KR100872384B1 - The facilitated olefin transporting composite membrane comprising nanosized copper or gold metal, and ionic liquid - Google Patents
The facilitated olefin transporting composite membrane comprising nanosized copper or gold metal, and ionic liquid Download PDFInfo
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- KR100872384B1 KR100872384B1 KR1020070024412A KR20070024412A KR100872384B1 KR 100872384 B1 KR100872384 B1 KR 100872384B1 KR 1020070024412 A KR1020070024412 A KR 1020070024412A KR 20070024412 A KR20070024412 A KR 20070024412A KR 100872384 B1 KR100872384 B1 KR 100872384B1
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- nanoparticles
- ionic liquid
- olefin
- composite membrane
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- 239000002608 ionic liquid Substances 0.000 title claims abstract description 53
- 239000010949 copper Substances 0.000 title claims abstract description 40
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 39
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 33
- 239000012528 membrane Substances 0.000 title claims abstract description 32
- 239000002131 composite material Substances 0.000 title claims abstract description 31
- 239000010931 gold Substances 0.000 title claims abstract description 31
- 229910052737 gold Inorganic materials 0.000 title claims abstract description 30
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 title claims abstract description 29
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 239000002184 metal Substances 0.000 title description 4
- 229910052751 metal Inorganic materials 0.000 title description 4
- 239000002105 nanoparticle Substances 0.000 claims abstract description 75
- 230000001737 promoting effect Effects 0.000 claims abstract description 6
- IQQRAVYLUAZUGX-UHFFFAOYSA-N 1-butyl-3-methylimidazolium Chemical compound CCCCN1C=C[N+](C)=C1 IQQRAVYLUAZUGX-UHFFFAOYSA-N 0.000 claims description 19
- 229920002492 poly(sulfone) Polymers 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 4
- WPHIMOZSRUCGGU-UHFFFAOYSA-N 1-butyl-3-methylimidazol-3-ium;nitrate Chemical compound [O-][N+]([O-])=O.CCCCN1C=C[N+](C)=C1 WPHIMOZSRUCGGU-UHFFFAOYSA-N 0.000 claims 2
- 150000001875 compounds Chemical class 0.000 claims 2
- 238000000926 separation method Methods 0.000 abstract description 23
- 230000035699 permeability Effects 0.000 abstract description 9
- 150000001450 anions Chemical class 0.000 abstract description 4
- 239000012188 paraffin wax Substances 0.000 abstract description 4
- 239000002245 particle Substances 0.000 abstract 1
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 14
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 8
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 8
- 229920005597 polymer membrane Polymers 0.000 description 7
- 239000001294 propane Substances 0.000 description 7
- 239000007789 gas Substances 0.000 description 6
- -1 salt compounds Chemical class 0.000 description 6
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 230000007246 mechanism Effects 0.000 description 4
- 239000000969 carrier Substances 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical group [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 3
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000007723 transport mechanism Effects 0.000 description 2
- 229910016467 AlCl 4 Inorganic materials 0.000 description 1
- JVTAAEKCZFNVCJ-REOHCLBHSA-N L-lactic acid Chemical compound C[C@H](O)C(O)=O JVTAAEKCZFNVCJ-REOHCLBHSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000007172 homogeneous catalysis Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229940116871 l-lactate Drugs 0.000 description 1
- 239000006193 liquid solution Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 150000002892 organic cations Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 125000005496 phosphonium group Chemical group 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical group 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 description 1
- KAKQVSNHTBLJCH-UHFFFAOYSA-N trifluoromethanesulfonimidic acid Chemical compound NS(=O)(=O)C(F)(F)F KAKQVSNHTBLJCH-UHFFFAOYSA-N 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
- B01D69/12—Composite membranes; Ultra-thin membranes
- B01D69/1213—Laminated layers
-
- 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
-
- 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
- B01D69/14—Dynamic membranes
- B01D69/141—Heterogeneous membranes, e.g. containing dispersed material; Mixed matrix membranes
- B01D69/1411—Heterogeneous membranes, e.g. containing dispersed material; Mixed matrix membranes containing dispersed material in a continuous matrix
- B01D69/14111—Heterogeneous membranes, e.g. containing dispersed material; Mixed matrix membranes containing dispersed material in a continuous matrix with nanoscale dispersed material, e.g. nanoparticles
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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
- B01D69/14—Dynamic membranes
- B01D69/141—Heterogeneous membranes, e.g. containing dispersed material; Mixed matrix membranes
- B01D69/148—Organic/inorganic mixed matrix membranes
-
- 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
- B01D71/02—Inorganic material
- B01D71/022—Metals
-
- 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
- B01D71/66—Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
- B01D71/68—Polysulfones; Polyethersulfones
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2256/00—Main component in the product gas stream after treatment
- B01D2256/24—Hydrocarbons
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/12—Specific ratios of components used
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/16—Membrane materials having positively charged functional groups
Abstract
본 발명은 이온성액체와 구리(Cu)나노입자 또는 이온성액체와 금(Au)나노입자의 복합분리막을 제공한다. 본 발명의 복합분리막에서는 이온성액체의 음이온에 의해 구리나노입자 또는 금나노입자가 부분적으로 양이온화되어 올레핀의 촉진수송이 가능한 전달체(carrier)의 역할을 수행하게 되며, 이러한 구리나노입자 또는 금나노입자의 올레핀 촉진수송전달체의 역할에 의하여 올레핀/파라핀 혼합가스의 분리에 있어서 올레핀의 투과도 및 선택도가 함께 증가하여, 올레핀의 효율적인 분리가 가능하다.The present invention provides a composite separator of ionic liquids and copper (Cu) nanoparticles or ionic liquids and gold (Au) nanoparticles. In the composite membrane of the present invention, the copper nanoparticles or the gold nanoparticles are partially cationized by the anion of the ionic liquid to serve as a carrier capable of promoting transport of the olefin, and the copper nanoparticles or the gold nanoparticles. The permeability and selectivity of the olefin increases in the separation of the olefin / paraffin mixed gas due to the role of the olefin facilitating transporter of the particles, thereby enabling efficient separation of the olefin.
구리나노입자, 금나노입자, 이온성액체, 복합분리막 Copper nanoparticles, gold nanoparticles, ionic liquid, composite membrane
Description
도 1은 본 발명의 복합분리막에서 이온성액체와 구리나노입자의 상호작용을 나타내는 설명도이다.1 is an explanatory diagram showing the interaction between ionic liquids and copper nanoparticles in the composite separator of the present invention.
본 발명은 이온성액체(Ionic Liquids, ILs)와 구리나노입자 또는 금나노입자를 포함하여 구성되며, 촉진수송 매커니즘을 이용하여 분자량이 비슷한 올레핀/파라핀의 분리가 가능한 이온성액체와 구리나노입자, 또는 이온성액체와 금나노입자 함유 복합분리막에 관한 것이다.The present invention comprises an ionic liquid (Ionic Liquids, ILs) and copper nanoparticles or gold nanoparticles, ionic liquid and copper nanoparticles capable of separation of olefins / paraffins of similar molecular weight using a facilitation transport mechanism, Or it relates to a composite separator containing an ionic liquid and gold nanoparticles.
고분자분리막을 이용한 각종 혼합 물질의 분리법은 종래에는 주로 이산화탄소와 메탄, 산소와 공기, 유기물 증기와 공기 등의 분리에만 적용되어 왔으나, 올 레핀과 파라핀 혼합물, 예를 들어, 프로필렌과 프로판의 분리, 부틸렌과 부탄의 분리 등의 경우에는 올레핀과 파라핀 분자의 크기와 물리적 성질이 매우 비슷하기 때문에 고전적인 고분자분리막을 이용하여서는 충분한 분리 성능을 얻을 수 없었다. 이러한 고전적인 고분자분리막을 이용하여 분자량이 비슷한 올레핀과 파라핀의 분리가 어려운 점에 대한 해결책으로서 촉진수송 개념이 도입되면서 올레핀과 파라핀의 분리에 고분자분리막을 적용하기 위한 연구가 활발히 이루어지고 있다. Separation of various mixed materials using a polymer membrane has conventionally been mainly applied to the separation of carbon dioxide and methane, oxygen and air, organic vapor and air, but the mixture of olefin and paraffin, for example, separation of propylene and propane, butyl In the case of the separation of ene and butane, since the size and physical properties of olefin and paraffin molecules are very similar, sufficient separation performance could not be obtained by using a conventional polymer membrane. As a solution to the difficult separation of olefins and paraffins having similar molecular weights by using the classical polymer membranes, the promotion transport concept has been introduced, and studies have been actively conducted to apply polymer membranes to separate olefins and paraffins.
분리하고자 하는 혼합물 중의 특정 성분과 가역적으로 반응할 수 있는 운반체(carrier)가 분리막에 존재하는 경우, 운반체와 혼합물 중의 특정 성분(예를 들어, 올레핀)과의 가역반응으로 인하여 물질 전달이 단순한 피크(Fick)의 농도 구배에 의한 전달뿐만 아니라, 운반체에 의한 촉진수송(facilitated transport)도 함께 일어나게 되어 선택도 및 투과도가 함께 증가하게 된다.If there is a carrier in the membrane that can react reversibly with a specific component in the mixture to be separated, the peak of the mass transfer is simple due to the reversible reaction of the carrier with the specific component (eg olefin) in the mixture ( In addition to delivery by a concentration gradient of Fick, facilitated transport by the carrier also occurs along with increased selectivity and permeability.
이러한 촉진수송을 이용한 종래의 고분자분리막의 예로 운반체(carrier)로 은염, 예를 들어 AgBF4, AgCF3SO3 등을 담지시켜 만든 지지 또는 고정된 액막을 사용하는 방법에 대한 기술이 개시되어 있으나, 이러한 기술에서는 분리시간의 증가와 함께 은염의 활성도가 떨어지는 단점이 있어 이를 보완하기 위하여 프탈레이트화합물이나 계면활성제를 이용하는 기술 등이 제안되었다. 본 발명자들은 종래의 은염 형태의 운반체가 아닌 은나노입자를 운반체로 이용하는 촉진수송에 대하여 관심을 갖고 연구한 결과, 대한민국특허출원 제 10-2006-33100호에서는 고분자, 은나노입자 및 p-벤조퀴논을 포함하여 이루어지는 은나노입자 함유 올레핀 촉진수송 고분자분리막에 대한 기술과, 대한민국특허출원 제10-2006-37430호에서는 은나노입자와 이온성액체를 포함하여 이루어지는 올레핀촉진수송 복합분리막을 제안한 바 있다.An example of a conventional polymer membrane using such accelerated transport is a silver salt as a carrier, for example AgBF 4 , AgCF 3 SO 3 A technique for using a supported or fixed liquid membrane made by supporting the back is disclosed, but in this technique, there is a disadvantage in that silver salt activity decreases with an increase in separation time. Technology and the like have been proposed. The present inventors have been interested in research on the promotion of using silver nanoparticles as carriers, which are not conventional silver salt carriers, and as a result, Korean Patent Application No. 10-2006-33100 includes a polymer, silver nanoparticles, and p -benzoquinone. Silver nanoparticle-containing olefin promoted transport polymer separation membrane technology, and Korean Patent Application No. 10-2006-37430 has proposed an olefin promoting transport composite separator comprising silver nanoparticles and ionic liquid.
본 발명에서도 상기 대한민국특허출원 제10-2006-37340호와 같이 나노입자를 이온성액체를 통하여 활성화시킨다는 점에서는 동일하나 상기 특허출원과는 달리 나노입자로서 은나노입자가 아닌 구리나노입자 또는 금나노입자를 사용한다는 점에서 상이하다.In the present invention, the same as that of activating the nanoparticles through the ionic liquid as in the Republic of Korea Patent Application No. 10-2006-37340, but unlike the patent application, the nanoparticles are not copper nanoparticles or gold nanoparticles as silver nanoparticles It is different in that it is used.
이온성액체는 통상의 금속 양이온과 비금속 음이온으로 이루어진 금속염 화합물과는 달리 100℃ 이하의 온도에서 액체로 존재하여 이온성액체(Ionic Liquids, ILs)라고 한다. 이온성액체는 유기양이온과 음이온으로 구성되어 있으며, 양이온으로서는 디알킬이미다졸륨, 알킬피리디늄, 4급 암모늄, 4급 포스포늄 등이 있으며, 음이온으로서는 NO3 -, BF4 -, PF6 -, AlCl4 -, Al2Cl7 -, AcO-, TfO-(Trifluoromethanesulfonate), Tf2N-(Trifluoromethanesulfonylamide), (CF3SO2)2N, CH3CH(OH)CO2 -(L-lactate) 등이 있다.Ionic liquids, unlike conventional metal salt compounds consisting of metal cations and non-metal anions, exist as liquids at temperatures below 100 ° C and are called ionic liquids (ILs). The ionic liquid is composed of organic cations and anions, and the like, cation as dialkylimidazolium, alkyl pyridinium, quaternary ammonium, quaternary phosphonium, as the negative ions NO 3 -, BF 4 -, PF 6 - , AlCl 4 -, Al 2 Cl 7 -, AcO -, TfO - (Trifluoromethanesulfonate), Tf 2 N - (Trifluoromethanesulfonylamide), (
이온성액체는 독특한 물리적, 화학적 성질로 인하여 균일계 촉매반응의 용매, HF와 같은 유해물질을 대체하는 촉매, 전지의 전해질, 가스-가스 분리 또는 액-액 분리의 분리 매개체로서 사용되기도 한다.Ionic liquids are often used as separation mediators for solvents in homogeneous catalysis, catalysts to replace harmful substances such as HF, electrolytes in batteries, gas-gas separation or liquid-liquid separation due to their unique physical and chemical properties.
본 발명은 구리나노입자 또는 금나노입자의 활성과 이온성액체의 분리 매개체로서의 역할에 착안하여 본 발명을 완성하게 되었다.The present invention has been completed by focusing on the activity of copper nanoparticles or gold nanoparticles and the role of a separation medium between ionic liquids.
본 발명의 목적은 분자량과 물리적 성질이 유사하여 종래의 방법으로는 분리하기가 어려웠던 분자량이 비슷한 올레핀과 파라핀의 분리가 가능하도록 올레핀의 촉진수송이 가능한 복합분리막을 제공하기 위하여, 구리나노입자 또는 금나노입자와 이온성액체를 이용한 올레핀 촉진수송 복합분리막을 제공하는 데 있다.SUMMARY OF THE INVENTION An object of the present invention is to provide a composite membrane capable of promoting transport of olefins to enable separation of olefins and paraffins having similar molecular weights, which are difficult to separate by conventional methods due to similar molecular weights and physical properties. An olefin promoted transport composite membrane using nanoparticles and an ionic liquid is provided.
상기의 목적을 달성하기 위하여, 본 발명은 다공성지지체 위에 구리나노입자 또는 금나노입자와, 이온성액체를 포함하여 이루어지는 올레핀 촉진수송 복합분리막을 제공한다.In order to achieve the above object, the present invention provides an olefin promoted transport composite membrane comprising a copper nanoparticles or gold nanoparticles and an ionic liquid on a porous support.
특히, 상기 다공성지지체가 폴리설폰 다공성지지체인 것이 더욱 바람직하다.In particular, it is more preferable that the porous support is a polysulfone porous support.
특히, 이온성액체 1 중량부에 대하여 구리나노입자 또는 금나노입자가 0.05 ~ 1 중량부인 것이 바람직하다.In particular, the copper nanoparticles or gold nanoparticles are preferably 0.05 to 1 parts by weight based on 1 part by weight of the ionic liquid.
특히, 상기 이온성액체로 BMIM+BF4 - 또는 BMIM+NO3 -인 것이 바람직하다. In particular, the ionic liquid in BMIM + BF 4 - is preferably - or BMIM + NO 3.
본 발명은 구리나노입자 또는 금나노입자와, 이온성액체를 포함하여 이루어지는 올레핀 촉진수송 복합분리막을 제공한다. 본 발명에서는 구리나노입자 또는 금나노입자가 올레핀의 촉진수송 전달체(carrier)로서 작용하기 위하여, 이온성액체를 구리나노입자 또는 금나노입자의 부분적인 양이온화의 도구로 이용하며, 고분자분리막 형태가 아닌 구리나노입자 또는 금나노입자와 이온성액체로 이루어진 복합분리막을 제공한다.The present invention provides an olefin promoted transport composite membrane comprising copper nanoparticles or gold nanoparticles and an ionic liquid. In the present invention, ionic liquid is used as a tool for partial cationization of copper nanoparticles or gold nanoparticles in order for the copper nanoparticles or gold nanoparticles to act as a carrier for olefins. The present invention provides a composite separator consisting of copper nanoparticles or gold nanoparticles and an ionic liquid.
본 발명에서 이온성액체와 구리나노입자의 상호작용을 살펴보면 다음과 같다. 도 1은 본 발명에서 이온성액체가 구리나노입자의 표면을 부분적으로 양이온화하는 매커니즘에 대한 설명도이다. 도 1과 같이, 구리나노입자에 이온성액체, 예를 들어 BMIM+BF4 - 중 음이온인 BF4 -가 구리나노입자의 표면으로 접근하여 구리나노입자를 부분적으로 양이온화시킴으로써, 구리나노입자가 올레핀의 π결합과 가역적으로 반응할 수 있는 올레핀의 전달체(carrier)로서 작용하게 된다. 상기 도 1의 매커니즘과 같이, 이러한 구리나노입자의 부분적인 양이온화를 위하여 통상의 이온성액체가 모두 가능하기 때문에 본 발명에서는 이온성액체의 종류에 제한을 두지 않으며, 이하 실시예는 발명의 이해를 돕기 위한 실시예일 뿐으로서 본 발명은 하기 실시예의 이온성액체에 한정되지 않는다. 상기 매커니즘은 금나노입자에도 동일하게 적용되며, 이는 본 발명자의 대한민국특허출원 제10-2006-37430호에서 은나노입자의 양이온 매커니즘과 동일하다.Looking at the interaction of the ionic liquid and copper nanoparticles in the present invention. 1 is an explanatory diagram of a mechanism in which an ionic liquid partially cations the surface of copper nanoparticles in the present invention. As shown in FIG. 1, an ionic liquid, for example, BMIM + BF 4 − Of the anion of BF 4 -, by the partially cationic by the copper nanoparticles to access the surface of the copper nano-particle formation, the copper nano-particles is to act as a carrier (carrier) of an olefin capable of reacting with π bond of the olefin and reversible . As in the mechanism of FIG. 1, since all conventional ionic liquids are possible for partial cationization of such copper nanoparticles, the present invention does not limit the type of ionic liquid, and the following examples are understood. The present invention is not limited to the ionic liquid of the following examples merely by way of example. The mechanism is equally applicable to gold nanoparticles, which is the same as the cationic mechanism of silver nanoparticles in Korean Patent Application No. 10-2006-37430.
본 발명에서 적절한 이온성액체와 구리나노입자 또는 금나노입자의 중량비는 1 : 0.05~1이 바람직하다. 나노입자의 함량이 너무 적으면 촉진수송의 효과를 볼 수 없으며, 너무 많으면 이온성액체와의 상분리가 일어나 분리막으로서의 역할을 할 수 없기 때문이다.
본 발명에서 미소기공 다공성지지체는 투과성이 충분하고 기계적인 강도를 유지할 수 있는 것이면 재질과 상관없이 사용가능하다. 예를 들면, 다공성 고분자막이나 세라믹막 모두 다공성지지체로서 사용가능하며, 그 형상도 평판형, 튜브형, 관형 등이 모두 가능하다. 특히, 고분자막 다공성지지체 재질로서 폴리설폰, 폴리에스테르가 많이 사용되며, 이 중 폴리설폰막이 가장 사용빈도가 높다.In the present invention, the weight ratio of the ionic liquid and the copper nanoparticles or the gold nanoparticles is preferably 1: 0.05 to 1. If the content of the nanoparticles is too small, the effect of the promotion transport can not be seen, if too much because the phase separation with the ionic liquid can not act as a separator.
In the present invention, the microporous porous support can be used irrespective of the material as long as it has sufficient permeability and can maintain mechanical strength. For example, both the porous polymer membrane and the ceramic membrane can be used as the porous support, and the shapes thereof can also be flat, tubular, tubular, or the like. In particular, polysulfone and polyester are widely used as a porous material of the polymer membrane, and among these, polysulfone membrane has the highest frequency of use.
실시예1Example 1 : : 구리나노입자와With copper nanoparticles 이온성액체로With ionic liquid BMIMBMIM ++ BFBF 44 - - 사용한 복합막Used composite membrane
구리나노입자(평균 100nm)는 Aldrich Chemical社로부터 구입하였으며, BMIM+BF4 -(1-butyl-3-methylimidazolium tetrafluoroborate)는 C-TRI사로부터 구입하여 별도의 처리없이 입수한 대로 실험에 사용하였다.Were purchased from the Aldrich Chemical社copper nanoparticles (average 100nm), BMIM + BF 4 - (1-butyl-3-methylimidazolium tetrafluoroborate) was used in the experiments as obtained by purchasing from the C-TRI captured without further processing.
이온성액체(ILs)와 나노입자의 복합분리막의 제조는, 이온성액체에 구리나노입자를 분산시켜 제조하였으며, BMIM+BF4 - 대 구리나노입자의 중량비는 1 : 0.4였다. BMIM+BF4 -의 경우 점도(viscosity)가 234 cP(at 25℃)로서, 점도가 매우 높아 구리나노입자와 이온성액체만으로 복합분리막의 제조가 가능하다.The composite separator of ionic liquids (ILs) and nanoparticles was prepared by dispersing copper nanoparticles in an ionic liquid, and the weight ratio of BMIM + BF 4 - to copper nanoparticles was 1: 0.4. BMIM + BF 4 - in the case the viscosity (viscosity) as a 234 cP (at 25 ℃), it is possible to manufacture the composite separator viscosity is very high, only the copper nano-particles with an ionic liquid.
상기 이온성액체와 구리나노입자의 혼합용액을 코팅하기 위한 지지체로, 미소기공(microporous) 폴리설폰(polysulfone) 지지체(새한인더스트리社)를 사용하였으며, RK Control Coater(Model 101, Control Coater RK Print-Coat Instruments LTD)을 이용하여 상기 지지체에 고분자 혼합용액을 코팅하였다.As a support for coating the mixed solution of the ionic liquid and the copper nanoparticles, a microporous polysulfone support (Saehan Industries, Inc.) was used, and RK Control Coater (Model 101, Control Coater RK Print-). Coat Instruments LTD) was used to coat the polymer mixture solution.
실시예 2 : 금나노입자와 이온성액체로 BMIM+BF4 - 사용한 복합막Example 2 Composite Membrane Using BMIM + BF 4 - with Gold Nanoparticles and Ionic Liquids
금나노입자(평균 50~130nm)는 Aldrich Chemical社로부터 구입하여 사용하였으며, BMIM+BF4 - 대 금나노입자의 중량비는 1 : 0.1인 것을 제외하고는 실시예1과 동일한 방법으로 제조하였다.Gold nanoparticles (average 50 ~ 130nm) was purchased from Aldrich Chemical Co., Ltd., and was prepared in the same manner as in Example 1 except that the weight ratio of BMIM + BF 4 - gold nanoparticles is 1: 0.1.
비교예Comparative example
구리나노입자 또는 금나노입자가 전혀 첨가되지 않은 점을 제외하고는 실시 예 1과 동일한 방법으로 제조하였다. 즉, 폴리설폰 지지체에 BMIM+BF4 - 만을 코팅하여 분리막을 제조하였다.It was prepared in the same manner as in Example 1 except that no copper nanoparticles or gold nanoparticles were added. That is, the membrane was prepared by coating only BMIM + BF 4 - on the polysulfone support.
실험예Experimental Example 1 : One : 비교예Comparative example 및 And 실시예Example 1 내지 1 to 실시예2의Example 2 총투과도 및 선택도 실험 Total Transmittance and Selectivity Experiment
비교예인 BMIM+BF4 -만으로 이루어진 분리막과 실시예 1 및 실시예2의 BMIM+BF4 -과 구리나노입자 1:0.4 또는 BMIM+BF4 -과 금나노입자 1:0.1로 이루어진 복합분리막에 대한 프로필렌과 프로판 혼합가스(1:1 부피비)의 총투과도 및 선택도에 대한 실험을 하였다.For a composite membrane consisting of only BMIM + BF 4 -as a comparative example and a composite membrane consisting of BMIM + BF 4 - and copper nanoparticles 1: 0.4 or BMIM + BF 4 - and gold nanoparticles 1: 0.1 of Examples 1 and 2 The total permeability and selectivity of the mixed propylene and propane gas (1: 1 volume ratio) were tested.
투과도에 대한 테스트는 mass flow meter(MFM)을 이용하여 측정하였다. 가스투과도(gas permeance)의 단위는 GPU이며, 1 GPU = 1 x 10-6cm3(STP)/(cm2 sec cmHg)이다. 프로필렌과 프로판의 혼합가스의 경우 MFM만으로는 각 성분별 투과도의 측정이 불가능하므로, MFM과 함께 가스크로마토그라피를 이용하여 프로필렌과 프로판의 투과도를 측정하였다. 사용된 가스크로마토그라피는 TCD 디텍터와 unibead 2S 60/80 팩킹칼럼을 장착한 가스크로마토그라피(휴렛팩커드사社 G1530A)를 사용하였다.The test for permeability was measured using a mass flow meter (MFM). The unit of gas permeance is GPU, 1 GPU = 1 x 10 -6 cm 3 (STP) / (cm 2 sec cmHg). In the case of the mixed gas of propylene and propane, the permeability of each component cannot be measured by MFM alone, so the permeability of propylene and propane was measured using gas chromatography with MFM. The gas chromatograph used was a gas chromatograph equipped with a TCD detector and an unibead 2S 60/80 packing column (H1 Packer G1530A).
하기 표 1은 실험예 1의 결과로서, 비교예의 BMIM+BF4 -만으로 이루어진 분리막의 경우 프로필렌/프로판의 선택도가 0.9밖에 되지 않으며, 총투과도 역시 0.5GPU로서 프로필렌과 프로판의 분리용 분리막으로 사용이 불가능함을 알 수 있다. 그러나, 본 발명의 실시예 1 및 실시예2의 복합분리막의 경우 프로필렌의 선택도가 각각 16, 12이며, 총투과도는 각각 5.2, 5.5로서, 선택도와 총투과도가 모두 매우 크게 증가하는 전형적인 촉진수송의 형태를 나타내고 있다. 즉, 본 발명의 실시예 1 및 실시예2의 복합분리막의 올레핀의 분리성능 향상은 이온성액체로 인하여 구리나노입자와 금나노입자가 부분적으로 양이온화되어 올레핀의 촉진수송이 가능하게 되었기 때문임을 확인할 수 있었다.Table 1 is a result of Experimental Example 1, in the case of the membrane consisting only of BMIM + BF 4 -of the comparative example only propylene / propane selectivity is only 0.9, the total permeability is also used as a separation membrane for propylene and propane as 0.5GPU It can be seen that this is impossible. However, in the composite membranes of Examples 1 and 2 of the present invention, the propylene selectivity is 16 and 12, respectively, and the total permeability is 5.2 and 5.5, respectively. It shows the form of. That is, the separation performance of olefins in the composite membranes of Examples 1 and 2 of the present invention is improved because copper nanoparticles and gold nanoparticles are partially cationized due to the ionic liquid, thereby facilitating the transport of olefins. I could confirm it.
표 1Table 1
지금까지 살펴본 바와 같이 본 발명은 이온성액체와 구리나노입자 또는 금나노입자의 복합분리막을 이용하여 올레핀/파라핀의 촉진수송분리가 가능한 복합분리 막을 제공할 수 있으며, 이러한 촉진수송이 가능한 이유는 이온성액체에 의하여 구리나노입자 또는 금나노입자가 양이온화되기 때문이다.As described above, the present invention can provide a composite separation membrane capable of facilitated transport separation of olefins / paraffins by using a composite separation membrane of ionic liquids and copper nanoparticles or gold nanoparticles. This is because copper nanoparticles or gold nanoparticles are cationized by the liquid solution.
상기의 실시예 및 실험예는 이온성액체로 BMIM+BF4 를 사용한 예를 보였으나, 이는 본 발명을 설명하기 위한 구체적인 실시예일 뿐으로서, 본 발명의 기술적 핵심은 금속염 형태가 아닌 구리나노입자 및 금나노입자를 촉진수송의 운반체로 사용 가능하며, 구리나노입자 및 금나노입자를 운반체로 활성화시키기 위하여 이온성액체를 사용한다는 것인 바, 본 발명의 권리범위는 이온성액체에 대한 제약이 없음이 당연하다.The above examples and experimental examples showed an example of using BMIM + BF 4 as an ionic liquid, but this is only a specific embodiment for explaining the present invention, the technical core of the present invention is not a metal salt form copper nanoparticles and Gold nanoparticles can be used as a carrier for promoting transport, and the use of ionic liquids to activate copper nanoparticles and gold nanoparticles as carriers, the scope of the present invention is not limited to ionic liquids This is natural.
지금까지 살펴본 바와 같이, 본 발명은 구리나노입자 또는 금나노입자를 이용한 올레핀/파라핀의 선택적인 촉진수송이 가능한 구리나노입자 또는 금나노입자와 이온성액체의 복합분리막을 제공한다. 본 발명의 복합분리막은 촉진수송 매커니즘을 이용한 복합분리막으로서, 올레핀과 파라핀의 분리, 예를 들어, 프로판과 프로필렌 등과 같이 분자량과 물리적인 특성이 유사하여 분리하기 어려운 물질의 경우에도 쉽게 분리가 가능하여 다양한 분리 공정에 적용 가능하다.As described above, the present invention provides a composite membrane of copper nanoparticles or gold nanoparticles and an ionic liquid capable of selectively promoting transport of olefins / paraffins using copper nanoparticles or gold nanoparticles. The composite membrane of the present invention is a composite membrane using a facilitation transport mechanism, the separation of olefin and paraffin, for example, propane and propylene can be easily separated even in the case of difficult to separate material similar in molecular weight and physical properties Applicable to various separation processes.
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|---|---|---|---|---|
| KR20010065737A (en) * | 1999-12-30 | 2001-07-11 | 박호군 | Solid State Facilitated Transport Membranes for Alkene Separation Using Polymer Electrolytes |
| KR20020068648A (en) * | 2001-02-21 | 2002-08-28 | 한국과학기술연구원 | Stabilized Solid State Polymer Electrolyte Facilitated Transport Membranes using Surfactants |
| KR100716470B1 (en) | 2006-04-26 | 2007-05-10 | 한양대학교 산학협력단 | The facilitated olefin transporting composite membrane comprising nanosized silver metal and ionic liquid |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20010065737A (en) * | 1999-12-30 | 2001-07-11 | 박호군 | Solid State Facilitated Transport Membranes for Alkene Separation Using Polymer Electrolytes |
| KR20020068648A (en) * | 2001-02-21 | 2002-08-28 | 한국과학기술연구원 | Stabilized Solid State Polymer Electrolyte Facilitated Transport Membranes using Surfactants |
| KR100716470B1 (en) | 2006-04-26 | 2007-05-10 | 한양대학교 산학협력단 | The facilitated olefin transporting composite membrane comprising nanosized silver metal and ionic liquid |
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