose propionate, cellulose acetate butyrate, cellulose acetate propionate, cellulose nitrate, cellulose sulfate, mixtures thereof, and the like.
본 발명에서 코팅층 형성용 도프용액 중 셀룰로스 에스테르의 사용량은 2 내지 10 중량%인 것이 바람직하다. 2 중량% 미만이면 내구성이 떨어지는 문제가 있고, 10 중량%를 초과하면 투과유량이 감소하는 문제가 있다.
In the present invention, the amount of the cellulose ester used in the coating solution for forming the coating layer is preferably 2 to 10% by weight. If the amount is less than 2% by weight, durability tends to deteriorate. If the amount is more than 10% by weight, there is a problem that the permeation flow rate decreases.
본 발명에 따라 지지층 및 지지층의 일면 또는 양면에 형성된 코팅층을 일체형으로 구비한 셀룰로스계 수처리 분리막 제조방법은 본 발명에 따른 지지층 형성용 도프용액을 사용하여 열유도 상분리법으로 지지층을 형성시키는 제1단계; 및 본 발명에 따른 코팅층 형성용 도프용액을 사용하여 비용매유도 상분리법으로 상기 지지층 상에 코팅층을 형성시키는 제2단계를 포함한다. According to the present invention, there is provided a method for manufacturing a cellulose-based water treatment separation membrane having a coating layer integrally formed on one surface or both surfaces of a support layer and a support layer, comprising the steps of: a first step of forming a support layer by a heat induction phase separation method using a dope solution for forming a support layer according to the present invention ; And a second step of forming a coating layer on the support layer by a non-solvent-derived phase separation method using the dope solution for forming a coating layer according to the present invention.
응고욕에는 본 발명에서 사용하는 아세틸화된 메틸 셀룰로스 고분자의 비용매를 사용할 수 있다.As the coagulating bath, a non-solvent of the acetylated methyl cellulose polymer used in the present invention can be used.
분리막 제조시, 노즐과 홀형성제를 사용하여 중공사 형태의 분리막을 제조할 수 있다.In the preparation of the separator, a hollow fiber type separator can be manufactured using a nozzle and a hole forming agent.
본 발명에서 사용가능한 노즐은 홀 형성제 이동 경로, 코팅층용 도프용액 이동 경로 및 지지층용 도프용액 이동 경로를 구비할 수 있다(도 1 참조).The nozzles usable in the present invention may include a hole forming agent migration path, a dope solution migration path for the coating layer, and a dope solution migration path for the support layer (see FIG. 1).
본 발명에 따른 분리막은 외부는 지지층이, 내부는 코팅층이 위치한 것인 중공사 막 형태일 수 있다.The separation membrane according to the present invention may be in the form of a hollow fiber membrane having a support layer on the outside and a coating layer on the inside.
홀형성제는 중공사막의 내부측에 통로를 형성시키기 위해 주입시키는 액체이다. 홀형성제는 비점이 150 ∼ 210 ℃인 고비점의 양용매와 비점이 80 ∼ 290 ℃인 비용매를 혼합하여 사용하는 것이 바람직하다. 홀형성제는 응고액 조성으로 막의 고화를 늦추어 주는 물질로 첨가하면 고화가 늦어지는 만큼 공경이 자라게 되어 공경의 크기를 원하는 만큼 키울 수 있다.The hole forming agent is a liquid to be injected to form a passage on the inner side of the hollow fiber membrane. It is preferable to use a mixture of a high boiling point solvent having a boiling point of 150 to 210 ° C and a non-solvent having a boiling point of 80 to 290 ° C. When the hole forming agent is added as a material to slow down the solidification of the film by the coagulating liquid composition, the pore size increases as the solidification is delayed, and the pore size can be increased as desired.
지지층 형성용 도프용액의 방사 온도는 90 ~ 170 ℃이고, 코팅층 형성용 도프용액의 방사 온도는 10 ~ 100 ℃이고, 응고욕의 온도는 5 ~ 60 ℃ 것이 바람직하다. 홀 형성제의 온도는 20 ~ 100 ℃인 것이 바람직하다.
It is preferable that the spinning temperature of the dope solution for forming the support layer is 90 to 170 캜, the spinning temperature of the dope solution for forming the coating layer is 10 to 100 캜, and the temperature of the coagulating bath is 5 to 60 캜. The temperature of the hole forming agent is preferably 20 to 100 ° C.
본 발명은 노즐을 이용하여 홀 형성제, 코팅층 도프용액, 및 지지층 도프용액을 동시에 방사하여 제1단계 및 제2단계를 동시에 수행하는 것이 바람직하다. 동시에 수행하지 않으면 코팅층과 지지층의 결합이 용이하지 않고 또한 공정도 복잡하여 어려운 점이 있다.
The present invention preferably simultaneously performs the first step and the second step by simultaneously spinning the hole forming agent, the coating layer doping solution, and the supporting layer doping solution using the nozzle. There is a drawback in that the bonding of the coating layer and the support layer is not easy and the process is complicated.
본 발명에 따른 분리막은 친수성 고분자를 활용하여 물성이 매우 우수하면서도 내오염성이 탁월하여 수처리용 공정에 매우 적합하다. 예컨대 정수기, 해수담수화 공정의 전처리 장치, 연수기, 정수처리 장치, 폐수 처리 장치 또는 식품 정제장치 등에 사용할 수 있다. The separation membrane according to the present invention utilizes a hydrophilic polymer and is excellent in physical properties and excellent in stain resistance, and thus is suitable for a water treatment process. For example, a water purifier, a pretreatment device for a seawater desalination process, a water softener, a water treatment device, a wastewater treatment device, or a food purification device.
한편, 본 발명에 따른 분리막은, 분획분자량은 50 ~ 500 (kDa)이고, 인장강도는 6 ~ 13 (MPa)이고, 수투과도는 200 ~ 2000 (L/m2hr)이고, 내오염도는 0.4 ~ 0.8 이고, 일체도는 2.0 ~ 6.0 kgf/cm2일 수 있다.
Meanwhile, the separation membrane according to the present invention has a fraction molecular weight of 50 to 500 (kDa), a tensile strength of 6 to 13 (MPa), a water permeability of 200 to 2000 (L / m 2 hr) To 0.8, and the integral may be 2.0 to 6.0 kgf / cm < 2 >.
본 발명은 셀룰로스계 고분자를 이용하여 열유도 상분리법과 비용매유도 상분리법을 동시에 활용하여 지지층과 코팅층이 일체형인 분리막을 제조함으로서 인장강도가 높으면서도 기공이 작고 투과유량이 높은 특성을 갖는다. 또한 기존의 소수성 소재의 분리막에 비해서 본 발명을 통해서 제조된 분리막의 경우 내오염성이 매우 우수하다.
The present invention provides a separator having an integrated support layer and a coating layer by utilizing heat-induced phase separation and a non-solvent-induced phase separation method using a cellulose-based polymer, and has a high tensile strength and a small pore size and a high permeate flow rate. In addition, the separator prepared according to the present invention has an excellent stain resistance as compared with the conventional hydrophobic separator.
도 1은 본 발명에 따른 중공사 분리막을 제조하기 위한 노즐의 단면도이다.1 is a cross-sectional view of a nozzle for manufacturing a hollow fiber membrane according to the present invention.
이하, 본 발명을 실시예를 통하여 보다 상세하게 설명한다. 그러나 이들 실시예는 본 발명을 예시적으로 설명하기 위한 것으로 본 발명의 범위가 이들 실시예에 한정되는 것은 아니다.
Hereinafter, the present invention will be described in more detail with reference to examples. However, these examples are for illustrative purposes only, and the scope of the present invention is not limited to these examples.
실시예Example 1: One: AMCAMC 고분자계Polymer system 중공사Hollow fiber 분리막 제조 Membrane manufacturing
메틸 셀룰로스 (PMA, 삼성정밀화학제품, DS:1.7)를 무수아세트산으로 아세틸화시키고 물에 고형화시켜서, 물에 용해되지 않고 유기용매에 용해되는 특성을 갖는 아세틸화된 메틸 셀룰로스(이하 AMC)를 준비하였다. Acetylated methyl cellulose (hereinafter abbreviated as AMC), which is acetylated with anhydrous acetic acid and solidified in water to have a property of being dissolved in an organic solvent without being dissolved in water, is prepared Respectively.
두가지 상분리법, 즉 지지층 제조를 위한 열유도 상분리법 및 코팅층 제조를 위한 비용매유도 상분리법을 이용하여 동시에 방사하면서 일체형의 중공사 분리막을 제조하였다.Two types of phase separation method, ie, heat - induced phase separation for supporting layer production and nonporous phase separation method for coating layer production, were simultaneously carried out to fabricate a monolithic hollow fiber membrane.
지지층용 도프용액은 AMC 25중량%, 희석제로 triethylene glycol (이하 TEG) 45중량%, 디메틸아세트아마이드 (이하 DMAc) 20중량%, 글리세린 10중량%를 포함하였다.The doping solution for the support layer contained 25% by weight of AMC, 45% by weight of triethylene glycol (TEG) as a diluent, 20% by weight of dimethylacetamide (DMAc) and 10% by weight of glycerin.
코팅층용 도프용액은 AMC 8중량%, CA 4중량%, 용매로 DMAc 78중량%, TEG 10중량%를 포함하였다.The dope solution for the coating layer contained 8% by weight of AMC, 4% by weight of CA, 78% by weight of DMAc as a solvent, and 10% by weight of TEG.
외부응고액은 물을 사용하였고 홀 형성제는 TEG/DMAc (70/30 중량%)를 사용하였다. 지지층용 도프용액의 온도는 140도, 코팅용액의 온도는 50도, 홀 형성제의 온도는 70도를 유지하였다.
Water was used as the external coagulation solution and TEG / DMAc (70/30 wt%) was used as the hole forming agent. The temperature of the dope solution for the support layer was maintained at 140 ° C, the temperature of the coating solution was maintained at 50 ° C, and the temperature of the hole forming agent was maintained at 70 ° C.
실험 1: 중공사막의 물성Experiment 1: Properties of Hollow Fiber Membrane
물성을 평가하기 위하여 인장강도 (MPa), 1kgf/cm2 하에서의 수투과도 (L/m2hr), 분자량이 다른 polyethylene glycol 1000ppm 용액을 이용한 제거율(HPLC 이용)을 활용한 분획분자량(kDa), 내오염성을 평가하기 위하여 bovine serum albumin (BSA) 20ppm 수용액을 이용한 1kgf/cm2 하에서의 6시간 후의 투과도 감소에 따른 상대 투과도 감소비율(-)을 사용하였다. In order to evaluate the physical properties, tensile strength (MPa), water permeability (L / m 2 hr) under 1 kgf / cm 2 , fraction molecular weight (kDa) using the removal rate (using HPLC) To evaluate the stain resistance, the relative permeability reduction ratio (-) with the reduction of permeability after 6 hours at 1 kgf / cm 2 using 20 ppm aqueous solution of bovine serum albumin (BSA) was used.
내오염성 수치는 높을수록 우수한 것이다. 즉 초기 순수투과도 대비 BSA 20ppm 용액으로 6시간 후의 수투과도를 나타낸 것이다. The higher the stain resistance value, the better. That is, the water permeability after 6 hours with 20 ppm of BSA versus initial pure water permeability is shown.
수투과도는 중공사 외부 쪽에 압력을 가하여 측정하였고 코팅층의 지지층과의 일체도 (kgf/cm2)는 중공사 내부에서 외부로 압력을 가하여 견딜 수 있는 압력으로 나타내었다. The water permeability was measured by applying pressure to the outside of the hollow fiber, and the integral (kgf / cm 2 ) of the coating layer with the support layer was expressed as a pressure that could withstand the external pressure from the inside of the hollow fiber.
하기 표 1은 실시예 1에서 제조된 AMC 고분자계 중공사 분리막의 결과를 나타내었다.Table 1 below shows the results of the AMC polymer hollow fiber membrane prepared in Example 1.
비교예Comparative Example 1: One: 도프용액의Of the dope solution 조성에 따른 성능 Performance by composition
하기와 같이 지지층용 도프용액의 조성을 변화시킨 것을 제외하고는, 실시예 1과 동일한 방법으로 AMC 고분자계 중공사 분리막을 제조하였다. The AMC polymer hollow fiber membrane was prepared in the same manner as in Example 1, except that the composition of the dope solution for the support layer was changed as described below.
비교예 1-1의 경우, 지지층용 도프용액의 조성은 AMC 25중량%, TEG 55중량%, DMAc 20중량%이었고, 코팅층용 도프용액은 실시예 1과 동일하였다.In the case of Comparative Example 1-1, the composition of the doping solution for the support layer was 25% by weight of AMC, 55% by weight of TEG and 20% by weight of DMAc, and the dope solution for the coating layer was the same as in Example 1.
비교예 1-2의 경우, 지지층용 도프용액의 조성은 AMC 25중량%, TEG 65중량%, 글리세린 10중량%이었고, 코팅층용 도프용액은 실시예 1과 동일하였다.In the case of Comparative Example 1-2, the composition of the doping solution for the support layer was 25% by weight of AMC, 65% by weight of TEG and 10% by weight of glycerin, and the dope solution for the coating layer was the same as in Example 1.
비교예 1-3의 경우, 지지층용 도프용액은 실시예 1과 동일하였고, 코팅층용 도프용액의 조성은 AMC 12중량%, DMAc 78중량%, TEG 10중량%이었다.In the case of Comparative Examples 1-3, the doping solution for the support layer was the same as that of Example 1, and the composition of the coating solution for the coating layer was 12% by weight of AMC, 78% by weight of DMAc and 10% by weight of TEG.
비교예 1에 따라 제조된 AMC 고분자계 중공사 분리막의 물성을 표 2에 나타내었다.The properties of the AMC polymer hollow fiber membrane prepared according to Comparative Example 1 are shown in Table 2.
비교예 1-1은 지지층 도프용액에서 글리세린 대신 희석제인 TEG를 추가로 더 사용하였다. 지지층과 코팅층 사이의 습윤제로서의 역할을 하는 글리세린을 제거함으로서 지지층과 코팅층의 일체도가 0.4(kgf/cm2)로 감소하였으며, 분획분자량이 5배 증가하였고, 또한 수투과도도 800(L/m2hr)으로 150(L/m2hr) 증가하였다. Comparative Example 1-1 further used TEG as a diluent instead of glycerin in the support layer doping solution. By removing glycerin, which acts as a wetting agent between the support layer and the coating layer, the integral of the support layer and the coating layer was reduced to 0.4 kgf / cm 2 , the molecular weight of the fraction was increased 5 times and the water permeability was 800 L / m 2 hr) to 150 (L / m 2 hr).
비교예 1-2는 지지층 도프용액에서 용매인 DMAc 대신 희석제인 TEG를 추가로 더 사용하였다. 지지층 도프용액에 용매인 DMAc를 사용하지 아니한 경우, 지지층과 코팅층의 일체도가 0.3(kgf/cm2)로 감소하였으며, 분획분자량이 10배 증가하였고, 수투과도도 1300(L/m2hr)으로 13배 증가하였다. In Comparative Example 1-2, TEG, which is a diluent, was used in place of DMAc as a solvent in the support layer doping solution. When the DMAc solution was not used in the support layer doping solution, the integral of the support layer and the coating layer was reduced to 0.3 kgf / cm 2 , the molecular weight of the fraction was increased by 10 times, the water permeability was 1300 (L / m 2 hr) .
비교예 1-3은 코팅층 도프용액에서 CA 대신 AMC를 더 사용하였다. 이 경우도, 지지층과 코팅층의 일체도가 0.4(kgf/cm2)로 감소하였으며, 분획분자량이 500(L/m2hr)으로 증가하였고, 수투과도도 950(L/m2hr)으로 증가하였다. In Comparative Example 1-3, AMC was used in place of CA in the coating layer doping solution. In this case, the integral of the support layer and the coating layer was reduced to 0.4 kgf / cm 2 , the fraction molecular weight increased to 500 L / m 2 hr, and the water permeability increased to 950 L / m 2 hr Respectively.
비교예에서 제조된 분리막의 경우, 일체도가 감소하며 기공의 크기가 증가함으로서 분획분자량 및 수투과도가 현저히 증가하게 되도록 하였다.
In the case of the separator prepared in the comparative example, the integral degree was decreased and the pore size was increased, so that the fraction molecular weight and water permeability were remarkably increased.
실시예Example 2 ~ 3: 지지층 용매 변화 2 ~ 3: Solvent change in support layer
실시예 1과 동일한 방법으로 실험하였으며 지지층 용매로 DMAc 대신 각각 DMF (실시예 2) 및 NMP (실시예 2)를 사용한 것을 제외하고는, 실시예 1과 동일한 방법으로 AMC 고분자계 중공사 분리막을 제조하였으며, 표 3에 그 결과를 나타내었다.An AMC polymer hollow fiber membrane was prepared in the same manner as in Example 1 except that DMF (Example 2) and NMP (Example 2) were used instead of DMAc as a support layer solvent, respectively. And the results are shown in Table 3.
실시예 2 내지 3은 용매인 DMAc를 대신하여 다른 양용매인 DMF 혹은 NMP를 사용하였다. 실시예 1과 비교하여 수투과도에서 조금 감소하였으나 분획분자량은 동일하고 일체도는 실시예 1과 비슷하였다. 또한 내오염성은 실시예 1과 비교하여 조금 나아진 값을 보였다.
In Examples 2 to 3, other two-solvent DMF or NMP was used instead of DMAc as a solvent. Although the water permeability was slightly reduced as compared with Example 1, the cutoff molecular weight was the same and the integrity was similar to that of Example 1. [ In addition, the stain resistance showed a slightly improved value as compared with Example 1.
2: 홀 형성제 이동 경로
4: 코팅층용 도프용액 이동 경로
6: 지지층용 도프용액 이동 경로 2: hole forming agent movement path
4: Dope solution movement path for coating layer
6: Dope solution movement path for supporting layer
Claims (18)
아세틸화된 메틸 셀룰로스 고분자; 셀룰로스 에스테르; 및 용매, 빈용매 또는 이의 혼합물을 함유하는 코팅층 형성용 도프용액;
을 구비한 셀룰로스계 수처리 분리막 제조용 키트.Acetylated methyl cellulose polymers; diluent; Wetting agents; And a solvent; And
Acetylated methyl cellulose polymers; Cellulose esters; And a dope solution for forming a coating layer containing a solvent, a poor solvent or a mixture thereof;
Wherein the cellulose-based water-treatment separator comprises:
The kit according to claim 1, wherein the doping solution for forming the support layer and the doping solution for forming the coating layer both use a polar solvent as a solvent.
아세틸화된 메틸 셀룰로스 고분자; 희석제; 습윤제; 및 용매를 함유하는 지지층 형성용 도프용액을 사용하여 열유도 상분리법으로 지지층을 형성시키는 제1단계; 및
아세틸화된 메틸 셀룰로스 고분자; 셀룰로스 에스테르; 및 용매, 빈용매 또는 이의 혼합물을 함유하는 코팅층 형성용 도프용액을 사용하여 비용매유도 상분리법으로 상기 지지층 상에 코팅층을 형성시키는 제2단계를 포함하는 것이 특징인 제조방법.A method for manufacturing a cellulose-based water treatment separation membrane having a support layer and a coating layer integrally formed on one surface or both surfaces of a support layer,
Acetylated methyl cellulose polymers; diluent; Wetting agents; A first step of forming a support layer by a heat induced phase separation method using a dope solution for forming a support layer containing a solvent; And
Acetylated methyl cellulose polymers; Cellulose esters; And a second step of forming a coating layer on the support layer by a non-solvent-derived phase separation method using a dope solution for forming a coating layer containing a solvent, a poor solvent or a mixture thereof.
The method according to claim 10, wherein the temperature of the hole-forming agent is 20 to 100 ° C.
지지층은 아세틸화된 메틸 셀룰로스 고분자; 희석제; 습윤제; 및 용매를 함유하는 지지층 형성용 도프용액을 이용하여 열유도 상분리법으로 형성된 것이고,
코팅층은 아세틸화된 메틸 셀룰로스 고분자; 셀룰로스 에스테르; 및 용매, 빈용매 또는 이의 혼합물을 함유하는 코팅층 형성용 도프용액을 이용하여 비용매유도 상분리법으로 형성되는 것으로, 지지층의 표면 기공들 내부에도 코팅되어 지지층과 일체형으로 연속적인 코팅층을 형성하는 것이 특징인 수처리 분리막.In a cellulose-based water treatment separator having a support layer and a coating layer integrally formed on one surface or both surfaces of the support layer,
The support layer comprises an acetylated methyl cellulose polymer; diluent; Wetting agents; And a heat-induced phase separation method using a dope solution for forming a support layer containing a solvent,
The coating layer comprises an acetylated methyl cellulose polymer; Cellulose esters; And a non-solvent-derived phase separation method using a dope solution for forming a coating layer containing a solvent, a poor solvent or a mixture thereof, and is also coated inside the surface pores of the support layer to form a continuous coating layer integral with the support layer Phosphorus treatment membrane.
14. The method of claim 13, wherein the tensile strength is from 6 to 13 MPa, the water permeability is from 200 to 2000 L / m 2 hr, the degree of contamination is from 0.4 to 0.8 and the integrity is from 2.0 to 6.0 kgf / cm 2 .
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| WO2020130674A1 (en) * | 2018-12-20 | 2020-06-25 | 롯데케미칼 주식회사 | Composition for forming filtration membrane, method for manufacturing filtration membrane by using same, and filtration membrane |
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