KR102103432B1 - Nanofiltration Composition Membrane Having Improved Acid and Heat Resistance And Manufacturing Method Thereof - Google Patents
Nanofiltration Composition Membrane Having Improved Acid and Heat Resistance And Manufacturing Method Thereof Download PDFInfo
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- KR102103432B1 KR102103432B1 KR1020180069032A KR20180069032A KR102103432B1 KR 102103432 B1 KR102103432 B1 KR 102103432B1 KR 1020180069032 A KR1020180069032 A KR 1020180069032A KR 20180069032 A KR20180069032 A KR 20180069032A KR 102103432 B1 KR102103432 B1 KR 102103432B1
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- diisocyanate
- heat resistance
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- 239000002253 acid Substances 0.000 title claims abstract description 91
- 239000012528 membrane Substances 0.000 title claims description 61
- 238000004519 manufacturing process Methods 0.000 title claims description 18
- 238000001728 nano-filtration Methods 0.000 title description 3
- -1 aliphatic diamine Chemical class 0.000 claims abstract description 47
- 150000001412 amines Chemical class 0.000 claims abstract description 35
- 239000000243 solution Substances 0.000 claims abstract description 29
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 24
- 239000007864 aqueous solution Substances 0.000 claims abstract description 22
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000012695 Interfacial polymerization Methods 0.000 claims abstract description 13
- YUDKYACWSLAJPM-UHFFFAOYSA-N butane-1,4-diamine butane-2,3-diamine Chemical compound NC(C(C)N)C.NCCCCN YUDKYACWSLAJPM-UHFFFAOYSA-N 0.000 claims abstract description 7
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims abstract description 7
- FFSWKVBKAAYGGH-UHFFFAOYSA-N pentane-1,5-diamine pentane-3,3-diamine Chemical compound NCCCCCN.NC(CC)(CC)N FFSWKVBKAAYGGH-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000000926 separation method Methods 0.000 claims description 39
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 16
- 150000002500 ions Chemical class 0.000 claims description 13
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical group CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 12
- 229920001477 hydrophilic polymer Polymers 0.000 claims description 11
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 10
- 229940008841 1,6-hexamethylene diisocyanate Drugs 0.000 claims description 8
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 8
- 239000004952 Polyamide Substances 0.000 claims description 8
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 8
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 8
- 229920002647 polyamide Polymers 0.000 claims description 8
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 8
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 8
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 8
- ALQLPWJFHRMHIU-UHFFFAOYSA-N 1,4-diisocyanatobenzene Chemical compound O=C=NC1=CC=C(N=C=O)C=C1 ALQLPWJFHRMHIU-UHFFFAOYSA-N 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 7
- RIHNBQZIPIBFRG-UHFFFAOYSA-N NCCCN.NC(=CC)N Chemical compound NCCCN.NC(=CC)N RIHNBQZIPIBFRG-UHFFFAOYSA-N 0.000 claims description 6
- 239000002202 Polyethylene glycol Substances 0.000 claims description 5
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 5
- FDQSRULYDNDXQB-UHFFFAOYSA-N benzene-1,3-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC(C(Cl)=O)=C1 FDQSRULYDNDXQB-UHFFFAOYSA-N 0.000 claims description 5
- 239000004202 carbamide Substances 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 229920001223 polyethylene glycol Polymers 0.000 claims description 5
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 5
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 claims description 5
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 4
- 230000008859 change Effects 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 2
- 230000007062 hydrolysis Effects 0.000 claims description 2
- 238000006460 hydrolysis reaction Methods 0.000 claims description 2
- 125000000524 functional group Chemical group 0.000 claims 2
- 150000002366 halogen compounds Chemical class 0.000 claims 2
- 239000012948 isocyanate Substances 0.000 claims 2
- 150000002513 isocyanates Chemical class 0.000 claims 2
- 238000005903 acid hydrolysis reaction Methods 0.000 claims 1
- 125000003368 amide group Chemical group 0.000 claims 1
- 125000006367 bivalent amino carbonyl group Chemical group [H]N([*:1])C([*:2])=O 0.000 claims 1
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 abstract 2
- 240000006394 Sorghum bicolor Species 0.000 abstract 1
- 235000011684 Sorghum saccharatum Nutrition 0.000 abstract 1
- 239000002351 wastewater Substances 0.000 description 13
- 229910052751 metal Inorganic materials 0.000 description 12
- 239000002184 metal Substances 0.000 description 12
- 239000000126 substance Substances 0.000 description 12
- 238000004458 analytical method Methods 0.000 description 9
- 150000002739 metals Chemical class 0.000 description 9
- 230000008569 process Effects 0.000 description 9
- UWCPYKQBIPYOLX-UHFFFAOYSA-N benzene-1,3,5-tricarbonyl chloride Chemical compound ClC(=O)C1=CC(C(Cl)=O)=CC(C(Cl)=O)=C1 UWCPYKQBIPYOLX-UHFFFAOYSA-N 0.000 description 8
- 238000011156 evaluation Methods 0.000 description 7
- 238000003723 Smelting Methods 0.000 description 6
- 239000010410 layer Substances 0.000 description 6
- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- 239000004745 nonwoven fabric Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 3
- 229920002396 Polyurea Polymers 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 150000001408 amides Chemical class 0.000 description 3
- 230000004907 flux Effects 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 150000004985 diamines Chemical class 0.000 description 2
- KIQKWYUGPPFMBV-UHFFFAOYSA-N diisocyanatomethane Chemical compound O=C=NCN=C=O KIQKWYUGPPFMBV-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000011133 lead Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
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- 229920002492 poly(sulfone) Polymers 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- 238000004483 ATR-FTIR spectroscopy Methods 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000004697 Polyetherimide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
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- 238000004132 cross linking Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920001601 polyetherimide Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229940124530 sulfonamide Drugs 0.000 description 1
- 150000003456 sulfonamides Chemical class 0.000 description 1
- 150000003461 sulfonyl halides Chemical class 0.000 description 1
- 238000005211 surface analysis Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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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
- B01D69/105—Support pretreatment
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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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
- B01D61/027—Nanofiltration
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0006—Organic membrane manufacture by chemical reactions
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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
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- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/56—Polyamides, e.g. polyester-amides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/58—Other polymers having nitrogen in the main chain, with or without oxygen or carbon only
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D2323/12—Specific ratios of components used
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B—PERFORMING OPERATIONS; TRANSPORTING
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Abstract
본 발명은 다공성 지지체; 및상기 다공성 지지체 표면에 하기 화학식 1의 선형 지방족 다이아민(linear aliphatic diamine)을 포함하는 아민수용액과 산할로겐 화합물 및 다이이소시아네이트(diisocyanate)를 포함하는 유기용액을 계면중합하여 형성된 내산성 및 내열성이 향상된 나노분리막에 관한 것이다.
[화학식1]
여기서, n은 2~6의 자연수수(에틸렌다이아민(ethylenediamine), 다이아미노프로펜(1,3-diaminopropane), 다이아미노부탄(1,4-diaminobutane), 헥센다이아민(1,6-hexanediamine), 다이아미노펜탄(1,5-diaminopentane)) The present invention is a porous support; And Nano-improved acid and heat resistance formed by interfacial polymerization of an amine aqueous solution containing a linear aliphatic diamine of Formula 1 and an organic solution containing an acid halide compound and diisocyanate on the surface of the porous support It relates to a separator.
[Formula 1]
Here, n is 2-6 natural sorghum (ethylenediamine, ethylenediamine, 1,3-diaminopropane), diaminobutane (1,4-diaminobutane), hexene diamine (1,6-hexanediamine ), Diaminopentane (1,5-diaminopentane))
Description
본 발명은 내산성 및 내열성이 향상된 나노분리막 및 이의 제조방법으로 보다 자세하게는 이온별(1가 및 2가이온) 분리성능이 우수하고 15중량% 황산 용액에 30일 이상 견디는 내산성 및 내열성이 향상된 나노분리막 및 이의 제조방법에 관한 것이다. The present invention is a nano-separation membrane having improved acid resistance and heat resistance, and a nano-membrane having improved ion-specific (monovalent and divalent ion) separation performance in more detail and a 15% by weight sulfuric acid solution withstanding acid resistance and heat resistance for more than 30 days. And a method for manufacturing the same.
금속을 함유한 폐수에는，광산 폐수，화학 공장 폐수，제련소 폐수，제철소 폐수，도금 공장 폐수，쓰레기 소각장 폐수 등이 있다. 이 중에서 제련소 폐수 즉, 제련 공정의 산세정 과정에서 방출되는 산폐수는 구리, 납, 철, 크롬 등의 유가 및 희소금속이 다량 함유하고 있으며 금속으로서 분리 회수할 수 있다면 자원으로서의 가치 창출이 가능하다. 하지만 전 세계적으로 산폐수 용액에서 유가 및 희소 금속을 회수하는 기술이 없어 실제 공정에서는 중화, 응집친전법, 흡착법, 이온교환 공정 등을 이용하여 산폐수를 중화한 후 폐기하고 있다. 이러한 공정은 비용이 많이 발생하여 경제적이지 않으며 다량의 폐기물 및 2차 오염을 발생시켜 친환경적이지 못한 단점이 있다. 이에 유가 및 희소금속을 함유한 산폐수액을 기술적, 경제적으로 재활용할 수 있는 새로운 처리 기술인 막 분리법을 적용하고자 한다. Metal-containing wastewater includes mine wastewater, chemical plant wastewater, smelter wastewater, steelworks wastewater, plating plant wastewater, and garbage incinerator wastewater. Among these, smelter wastewater, that is, acid wastewater discharged during the acid cleaning process of the smelting process contains a large amount of oil and rare metals such as copper, lead, iron, and chromium. If it can be recovered separately as a metal, it is possible to create value as a resource. . However, there is no technology to recover oil and rare metals from acid waste water solutions worldwide. In the actual process, neutralization, coagulation, adsorption, and ion exchange processes are used to neutralize and discard acid waste water. This process has a disadvantage that it is not economical due to its high cost and is not environmentally friendly because it generates a large amount of waste and secondary pollution. To this end, we intend to apply a membrane separation method, a new treatment technology that can technically and economically recycle acid and waste liquids containing oil and rare metals.
따라서, 상기와 같은 폐수로부터 희소금속 및 유가 금속을 회수하기 위해 강산 및 고열 조건에서 사용할 수 있는 내산성 분리막에 대한 개발이 필요성이 대두되고 있다. 특히, 일반적인 습식제련공정에서의 침출액은 10~15% 황산 용액 상태이며, 다량의 1가이온(Na, Cl, F)와 다가이온(Ca, Mg, Pb, As) 등을 함께 포함하고 있어 이온별 분리성능이 우수해야하며, 지속적인 분리/농축을 위해서는 산에 대한 화학적 안정성이 무엇보다 중요하다. Accordingly, there is a need to develop an acid-resistant separator that can be used in strong acid and high-temperature conditions to recover rare metals and valuable metals from the wastewater. In particular, the leaching solution in the general wet smelting process is in the state of 10-15% sulfuric acid, and contains a large amount of monovalent ions (Na, Cl, F) and polyvalent ions (Ca, Mg, Pb, As). Star separation performance should be excellent, and chemical stability to acid is the most important for continuous separation / concentration.
한편, 미국등록특허 제7138058호는 나노 여과를 위한 산 안정성 멤브레인에 관한 것으로 아민 수용액에 설포닐 할라이드를 도입하여 술폰 아미드층을 형성시켜 내산성을 갖는 나노분리막을 제조할 수 있었다. 이는 내산성이 필요한 제련 산업 등 산폐수가 발생하는 공정에 적용될 수 있으나, 제련공정에서 발생하는 희소금속 및 유가 금속 등을 회수하기 위하여 강산 및 고열조건에서도 사용가능하고, 유량이 우수한 동시에 내산성능이 우수한 효과를 나타내기 어려운 문제점이 있다. On the other hand, U.S. Patent No. 7138058 relates to an acid-stable membrane for nanofiltration, and by introducing a sulfonyl halide in an amine aqueous solution to form a sulfonamide layer, a nano-separation membrane having acid resistance can be prepared. This can be applied to processes that generate acid waste water, such as the smelting industry, which requires acid resistance, but can be used in strong acids and high-temperature conditions to recover rare metals and valuable metals, etc. generated in the smelting process. There is a problem difficult to exhibit the effect.
또한 국내 제조사의 상용 나노 여과막의 경우 내산성은 우수하지만 1, 2가 이온 제거율이 높다. 1가 제거율이 높으면 높은 압력이 요구되고 투과 유량이 현저히 낮아 에너지 소모가 많고 운전비용이 높아 경제성이 저하되는 문제점이 있다.In addition, in the case of a commercial nano-filtration membrane of a domestic manufacturer, the acid resistance is excellent, but the removal rate of 1 and 2 ions is high. When the monovalent removal rate is high, high pressure is required, and the permeate flow rate is remarkably low, resulting in high energy consumption and high operating cost, which results in a problem of deteriorating economic efficiency.
본 발명의 목적은 제련 공정에서 발생하는 희소금속 및 유가 금속 등을 회수하기 위하여 강산 및 고온조건에서도 사용 가능하고, 동시에 유량이 우수한 효과가 있는 내산성 및 내열성이 향상된 나노분리막 및 이의 제조방법을 제공하는 데 있다.It is an object of the present invention to provide rare metals and valuable metals, etc. generated in a smelting process and can be used in strong acid and high temperature conditions, and at the same time, to provide a nano-separation membrane having improved acid resistance and heat resistance with excellent flow rate and a method of manufacturing the same Having
상기와 같은 문제점을 해결하기 위해 본 발명은 다공성 지지체; 및The present invention to solve the above problems is a porous support; And
상기 다공성 지지체 표면에 하기 화학식 1의 선형 지방족 다이아민(linear aliphatic diamine)을 포함하는 아민수용액과 산할로겐 화합물 및 다이이소시아네이트(diisocyanate)를 포함하는 유기용액을 계면중합하여 형성된 내산성 및 내열성이 향상된 나노분리막을 제공한다. A nano-separation membrane having improved acid and heat resistance formed by interfacial polymerization of an aqueous amine solution containing a linear aliphatic diamine of
[화학식1][Formula 1]
여기서, n은 1~6의 자연수(에틸렌다이아민(ethylenediamine), 다이아미노프로펜(1,3-diaminopropane), 다이아미노부탄(1,4-diaminobutane), 헥센다이아민(1,6-hexanediamine), 다이아미노펜탄(1,5-diaminopentane)) Here, n is a natural number of 1 to 6 (ethylenediamine (ethylenediamine), diaminopropene (1,3-diaminopropane), diaminobutane (1,4-diaminobutane), hexene diamine (1,6-hexanediamine)) , Diaminopentane (1,5-diaminopentane)
또한 본 발명은 상기 아민수용액은 친수성 고분자를 0.01 ~ 1 중량 % 포함하는 것을 특징으로 하는 내산성 및 내열성이 향상된 나노분리막을 제공한다. In addition, the present invention provides a nano-separation membrane having improved acid resistance and heat resistance, characterized in that the amine aqueous solution contains 0.01 to 1% by weight of a hydrophilic polymer.
또한 본 발명은 상기 친수성 고분자는 폴리비닐피롤리돈, 폴리에틸렌글리콜, 폴리비닐 알코올 하이드로퀴논으로 이루어진 군으로부터 선택되는 1종 이상을 포함하는 것을 특징으로 하는 내산성 및 내열성이 향상된 나노분리막을 제공한다. In addition, the present invention provides a nano-separation membrane having improved acid and heat resistance, characterized in that the hydrophilic polymer comprises at least one selected from the group consisting of polyvinylpyrrolidone, polyethylene glycol, and polyvinyl alcohol hydroquinone.
또한 본 발명은 상기 아민수용액은 상기 화학식 1의 선형 지방족 다이아민(linear aliphatic diamine)이 아민수용액 전체 중량에 대하여 0.1~10중량%로 포함하는 것을 특징으로 하는 내산성 및 내열성이 향상된 나노분리막을 제공한다. In addition, the present invention provides a nano-separation membrane having improved acid resistance and heat resistance, characterized in that the amine aqueous solution contains 0.1 to 10% by weight of the total weight of the amine aqueous solution in the linear aliphatic diamine of Chemical Formula 1 .
또한 본 발명은 상기 산할로겐 화합물은 이소프탈로일클로라이드, 트리메조일클로라이드 또는 테레프탈로일클로라이드 중에서 선택된 1종 이상을 포함하는 것을 특징으로 하는 내산성 및 내열성이 향상된 나노분리막을 제공한다. In addition, the present invention provides a nano-separation membrane having improved acid resistance and heat resistance, characterized in that the acid halide compound comprises at least one selected from isophthaloyl chloride, trimethoyl chloride or terephthaloyl chloride.
또한 본 발명은 상기 다이이소시아네이트(diisocyanate)는 톨릴렌 2,4-다이아이소시아네이트(tolylene 2,4-diisocyanate), 1,4-페닐렌 다이아이소시아네이트(1,4-phenylene diisocyanate), 1,6-헥사메틸렌 다이아이소시아네이트(1,6-hexamethylene diisocyanate) 및 아이소포론 다이아이소시아네이트(isophorone diisocyanate)중에서 선택된 1종 이상을 포함하는 것을 특징으로 하는 내산성 및 내열성이 향상된 나노분리막을 제공한다. In addition, the present invention, the diisocyanate (diisocyanate) is tolylene 2,4-diisocyanate (tolylene 2,4-diisocyanate), 1,4-phenylene diisocyanate (1,4-phenylene diisocyanate), 1,6-hexa It provides a nano-separation membrane having improved acid resistance and heat resistance, characterized in that it comprises at least one selected from methylene diisocyanate (1,6-hexamethylene diisocyanate) and isophorone diisocyanate.
또한 본 발명은 상기 유기용액은 산할로겐 화합물을 0.001~1중량%로 포함하는 것을 특징으로 하는 내산성 및 내열성이 향상된 나노분리막을 제공한다. In addition, the present invention provides a nano-separation membrane having improved acid resistance and heat resistance, characterized in that the organic solution contains an acid halide compound in an amount of 0.001 to 1% by weight.
또한 본 발명은 상기 나노분리막은 15중량%의 황산 수용액에 30일간 침지시 25℃ 및 75psi에서 유량이 15gfd 이상이고, 2가 이온제거율이 98%이상인 것을 특징으로 하는 내산성 및 내열성이 향상된 나노분리막을 제공한다.In addition, the present invention, the nano-separation membrane is immersed in 15% by weight of an aqueous sulfuric acid solution for 30 days at 25 ℃ and 75psi flow rate of 15gfd or more, the divalent ion removal rate is 98% or more improved nano-membrane membrane is improved to provide.
또한 본 발명은 상기 나노분리막은 60℃에서의 2가이온 제거율 변화가 초기온도(25℃) 대비 10% 이하인 97% 이상인 것을 특징으로 하는 내산성 및 내열성이 향상된 나노분리막을 제공한다. In addition, the present invention provides a nano-separation membrane having improved acid resistance and heat resistance, characterized in that the change in the removal rate of divalent ions at 60 ° C is 10% or less compared to the initial temperature (25 ° C).
또한 본 발명은 다공성 지지체를 하기 화학식 1의 선형 지방족 다이아민(linear aliphatic diamine)을 포함하는 아민수용액에 침지하는 1단계; 및In addition, the present invention is a first step of immersing the porous support in an aqueous amine solution containing a linear aliphatic diamine of Formula 1 below; And
상기 다공성 지지체를 산할로겐 화합물 및 다이이소시아네이트(diisocyanate)를 포함하는 유기용액하에서 계면중합한 후, 건조하여 다공성 지지체의 표면에 폴리아미드층을 형성하는 2단계;를 포함하는 내산성 및 내열성이 향상된 나노분리막 제조방법을 제공한다. After the interfacial polymerization of the porous support under an organic solution containing an acid halide compound and a diisocyanate (diisocyanate), drying to form a polyamide layer on the surface of the porous support; nano-membrane membrane containing improved acid resistance and heat resistance Provide a manufacturing method.
[화학식1][Formula 1]
여기서, n은 1~6의 자연수(에틸렌다이아민(ethylenediamine), 다이아미노프로펜(1,3-diaminopropane), 다이아미노부탄(1,4-diaminobutane), 헥센다이아민(1,6-hexanediamine), 다이아미노펜탄(1,5-diaminopentane)) Here, n is a natural number of 1 to 6 (ethylenediamine (ethylenediamine), diaminopropene (1,3-diaminopropane), diaminobutane (1,4-diaminobutane), hexene diamine (1,6-hexanediamine)) , Diaminopentane (1,5-diaminopentane)
또한 본 발명은 상기 아민수용액은 친수성 고분자를 0.01 ~ 1 중량 % 포함하는 것을 특징으로 하는 내산성 및 내열성이 향상된 나노분리막 제조방법을 제공한다. In addition, the present invention provides a method for producing a nano-separation membrane having improved acid resistance and heat resistance, characterized in that the amine aqueous solution contains 0.01 to 1% by weight of a hydrophilic polymer.
또한 본 발명은 상기 친수성 고분자는 폴리비닐피롤리돈, 폴리에틸렌글리콜, 폴리비닐 알코올 하이드로퀴논으로 이루어진 군으로부터 선택되는 1종 이상을 포함하는 것을 특징으로 하는 내산성 및 내열성이 향상된 나노분리막 제조방법을 제공한다. In addition, the present invention provides a method for producing a nano-separation membrane having improved acid and heat resistance, characterized in that the hydrophilic polymer comprises at least one selected from the group consisting of polyvinylpyrrolidone, polyethylene glycol, and polyvinyl alcohol hydroquinone. .
또한 본 발명은 상기 아민수용액은 상기 화학식 1의 선형 지방족 다이아민(linear aliphatic diamine)이 아민수용액 전체 중량에 대하여 0.1~10중량%로 포함하는 것을 특징으로 하는 내산성 및 내열성이 향상된 나노분리막 제조방법을 제공한다. In addition, the present invention is an amine aqueous solution is a linear aliphatic diamine of the formula 1 (linear aliphatic diamine) is characterized in that it comprises 0.1 to 10% by weight relative to the total weight of the amine aqueous solution nano-membrane manufacturing method with improved acid resistance and heat resistance to provide.
또한 본 발명은 상기 산할로겐 화합물은 이소프탈로일클로라이드, 트리메조일클로라이드 또는 테레프탈로일클로라이드 중에서 선택된 1종 이상을 포함하는 것을 특징으로 하는 내산성 및 내열성이 향상된 나노분리막 제조방법을 제공한다. In addition, the present invention provides a method for producing a nano-membrane membrane having improved acid and heat resistance, characterized in that the acid halide compound comprises at least one selected from isophthaloyl chloride, trimethoyl chloride or terephthaloyl chloride.
또한 본 발명은 상기 다이이소시아네이트(diisocyanate)는 톨릴렌 2,4-다이아이소시아네이트(tolylene 2,4-diisocyanate), 1,4-페닐렌 다이아이소시아네이트(1,4-phenylene diisocyanate), 1,6-헥사메틸렌 다이아이소시아네이트(1,6-hexamethylene diisocyanate) 및 아이소포론 다이아이소시아네이트(isophorone diisocyanate)중에서 선택된 1종 이상을 포함하는 것을 특징으로 하는 내산성 및 내열성이 향상된 나노분리막 제조방법을 제공한다. In addition, the present invention, the diisocyanate (diisocyanate) is tolylene 2,4-diisocyanate (tolylene 2,4-diisocyanate), 1,4-phenylene diisocyanate (1,4-phenylene diisocyanate), 1,6-hexa It provides a method for producing a nano-membrane membrane having improved acid and heat resistance, characterized in that it comprises at least one selected from methylene diisocyanate (1,6-hexamethylene diisocyanate) and isophorone diisocyanate.
또한 본 발명은 상기 유기용액은 산할로겐 화합물을 0.001~1중량%로 포함하는 것을 특징으로 하는 내산성 및 내열성이 향상된 나노분리막 제조방법을 제공한다. In addition, the present invention provides a method for producing a nano-separation membrane having improved acid resistance and heat resistance, characterized in that the organic solution contains an acid halide compound in an amount of 0.001 to 1% by weight.
본 발명은 계면중합용 모노머로 선형 지방족 다이아민(linear aliphatic diamine)과 유기상 용액의 다이이소시아네이트(diisocyanate)를 이용한 것으로 내산, 내열이 우수한 특징을 갖는다. The present invention uses a linear aliphatic diamine and a diisocyanate of an organic phase solution as a monomer for interfacial polymerization, and has excellent acid and heat resistance characteristics.
도 1은 실시예 3의 15중량% 황산조건에서 내산성 평가 그래프이다.
도 2는 실시예 3의 XPS 분석 스펙트라이다.
도 3은 실시예 3의 FTIR 분석 그래프이다.
도 4는 실시예 3의 5중량% 황산조건에서 시간에 따른 분리막 표면 FE-SEM사진이다. 1 is a graph of acid resistance evaluation in 15 wt% sulfuric acid conditions of Example 3.
2 is an XPS analysis spectra of Example 3.
3 is a graph of FTIR analysis of Example 3.
Figure 4 is a FE-SEM picture of the separator surface over time under 5 wt% sulfuric acid conditions of Example 3.
이하 본 발명의 바람직한 실시예를 상세히 설명하기로 한다. 우선, 본 발명을 설명함에 있어, 관련된 공지기능 혹은 구성에 대한 구체적인 설명은 본 발명의 요지를 모호하지 않게 하기 위하여 생략한다.Hereinafter, a preferred embodiment of the present invention will be described in detail. First, in describing the present invention, detailed descriptions of related known functions or configurations will be omitted so as not to obscure the subject matter of the present invention.
본 명세서에서 사용되는 정도의 용어 '약', '실질적으로' 등은 언급된 의미에 고유한 제조 및 물질 허용오차가 제시될 때 그 수치에서 또는 그 수치에 근접한 의미로 사용되고, 본 발명의 이해를 돕기 위해 정확하거나 절대적인 수치가 언급된 개시 내용을 비양심적인 침해자가 부당하게 이용하는 것을 방지하기 위해 사용된다.As used herein, the terms 'about', 'substantially', etc. are used in or at a value close to that value when manufacturing and substance tolerances specific to the stated meaning are presented, and the understanding of the invention To aid, accurate or absolute figures are used to prevent unconscionable abusers from unduly using the disclosed disclosure.
본 발명은 내산성 및 내열성이 향상된 나노분리막에 관한 것으로 다공성 지지체; 및 상기 다공성 지지체 표면에 하기 화학식 1의 선형 지방족 다이아민(linear aliphatic diamine)을 포함하는 아민수용액과 산할로겐 화합물 및 다이이소시아네이트(diisocyanate)를 포함하는 유기용액을 계면중합하여 형성된 것에 특징이 있다.The present invention relates to a nano-separation membrane having improved acid resistance and heat resistance, a porous support; And it characterized in that the surface of the porous support is formed by interfacial polymerization of an amine aqueous solution containing a linear aliphatic diamine of
여기서, n은 2~6의 자연수이며, 에틸렌다이아민(ethylenediamine), 다이아미노프로펜(1,3-diaminopropane), 다이아미노부탄(1,4-diaminobutane), 헥센다이아민(1,6-hexanediamine), 다이아미노펜탄(1,5-diaminopentane)의 아민 고분자로 이루어진 군에서 선택된 하나 이상의 아민으로 아민 수용액을 이룬다.Here, n is a natural number of 2 to 6, ethylenediamine (ethylenediamine), diaminopropene (1,3-diaminopropane), diaminobutane (1,4-diaminobutane), hexene diamine (1,6-hexanediamine ), Diaminopentane (1,5-diaminopentane) amine polymer consisting of at least one amine selected from the group consisting of an amine aqueous solution.
상기 다공성 지지체는 폴리에스테르 부직포에 폴리설폰, 폴리에테르설폰, 폴리이미드, 폴리아마이드, 폴리에테르이미드, 폴리아크릴로니트릴, 폴리(메틸메타크릴레이트), 폴리에틸렌, 폴리프로필렌, 및 할로겐화 고분자로 이루어진 군에서 선택된 하나 이상의 고분자로 캐스팅되어 형성된 것이다.The porous support is in the group consisting of polysulfone, polyethersulfone, polyimide, polyamide, polyetherimide, polyacrylonitrile, poly (methylmethacrylate), polyethylene, polypropylene, and halogenated polymer on a polyester nonwoven fabric. It is formed by casting with one or more selected polymers.
이때, 상기 폴리에스테르 부직포의 평균 두께는 30~300㎛이고, 상기 폴리에스테르 부직포의 일면 또는 양면에 캐스팅될 수 있으며, 상기 캐스팅 두께는 20~ 100㎛이다. At this time, the average thickness of the polyester nonwoven fabric is 30 ~ 300㎛, can be cast on one or both sides of the polyester nonwoven fabric, the casting thickness is 20 ~ 100㎛.
상기 선형 지방족 디이아민(linear aliphatic diamine)은 친수성 고분자과 혼합되여 아민수용액을 이룬다. 상기 친수성 고분자는 아민수용액에 0.01 ~ 1 중량 %되는 것이 바람직하다.The linear aliphatic diamine is mixed with a hydrophilic polymer to form an aqueous amine solution. The hydrophilic polymer is preferably 0.01 to 1% by weight in amine aqueous solution.
상기 친수성 고분자는 폴리비닐피롤리돈, 폴리에틸렌글리콜, 폴리비닐 알코올, 하이드로퀴논로 이루어진 군으로부터 선택되는 1종 이상을 포함하며, 상기 선형 지방족 다이아민(linear aliphatic diamine)이 아민수용액 전체 중량에 대하여 0.1~10중량%로 구성된다.The hydrophilic polymer includes at least one selected from the group consisting of polyvinylpyrrolidone, polyethylene glycol, polyvinyl alcohol, and hydroquinone, and the linear aliphatic diamine is 0.1 based on the total weight of the amine aqueous solution. It is composed of ~ 10% by weight.
상기 아민수용액과 계면중합을 하는 유기용액은 산할로겐 화합물 및 다이이소시아네이트(diisocyanate)로 구성된다.The organic solution for interfacial polymerization with the aqueous amine solution is composed of an acid halide compound and a diisocyanate.
상기 산할로겐 화합물은 이소프탈로일클로라이드, 트리메조일클로라이드 또는 테레프탈로일클로라이드 중에서 선택된 1종 이상을 포함하며,The acid halide compound includes at least one selected from isophthaloyl chloride, trimethoyl chloride or terephthaloyl chloride,
상기 다이이소시아네이트(diisocyanate)는 톨릴렌 2,4-다이아이소시아네이트(tolylene 2,4-diisocyanate), 1,4-페닐렌 다이아이소시아네이트(1,4-phenylene diisocyanate), 1,6-헥사메틸렌 다이아이소시아네이트(1,6-hexamethylene diisocyanate) 및 아이소포론 다이아이소시아네이트(isophorone diisocyanate)중에서 선택된 1종 이상을 포함한다.The diisocyanate is tolylene 2,4-diisocyanate, 1,4-phenylene diisocyanate, 1,6-hexamethylene diisocyanate ( 1,6-hexamethylene diisocyanate) and isophorone diisocyanate (isophorone diisocyanate).
여기서 상기 유기용액은 산할로겐 화합물을 0.001~1중량%로 포함한다. Here, the organic solution contains an acid halide compound in an amount of 0.001 to 1% by weight.
본 발명은 제련공정에서 발생하는 희소 금속을 함유한 폐산용액을 막분리법으로 적용하는 것에 특징이 있다. 현재 상용화된 나노분리막은 폴리피페라진 (polypiperazine)으로 구성되어 있으며 강산 및 고온 등 사용 조건에 적합하지 않다. 이에 이온별 분리성능이 우수하고 15중량% 황산 용액에 30일 이상 견디는 나노 분리막을 제조하고자 신규 모노머로 선형 지방족 디이아민(linear aliphatic diamine)를 포함하여 사용하였고, 유기상 용액으로 다이이소시아네이트(diisocyanate)를 첨가하였다. The present invention is characterized in that the waste acid solution containing the rare metal generated in the smelting process is applied by a membrane separation method. Currently commercially available nano-separation membranes are composed of polypiperazine and are not suitable for use conditions such as strong acids and high temperatures. Accordingly, a linear aliphatic diamine was used as a new monomer to produce a nano-separation membrane having excellent separation performance for each ion and enduring 30 days in a 15% by weight sulfuric acid solution, and diisocyanate was used as an organic phase solution. Was added.
상기 화학식 1과 같이 n이 2~6인 비교적 길이가 짧은 다이아민(diamine)을 사용함으로써, 가교결합이 증가하고 또한 강한 수소결합이 고분자 사슬을 따라 조밀하게 배열되고 산에 의한 가수분해가 쉽게 일어나지 않아 황산에 안정성을 가진다. By using a diamine having a relatively short n of 2 to 6 as in
2개의 NCO기를 가지는 다이이소시아네이트(diisocyanate)는 아민과 빠른 연쇄 반응을 일으켜 공명구조를 가지고 전자제공(electron-donating)그룹인 폴리우레아(polyurea) 결합으로 산과 열에 대한 안정성이 증가해 내산, 내열, 내화학성 등 우수한 물성을 가지는 폴리우레아(polyurea)를 형성한다. Diisocyanate having two NCO groups has a fast chain reaction with amines and has a resonance structure, and the electron-donating group polyurea bond increases the stability to acid and heat, thereby increasing acid, heat and heat resistance. A polyurea having excellent physical properties such as chemical properties is formed.
또한, 부분적 극성구조로 인하여 분자 간 인력이 용매, 열 및 화학적 안정성까지 우수한 장점이 있다. In addition, due to the partial polar structure, the intermolecular attraction has excellent advantages such as solvent, thermal and chemical stability.
일 예로 다이아민(Diamine)과 아이이소시아네이트(diisocyanate) 및 트리메조일클로라이드(trimesoylchloride,TMC)의 화학반응식을 아래 화학식 2에 나타내었다. For example, the chemical reaction formulas of diamine, diisocyanate and trimesoylchloride (TMC) are shown in Chemical Formula 2 below.
[화학식2]
삭제delete
여기서, n은 2~6의 자연수이며, 에틸렌다이아민(ethylenediamine), 다이아미노프로펜(1,3-diaminopropane), 다이아미노부탄(1,4-diaminobutane), 헥센다이아민(1,6-hexanediamine), 다이아미노펜탄(1,5-diaminopentane)과 같은 화합물로 이루어진 군으로부터 선택되는 1종 이상을 포함하는 아민수용액을 이용하여 계면중합되어 형성된 것을 특징으로 하는 내산성 및 내열성이 향상된 나노분리막을 제공한다.Here, n is a natural number of 2 to 6, ethylenediamine (ethylenediamine), diaminopropene (1,3-diaminopropane), diaminobutane (1,4-diaminobutane), hexene diamine (1,6-hexanediamine ), Diaminopentane (1,5-diaminopentane) provides a nano-separation membrane having improved acid and heat resistance, characterized in that formed by interfacial polymerization using an amine aqueous solution containing at least one member selected from the group consisting of compounds .
이상에서 설명한 바와 같은 본 설명의 특징 및 기타의 장점은 후술되는 실시예로부터 보다 명백하게 될 것이며,하기 실시예는 예시적인 목적으로 기재될 뿐 본 발명의 보호범위를 한정하거나 제한하는 것으로 해석될 수 없다.The features and other advantages of the present description as described above will become more apparent from the examples described below, and the following examples are described for illustrative purposes only and cannot be interpreted as limiting or limiting the protection scope of the present invention. .
<내산성 나노분리막의 제조 : 실시예> <Preparation of acid-resistant nano-separation membrane: Example>
* * 실시예Example 1 : One : 내산성Acid resistance 나노분리막의 제조 Preparation of nano separator
평균두께가 100㎛인 부직포 위에 캐스팅된 140㎛ 두께의 다공성 폴리설폰 지지체를 0.05중량% 에틸렌다이아민(EDA), 0.06 중량% 폴리비닐피롤리돈(PVP)을 혼합한 아민수용액에 40초간 침지한 후 지지체로부터 아민 수용액이 도포된 지지체를 0.1중량% 트리메조일클로라이드(TMC) 및 톨루엔 2,4-다이아이소시아네이트(tolylene 2,4-diisocyanate, TDI) 가 함유된 유기용액에 분간 침지하여 계면중합하였다. 계면 중합 반응 직후 상온에서 1분 30초간 자연건조시켜 폴리아미드층을 형성한 후 소듐카보네이트 중량 수용액에 2시간 동안 침지하여 산 또는 미반응 잔여물들을 제거하여 폴리아미드 나노분리막을 제조하였다A porous polysulfone support having a thickness of 140 μm cast on a nonwoven fabric having an average thickness of 100 μm was immersed for 40 seconds in an amine aqueous solution mixed with 0.05 wt% ethylenediamine (EDA) and 0.06 wt% polyvinylpyrrolidone (PVP). After that, the support coated with the aqueous amine solution from the support was immersed in an organic solution containing 0.1% by weight of trimethoyl chloride (TMC) and toluene 2,4-diisocyanate (TDI) for minutes to perform interfacial polymerization. . After the interfacial polymerization reaction, the polyamide layer was naturally dried at room temperature for 1 minute and 30 seconds to form a polyamide layer, and then immersed in an aqueous sodium carbonate solution for 2 hours to remove acids or unreacted residues to prepare a polyamide nanoseparation membrane.
* * 실시예Example 2~4 : 2-4: 내산성Acid resistance 나노분리막의 제조 Preparation of nano separator
하기 표1의 트리메조일클로라이드(TMC) 및 톨루엔 2,4-다이아이소시아네이트(tolylene 2,4-diisocyanate, TDI)의 함량값이외에는 실시예 1과 동일하다.It is the same as in Example 1 except for the content values of trimeyl chloride (TMC) and toluene 2,4-diisocyanate (TDI) in Table 1 below.
<특성평가> <Characteristic evaluation>
1. One. 실시예Example 1~4의 초기 투과 특성 평가 Evaluation of initial transmission characteristics of 1 ~ 4
표2는 실시예의 나노분리막의 초기 투과 특성 평가를 보여주는 측정값이다. Table 2 is a measurement value showing the evaluation of the initial transmission properties of the nano-separation membrane of the Example.
초기 유랑값이 7.24~15 Flux(GFD)이고 2가 이온 제거율인 92.4~98.01%값을 보여주고 있다.The initial flow value is 7.24 ~ 15 Flux (GFD) and the divalent ion removal rate is 92.4 ~ 98.01%.
2. 나노분리막의 내열성 투과 특성 평가2. Evaluation of heat-resistant permeability of nano-separation membrane
초기 투과 특성 및 2가 이온 제거율이 가장 좋은 실시예 3을 대상으로 온도 25~60℃ 사이의 특정 온도에서 투과율 및 제거율을 평가하였다. 온도가 증가함에 따라 투과율은 증가하였으며, 제거율은 다소 줄어들었다. For Example 3, which has the best initial permeability and divalent ion removal rate, the transmittance and removal rate were evaluated at a specific temperature between 25 and 60 ° C. As the temperature increased, the transmittance increased and the removal rate decreased somewhat.
3. 나노분리막의 3. Nano-separation membrane 내산성Acid resistance 특성 평가 Characteristic evaluation
도 1은 실시예 3의 15중량% 황산조건에서 내산성 평가 그래프이다. 투과량 15gfd 이상, 2가 이온제거율은 98% 이상으로 30일 동안 성능이 유지됨을 확인하였다. 내산성 30일을 만족하였지만 추가적으로 80일 이상 내산성 실험을 진행하였고, 83일 이후에도 내산성이 약 98% 이상 유지됨을 확인하였다. 1 is a graph of acid resistance evaluation in 15 wt% sulfuric acid conditions of Example 3. It was confirmed that the permeation amount was 15 gfd or more and the divalent ion removal rate was 98% or more, and the performance was maintained for 30 days. Although the acid resistance was satisfied for 30 days, an acid resistance experiment was conducted for more than 80 days, and it was confirmed that the acid resistance was maintained at about 98% or more after 83 days.
4. 4. 실시예Example 3의 분리막 표면분석 3, Membrane surface analysis
① XPS 분석① XPS analysis
도 2는 실시예 3의 XPS 분석스펙트라이다. 실시예 3의 활성층 화학적 구조를 확인하고자 XPS 분석을 진행하였고 그 결과를 그림 3에 나타내었다. C1s, N1s의 스펙트럼을 통해 아민과 TMC, diisocyanate의 중합을 확인하였다. 2 is an XPS analysis spectrum of Example 3. To confirm the chemical structure of the active layer of Example 3, XPS analysis was performed and the results are shown in Figure 3. The polymerization of amine, TMC and diisocyanate was confirmed through the spectrum of C1s and N1s.
C1s 스펙트럼을 통해 기본적인 polyamide의 화학구조인 C-H, C-C (285 eV), C-O (286 eV), O=C-O, O=C-N (288 eV) 결합을 확인하였다. N1s 스펙트럼을 통해 401.7, 399.2 eV에서 일반적인 amide와 urea의 화학구조인 N-C=O와 N-C 결합을 확인하였다. 또한, 400.4 eV에서 urea 화학 구조인 N=C 결합을 확인할 수 있었으며 이를 통해 아민이 TMC의 COCl기와 diisocyanate의 NCO기와 결합하여 NF 분리막이 성공적으로 제조된 것을 확인하였다. The C1s spectrum confirmed the basic polyamide chemical structures C-H, C-C (285 eV), C-O (286 eV), O = C-O, and O = C-N (288 eV). Through the N1s spectrum, the chemical structures of general amide and urea, N-C = O and N-C, were confirmed at 401.7 and 399.2 eV. In addition, at 400.4 eV, the urea chemical structure, N = C bond, was confirmed, and it was confirmed that the NF membrane was successfully prepared by combining amine with COCl of TMC and NCO of diisocyanate.
② FTIR 분석② FTIR analysis
도 3은 실시예 3의 FTIR 분석그래프이다. 실시예 3의 NF 분리막의 모폴로지를 확인하기 위해 ATR-FTIR 분석을 진행하였고 그 결과를 도 3에 나타내었다. 1660, 1510cm-1에서 amideⅠ과 amideⅡ bond를 확인하였고, 이는 NH2와 TMC의 COCl, diisocyanate의 NCO기의 합성으로 폴리아미드 혹은 폴리우레아 활성층이 형성되었다고 볼 수 있다. 또한, 30일 이후에도 IR 피크 변화가 없는 것을 통해 제조된 니노분리막의 내산성을 확인하였다. 3 is an FTIR analysis graph of Example 3. ATR-FTIR analysis was performed to confirm the morphology of the NF membrane of Example 3, and the results are shown in FIG. 3. The amide I and amide II bonds were confirmed at 1660 and 1510 cm -1 , and it can be seen that a polyamide or polyurea active layer was formed by the synthesis of NCO groups of CO 2 and diisocyanate of NH 2 and TMC. In addition, after 30 days, the acid resistance of the Nino-separated membrane prepared through the absence of an IR peak change was confirmed.
③ FE-SEM 분석③ FE-SEM analysis
도 4는 실시예 3의 15중량% 황산조건에서 시간에 따른 분리막 표면 FE-SEM사진이다. Figure 4 is a FE-SEM picture of the separator surface over time under 15% by weight sulfuric acid condition of Example 3.
실시예 3의 나노분리막의 표면을 FE-SEM을 통해 분석하였으며, 도 4는 50,000배로 확대한 FE-SEM 사진 결과이다. 도 4의(a)는 제조된 막의 표면이며, (b)와 (c)는 15중량% 황산 용액에 23일, 30일 이상 침지한 후 표면을 관찰한 결과이다. (c)는 코팅층이 파손되지 않고 표면 변화 없이 (a)와 같은 결과를 보이며, 이를 통해 내산성이 30일 이상 유지되는 것을 확인할 수 있었다The surface of the nano-separation membrane of Example 3 was analyzed through FE-SEM, and FIG. 4 is an FE-SEM photograph result enlarged to 50,000 times. Figure 4 (a) is the surface of the prepared film, (b) and (c) is a result of observing the surface after immersion in 15 wt% sulfuric acid solution for 23 days, 30 days or more. (c) shows that the coating layer does not break and shows the same result as (a) without changing the surface, and through this, it was confirmed that the acid resistance was maintained for more than 30 days.
이상에서 설명한 본 발명은 전술한 실시예 및 첨부된 도면에 의해 한정되는 것이 아니고, 본 발명의 기술적 사상을 벗어나지 않는 범위 내에서 여러 가지 치환, 변형 및 변경이 가능함은 본 발명이 속하는 기술 분야에서 통상의 지식을 가진 자에게 있어서 명백할 것이다. The present invention described above is not limited by the above-described embodiments and the accompanying drawings, and various substitutions, modifications and changes are possible within the scope of the present invention without departing from the technical spirit of the present invention. It will be clear to those who have the knowledge of
Claims (16)
상기 다공성 지지체 표면에 하기 화학식 1의 선형 지방족 다이아민(linear aliphatic diamine)을 포함하는 아민수용액과 산할로겐 화합물 및 다이이소시아네이트(diisocyanate)를 포함하는 유기용액을 계면중합하여 형성되되,
상기 계면중합반응은 산할로겐 화합물의 하나의 관능기가 상기 선형 지방족 다이아민의 하나의 아민과 아마이드 결합하여 강한 수소결합력을 가지고 산 가수분해에 안정한 아마이드 그룹 (NHCO)을 형성하고,
상기 선형 지방족 다이아민의 다른 아민과 상기 다이이소시아네이트의 하나의 이소시아네이트와 우레아 결합하여 우레아 그룹의 공명구조와 EDA와의 결합으로 강한 quadruple 수소 결합에 의해 산의 공격에 의해 가수분해가 일어나지 않는 것에 특징이 있는 내산성 및 내열성이 향상된 나노분리막.
[화학식1]
여기서, n은 2~6의 자연수(에틸렌다이아민(ethylenediamine), 다이아미노프로펜(1,3-diaminopropane), 다이아미노부탄(1,4-diaminobutane), 헥센다이아민(1,6-hexanediamine), 다이아미노펜탄(1,5-diaminopentane))
Porous support; And
The surface of the porous support is formed by interfacial polymerization of an amine aqueous solution containing a linear aliphatic diamine of Formula 1 and an organic solution containing an acid halide compound and diisocyanate,
In the interfacial polymerization reaction, one functional group of an acid halide compound is amide-bonded with one amine of the linear aliphatic diamine to form an amide group (NHCO) having strong hydrogen bonding strength and stable for acid hydrolysis,
Acid resistance, characterized in that hydrolysis does not occur due to acid attack due to strong quadruple hydrogen bonding due to the urea bond of the urea group and urea bonding with the urea of another isocyanate of the diisocyanate and the other amine of the linear aliphatic diamine And a nano separator having improved heat resistance.
[Formula 1]
Here, n is a natural number of 2 to 6 (ethylenediamine (ethylenediamine), diaminopropene (1,3-diaminopropane), diaminobutane (1,4-diaminobutane), hexene diamine (1,6-hexanediamine)) , Diaminopentane (1,5-diaminopentane)
상기 아민수용액은 친수성 고분자를 0.01 ~ 1 중량% 포함하는 것을 특징으로 하는 내산성 및 내열성이 향상된 나노분리막.
According to claim 1,
The amine aqueous solution is a nano-separation membrane having improved acid resistance and heat resistance, characterized in that it contains 0.01 to 1% by weight of a hydrophilic polymer.
상기 친수성 고분자는 폴리비닐피롤리돈, 폴리에틸렌글리콜, 폴리비닐 알코올 하이드로퀴논으로 이루어진 군으로부터 선택되는 1종 이상을 포함하는 것을 특징으로 하는 내산성 및 내열성이 향상된 나노분리막.
According to claim 2,
The hydrophilic polymer is a polyvinylpyrrolidone, polyethylene glycol, polyvinyl alcohol nano-membrane having improved heat resistance and acid resistance, characterized in that it comprises at least one member selected from the group consisting of hydroquinone.
상기 아민수용액은 상기 화학식 1의 선형 지방족 다이아민(linear aliphatic diamine)이 아민수용액 전체 중량에 대하여 0.1~10중량%로 포함하는 것을 특징으로 하는 내산성 및 내열성이 향상된 나노분리막.
According to claim 1,
The amine aqueous solution is a nano-separation membrane having improved acid and heat resistance, characterized in that the linear aliphatic diamine of Formula 1 includes 0.1 to 10% by weight based on the total weight of the amine aqueous solution.
상기 산할로겐 화합물은 이소프탈로일클로라이드, 트리메조일클로라이드 또는 테레프탈로일클로라이드 중에서 선택된 1종 이상을 포함하는 것을 특징으로 하는 내산성 및 내열성이 향상된 나노분리막.
According to claim 1,
The acid halide compound is nanophthalic acid membrane having improved acid resistance and heat resistance, characterized in that it comprises at least one selected from isophthaloyl chloride, trimethoyl chloride or terephthaloyl chloride.
상기 다이이소시아네이트(diisocyanate)는 톨릴렌 2,4-다이아이소시아네이트(tolylene 2,4-diisocyanate), 1,4-페닐렌 다이아이소시아네이트(1,4-phenylene diisocyanate), 1,6-헥사메틸렌 다이아이소시아네이트(1,6-hexamethylene diisocyanate) 및 아이소포론 다이아이소시아네이트(isophorone diisocyanate)중에서 선택된 1종 이상을 포함하는 것을 특징으로 하는 내산성 및 내열성이 향상된 나노분리막.
According to claim 1,
The diisocyanate is tolylene 2,4-diisocyanate, 1,4-phenylene diisocyanate, 1,6-hexamethylene diisocyanate ( 1,6-hexamethylene diisocyanate) and isophorone diisocyanate (isophorone diisocyanate) characterized in that it comprises at least one selected from the nano-membrane having improved acid and heat resistance.
상기 유기용액은 산할로겐 화합물을 0.001~1중량%로 포함하는 것을 특징으로 하는 내산성 및 내열성이 향상된 나노분리막.
According to claim 1,
The organic solution is a nano-separation membrane having improved acid resistance and heat resistance, characterized in that it contains an acid halide compound in an amount of 0.001 to 1% by weight.
상기 나노분리막은 15중량%의 황산 수용액에 80일 이상 침지시 25℃ 및 75psi에서 유량이 15gfd 이상이고, 2가 이온 제거율이 98%이상인 것을 특징으로 하는 내산성 및 내열성이 향상된 나노분리막.
According to claim 1,
The nano-separation membrane is a nano-separation membrane having improved acid resistance and heat resistance, characterized in that the flow rate is 15 gfd or higher at 25 ° C. and 75 psi, and the divalent ion removal rate is 98% or higher when immersed in 15 wt% aqueous sulfuric acid solution for 80 days or more.
상기 나노분리막은 60℃에서의 2가 이온 제거율 변화가 초기온도(25℃) 대비 10% 이하인 97% 이상인 것을 특징으로 하는 내산성 및 내열성이 향상된 나노분리막.
According to claim 1,
The nano-separation membrane is a nano-separation membrane having improved acid resistance and heat resistance, characterized in that the change in the removal rate of the divalent ion at 60 ° C is 10% or less compared to the initial temperature (25 ° C).
상기 다공성 지지체를 산할로겐 화합물 및 다이이소시아네이트(diisocyanate)를 포함하는 유기용액하에서 계면중합한 후, 건조하여 다공성 지지체의 표면에 폴리아미드층을 형성하는 2단계;를 포함하되,
상기 계면중합반응은 산할로겐 화합물의 하나의 관능기가 상기 선형 지방족 다이아민의 하나의 아민과 아마이드 결합하고, 상기 선형 지방족 다이아민의 다른 아민과 상기 다이이소시아네이트의 하나의 이소시아네이트와 우레아 결합하는 것에 특징이 있는 내산성 및 내열성이 향상된 나노분리막 제조방법.
[화학식1]
여기서, n은 2~6의 자연수(에틸렌다이아민(ethylenediamine), 다이아미노프로펜(1,3-diaminopropane), 다이아미노부탄(1,4-diaminobutane), 헥센다이아민(1,6-hexanediamine), 다이아미노펜탄(1,5-diaminopentane))
A first step of immersing the porous support in an amine aqueous solution containing a linear aliphatic diamine of Formula 1; And
After the interfacial polymerization of the porous support under an organic solution containing an acid halide compound and diisocyanate, drying to form a polyamide layer on the surface of the porous support;
The interfacial polymerization reaction is acid-resistant, characterized in that one functional group of the acid halogen compound is amide-bonded with one amine of the linear aliphatic diamine, and another amine of the linear aliphatic diamine with one isocyanate of the diisocyanate. And nano-membrane manufacturing method with improved heat resistance.
[Formula 1]
Here, n is a natural number of 2 to 6 (ethylenediamine (ethylenediamine), diaminopropene (1,3-diaminopropane), diaminobutane (1,4-diaminobutane), hexene diamine (1,6-hexanediamine)) , Diaminopentane (1,5-diaminopentane)
상기 아민수용액은 친수성 고분자를 0.01 ~ 1 중량 % 포함하는 것을 특징으로 하는 내산성 및 내열성이 향상된 나노분리막 제조방법.
The method of claim 10,
The amine aqueous solution is a method for producing a nano-separation membrane having improved acid resistance and heat resistance, characterized in that it contains 0.01 to 1% by weight of a hydrophilic polymer.
상기 친수성 고분자는 폴리비닐피롤리돈, 폴리에틸렌글리콜, 폴리비닐 알코올 하이드로퀴논으로 이루어진 군으로부터 선택되는 1종 이상을 포함하는 것을 특징으로 하는 내산성 및 내열성이 향상된 나노분리막 제조방법.
The method of claim 11,
The hydrophilic polymer is polyvinylpyrrolidone, polyethylene glycol, polyvinyl alcohol hydroquinone, nano-membrane production method improved acid resistance and heat resistance, characterized in that it comprises at least one member selected from the group consisting of.
상기 아민수용액은 상기 화학식 1의 선형 지방족 다이아민(linear aliphatic diamine)이 아민수용액 전체 중량에 대하여 0.1~10중량%로 포함하는 것을 특징으로 하는 내산성 및 내열성이 향상된 나노분리막 제조방법.
The method of claim 10,
The amine aqueous solution is a linear aliphatic diamine of the formula (1), characterized in that it comprises 0.1 to 10% by weight relative to the total weight of the amine aqueous solution Nano-membrane manufacturing method with improved acid resistance and heat resistance.
상기 산할로겐 화합물은 이소프탈로일클로라이드, 트리메조일클로라이드 또는 테레프탈로일클로라이드 중에서 선택된 1종 이상을 포함하는 것을 특징으로 하는 내산성 및 내열성이 향상된 나노분리막 제조방법.
The method of claim 10,
The acid halogen compound is isophthaloyl chloride, trimethoyl chloride or terephthaloyl chloride, nano-membrane manufacturing method having improved acid and heat resistance, characterized in that it comprises at least one selected from.
상기 다이이소시아네이트(diisocyanate)는 톨릴렌 2,4-다이아이소시아네이트(tolylene 2,4-diisocyanate), 1,4-페닐렌 다이아이소시아네이트(1,4-phenylene diisocyanate), 1,6-헥사메틸렌 다이아이소시아네이트(1,6-hexamethylene diisocyanate) 및 아이소포론 다이아이소시아네이트(isophorone diisocyanate)중에서 선택된 1종 이상을 포함하는 것을 특징으로 하는 내산성 및 내열성이 향상된 나노분리막 제조방법.
The method of claim 10,
The diisocyanate is tolylene 2,4-diisocyanate, 1,4-phenylene diisocyanate, 1,6-hexamethylene diisocyanate ( 1,6-hexamethylene diisocyanate) and isophorone diisocyanate (isophorone diisocyanate) characterized in that it comprises at least one selected from the nano-membrane manufacturing method with improved acid resistance and heat resistance.
상기 유기용액은 산할로겐 화합물을 0.001~1중량%로 포함하는 것을 특징으로 하는 내산성 및 내열성이 향상된 나노분리막 제조방법.
The method of claim 10,
The organic solution is a method for producing a nano-separation membrane having improved acid resistance and heat resistance, characterized in that it contains an acid halide compound in an amount of 0.001 to 1% by weight.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100823628B1 (en) | 2006-12-04 | 2008-04-21 | 웅진케미칼 주식회사 | Manufacturing method of polyamide nano composite membrane for water ionizer |
| JP2011131208A (en) | 2009-11-25 | 2011-07-07 | Fujifilm Corp | Crystalline polymer microporous membrane, method for producing the same, and filtration filter |
| KR101747028B1 (en) | 2016-03-31 | 2017-06-13 | 도레이케미칼 주식회사 | Flow rate improved Acid resistant nanomembrane and manufacturing method thereof |
| JP7022688B2 (en) * | 2015-08-14 | 2022-02-18 | ジー－モジュラー ホールディング，インコーポレイテッド | Modular building connector |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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| JP2011131208A (en) | 2009-11-25 | 2011-07-07 | Fujifilm Corp | Crystalline polymer microporous membrane, method for producing the same, and filtration filter |
| JP7022688B2 (en) * | 2015-08-14 | 2022-02-18 | ジー－モジュラー ホールディング，インコーポレイテッド | Modular building connector |
| KR101747028B1 (en) | 2016-03-31 | 2017-06-13 | 도레이케미칼 주식회사 | Flow rate improved Acid resistant nanomembrane and manufacturing method thereof |
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|---|---|---|---|
| A201 | Request for examination | ||
| E902 | Notification of reason for refusal | ||
| AMND | Amendment | ||
| E601 | Decision to refuse application | ||
| X091 | Application refused [patent] | ||
| AMND | Amendment | ||
| X701 | Decision to grant (after re-examination) |