KR101269857B1 - Catalyst for Selective Hydrogenation of Alkynes - Google Patents
Catalyst for Selective Hydrogenation of Alkynes Download PDFInfo
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- KR101269857B1 KR101269857B1 KR1020110034893A KR20110034893A KR101269857B1 KR 101269857 B1 KR101269857 B1 KR 101269857B1 KR 1020110034893 A KR1020110034893 A KR 1020110034893A KR 20110034893 A KR20110034893 A KR 20110034893A KR 101269857 B1 KR101269857 B1 KR 101269857B1
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- catalyst
- mixed metal
- copper
- metal oxide
- iron
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- 239000003054 catalyst Substances 0.000 title claims abstract description 93
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 38
- 150000001345 alkine derivatives Chemical class 0.000 title claims abstract description 28
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 100
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 70
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 63
- 229910003455 mixed metal oxide Inorganic materials 0.000 claims abstract description 49
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 39
- 229910052742 iron Inorganic materials 0.000 claims abstract description 32
- 239000010949 copper Substances 0.000 claims abstract description 30
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 29
- 150000001336 alkenes Chemical class 0.000 claims abstract description 29
- 229910052802 copper Inorganic materials 0.000 claims abstract description 27
- 239000011148 porous material Substances 0.000 claims abstract description 17
- 229910003445 palladium oxide Inorganic materials 0.000 claims abstract description 12
- 239000002245 particle Substances 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 8
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 6
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 125000000623 heterocyclic group Chemical group 0.000 claims description 3
- 229910052596 spinel Inorganic materials 0.000 claims description 3
- 239000011029 spinel Substances 0.000 claims description 3
- 239000005751 Copper oxide Substances 0.000 claims description 2
- 229910000431 copper oxide Inorganic materials 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 125000001931 aliphatic group Chemical group 0.000 claims 1
- 239000007809 chemical reaction catalyst Substances 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 39
- 230000003993 interaction Effects 0.000 abstract description 3
- 230000008901 benefit Effects 0.000 abstract description 2
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- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 16
- 239000000243 solution Substances 0.000 description 16
- 238000002360 preparation method Methods 0.000 description 15
- -1 alkynes compounds Chemical class 0.000 description 14
- 239000000377 silicon dioxide Substances 0.000 description 13
- UEXCJVNBTNXOEH-UHFFFAOYSA-N Ethynylbenzene Chemical group C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 description 12
- 239000002105 nanoparticle Substances 0.000 description 11
- 239000000843 powder Substances 0.000 description 11
- 230000000694 effects Effects 0.000 description 10
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- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 239000000376 reactant Substances 0.000 description 7
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 5
- 229910004298 SiO 2 Inorganic materials 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 150000001335 aliphatic alkanes Chemical class 0.000 description 4
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 101150003085 Pdcl gene Proteins 0.000 description 3
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 3
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- 238000003786 synthesis reaction Methods 0.000 description 3
- 229910021642 ultra pure water Inorganic materials 0.000 description 3
- 239000012498 ultrapure water Substances 0.000 description 3
- NKJOXAZJBOMXID-UHFFFAOYSA-N 1,1'-Oxybisoctane Chemical compound CCCCCCCCOCCCCCCCC NKJOXAZJBOMXID-UHFFFAOYSA-N 0.000 description 2
- AUHZEENZYGFFBQ-UHFFFAOYSA-N 1,3,5-trimethylbenzene Chemical compound CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 2
- QXSWHQGIEKUBAS-UHFFFAOYSA-N 1-ethynyl-4-fluorobenzene Chemical group FC1=CC=C(C#C)C=C1 QXSWHQGIEKUBAS-UHFFFAOYSA-N 0.000 description 2
- KSZVOXHGCKKOLL-UHFFFAOYSA-N 4-Ethynyltoluene Chemical group CC1=CC=C(C#C)C=C1 KSZVOXHGCKKOLL-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- IPBVNPXQWQGGJP-UHFFFAOYSA-N acetic acid phenyl ester Natural products CC(=O)OC1=CC=CC=C1 IPBVNPXQWQGGJP-UHFFFAOYSA-N 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 239000000908 ammonium hydroxide Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 229940049953 phenylacetate Drugs 0.000 description 2
- WLJVXDMOQOGPHL-UHFFFAOYSA-N phenylacetic acid Chemical compound OC(=O)CC1=CC=CC=C1 WLJVXDMOQOGPHL-UHFFFAOYSA-N 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000011949 solid catalyst Substances 0.000 description 2
- 239000012798 spherical particle Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- JWVTWJNGILGLAT-UHFFFAOYSA-N 1-ethenyl-4-fluorobenzene Chemical compound FC1=CC=C(C=C)C=C1 JWVTWJNGILGLAT-UHFFFAOYSA-N 0.000 description 1
- FGRBYDKOBBBPOI-UHFFFAOYSA-N 10,10-dioxo-2-[4-(N-phenylanilino)phenyl]thioxanthen-9-one Chemical compound O=C1c2ccccc2S(=O)(=O)c2ccc(cc12)-c1ccc(cc1)N(c1ccccc1)c1ccccc1 FGRBYDKOBBBPOI-UHFFFAOYSA-N 0.000 description 1
- PITRRWWILGYENJ-UHFFFAOYSA-N 2-[2-[2-[2-[2-(4-nonylphenoxy)ethoxy]ethoxy]ethoxy]ethoxy]ethanol Chemical compound CCCCCCCCCC1=CC=C(OCCOCCOCCOCCOCCO)C=C1 PITRRWWILGYENJ-UHFFFAOYSA-N 0.000 description 1
- JVKRKMWZYMKVTQ-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]pyrazol-1-yl]-N-(2-oxo-3H-1,3-benzoxazol-6-yl)acetamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C=1C=NN(C=1)CC(=O)NC1=CC2=C(NC(O2)=O)C=C1 JVKRKMWZYMKVTQ-UHFFFAOYSA-N 0.000 description 1
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 229910002554 Fe(NO3)3·9H2O Inorganic materials 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 150000007824 aliphatic compounds Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001722 carbon compounds Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- DIOQZVSQGTUSAI-NJFSPNSNSA-N decane Chemical compound CCCCCCCCC[14CH3] DIOQZVSQGTUSAI-NJFSPNSNSA-N 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000003203 everyday effect Effects 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 239000011981 lindlar catalyst Substances 0.000 description 1
- 238000013507 mapping Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- DIOQZVSQGTUSAI-UHFFFAOYSA-N n-butylhexane Natural products CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- SLYCYWCVSGPDFR-UHFFFAOYSA-N octadecyltrimethoxysilane Chemical compound CCCCCCCCCCCCCCCCCC[Si](OC)(OC)OC SLYCYWCVSGPDFR-UHFFFAOYSA-N 0.000 description 1
- 239000010412 oxide-supported catalyst Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000000527 sonication Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/51—Spheres
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
- C07C5/08—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of carbon-to-carbon triple bonds
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Abstract
본 발명은 알킨으로부터 알켄의 선택적 수소화 반응용 촉매에 관한 것으로서, 더욱 상세하게는 코어-다공성 쉘 구조를 갖는 실리카 입자의 쉘 기공에 팔라듐, 및 철과 구리를 함유하는 혼합금속 산화물을 담지시킨 알킨으로부터 알켄의 선택적 수소화 반응용 촉매에 관한 것이다. 본 발명의 촉매는 팔라듐과 철과 구리를 함유하는 혼합금속 산화물과의 근접 상호 작용(proximal interaction), 그리고 구조적 특성으로 알킨을 선별적으로 알켄으로 전환하는 뛰어난 선택성을 갖는다. 또한, 자성을 갖는 철을 함유하는 혼합금속 산화물은 초상자성 (superparamagnetic) 특성을 갖게 되어 사용 후 자석으로 쉽게 분리해서 다시 활용할 수 있는 장점이 있다.The present invention relates to a catalyst for the selective hydrogenation of alkenes from alkynes, and more particularly from alkyne in which palladium and mixed metal oxides containing iron and copper are supported in shell pores of silica particles having a core-porous shell structure. A catalyst for the selective hydrogenation of alkenes. The catalyst of the present invention has excellent selectivity for the selective conversion of alkynes to alkenes due to the proximal interaction of palladium with mixed metal oxides containing iron and copper, and structural properties. In addition, the mixed metal oxide containing iron having a magnetic has the superparamagnetic (superparamagnetic) characteristics there is an advantage that can be easily separated and reused by a magnet after use.
Description
본 발명은 삼중결합을 가지는 알킨을 수소화 반응을 통해서 이중결합을 갖는 알켄으로 전환하는, 높은 선택성을 가진 촉매에 관한 것이다.
The present invention relates to a catalyst having a high selectivity for converting alkyne having a triple bond to an alkene having a double bond through a hydrogenation reaction.
불포화 탄화수소의 선택적 수소화 반응 공정은 공업적으로 매우 중요하다. 특히, 나프타를 분해해서 생기는 기초 생성물 중에서 탄소의 수가 2 ~ 4 개인 지방족 화합물, 그리고 방향족 화합물인 스티렌 계열 물질들은 고분자 화합물의 단량체로 활용되기 때문에 공업적으로 매우 중요한 탄소 화합물들이다. 이러한 화합물들을 제조하는 공정 중에 필연적으로 삼중결합을 갖는 알킨(alkynes) 화합물들이 다량 포함되어 있는데, 이러한 알킨은 고분자 중합 반응에 있어 촉매의 기능을 감소시키는 독(poison) 성분으로 작용하거나, 중합도를 낮추는데 결정적인 역할을 하는 것으로 알려져 있다. 예를 들면, 일상생활에서 많이 사용되고 있는 고분자 재료인 폴리에틸렌, 폴리프로필렌, 폴리스타이렌 등을 만들기 위해서 에틸렌, 프로필렌, 스티렌 단량체를 원료로 사용하고 있는데, 이들 단량체에 삼중결합을 가지는 대응되는 알킨의 함량을 수 ppm 이하로 조절해야만 높은 수율로 고분자 재료를 제조할 수 있다. 따라서 나프타에서 생성된 다량의 아세틸렌을 포함한 에틸렌에서, 포화 탄화수소인 에탄을 생성하지 않으면서 아세틸렌을 에틸렌으로만 선택적으로 전환하는 촉매를 개발한다면 에틸렌 단량체로부터 매우 효율적으로 고순도의 폴리에틸렌을 제조할 수 있다. 이러한 이유에서 잔존하는 알킨을 선택적으로 수소화 반응시켜서 순도가 높은 알켄으로 전환시켜 주는 촉매를 개발하는 연구가 그 동안 꾸준하게 진행되어져 오고 있다.The selective hydrogenation process of unsaturated hydrocarbons is of great industrial importance. In particular, aliphatic compounds having 2 to 4 carbons and aromatic styrene-based materials among the basic products produced by decomposing naphtha are industrially important carbon compounds because they are used as monomers of high molecular compounds. In the process of preparing these compounds, a large amount of alkynes compounds having triple bonds are inevitably included, and these alkynes act as a poison component that reduces the function of the catalyst in the polymerization of polymers or decreases the degree of polymerization. It is known to play a decisive role. For example, ethylene, propylene, and styrene monomers are used as raw materials to make polyethylene, polypropylene, and polystyrene, which are polymer materials commonly used in everyday life, and the amount of the corresponding alkyne having triple bonds to these monomers can be determined. It should be adjusted to below ppm to produce polymer materials in high yield. Therefore, if ethylene including a large amount of acetylene produced in naphtha is developed, a catalyst capable of selectively converting acetylene to ethylene without producing ethane, a saturated hydrocarbon, can be produced from polyethylene ethylene monomer with high purity. For this reason, researches on developing catalysts that selectively convert remaining alkynes to high-purity alkenes have been steadily progressing.
이러한 알킨에서 알켄으로 전환하는 공정은 다음 반응식 1과 같이 도식적으로 표시할 수 있다.This alkyne to alkene conversion process can be represented schematically as in the following Scheme 1.
[반응식 1][Reaction Scheme 1]
상기 반응식 1에 보인 것처럼 이상적인 촉매는 수소화 반응을 삼중결합을 가지는 알킨(1)에서 이중결합을 가지는 알켄(2)까지 일어나게 하고 더 이상 반응이 진행되지 않도록 하는 것이다. 하지만 실제적으로는 알켄 화합물을 생성하는 최적의 촉매는 알킨에서 알켄으로 반응하는 속도는 빠르게 진행되게 하고, 알켄(2)에서 알칸(3)으로의 반응은 진행하지 않거나 또는 가능한 느리게 하는 것이다. 이러한 반응 속도의 차이에 입각해서 초기에는 수소화 반응을 잘 촉진시켜 주는 팔라듐 촉매를 부분적으로 비활성화 시킨 린들라(Lindlar) 촉매를 사용하여 삼중결합 화합물을 이중결합 화합물로 선택적으로 전환하는데 사용하였다. 이러한 린들라 촉매에서는 팔라듐을 촉매 활성 금속으로 활용하고, 담체로는 주로 칼슘 카보네이트(CaCO3)를 사용하고, 팔라듐 촉매의 활성을 부분적으로 비활성화하기 위해서 납(Pb)과 같은 중금속 화합물을 넣는다. 린들라 촉매는 활성은 우수하나 재사용이 어렵고 무엇보다도 납과 같은 중금속을 분리할 수가 없어서 환경적으로 여러 문제를 야기하고 있다. 이러한 문제점을 극복하기 위하여 린들라 촉매를 대체할 수 있는 선택 촉매를 개발하기 위해서 많은 연구가 지금까지 지속적으로 진행되어 오고 있다.As shown in Scheme 1, the ideal catalyst is to cause the hydrogenation reaction to occur from alkyne ( 1 ) having a triple bond to alkene ( 2 ) having a double bond, so that the reaction does not proceed any further. In practice, however, the optimal catalyst to produce the alkene compound is to speed up the reaction from alkynes to alkenes, and the reaction from alkenes ( 2 ) to alkanes ( 3 ) does not proceed or is as slow as possible. Based on this difference in reaction rate, it was initially used to selectively convert triple bond compounds to double bond compounds using Lindlar catalyst which partially deactivated the palladium catalyst which promotes the hydrogenation reaction well. In such a Lindla catalyst, palladium is used as a catalytically active metal, mainly a calcium carbonate (CaCO 3 ) as a carrier, and a heavy metal compound such as lead (Pb) is added to partially deactivate the activity of the palladium catalyst. Lindlar catalysts have high activity but are difficult to reuse, and above all, they are unable to separate heavy metals such as lead, causing environmental problems. In order to overcome this problem, many studies have been continuously conducted to develop a selective catalyst that can replace the Lindla catalyst.
최근에는 미국 공개특허 제 2009/0221861 호, 제 2008/0033221 호, 그리고 미국 등록특허 제 6,689,926 호에서 보고된 것처럼 다양한 종류의 금속이 함유된 촉매를 이용해서 아세틸렌 화합물들을 선택적으로 수소화하고 있다. 하지만 이들 촉매들도 린들라 촉매와 비슷한 문제점을 가지고 있다. 첫째는 공업적으로 활용하기에는 선택성이 너무 낮고, 둘째는 조촉매(promoter)를 과량으로 사용해야만 높은 선택성을 보여주고, 셋째는 반응 후 분리가 어렵고 촉매 성분이 감소해서 재사용이 어렵다.Recently, acetylene compounds have been selectively hydrogenated using catalysts containing various kinds of metals, as reported in US 2009/0221861, 2008/0033221, and US Pat. No. 6,689,926. However, these catalysts also have similar problems as the Lindla catalyst. Firstly, the selectivity is too low for industrial use, and secondly, the selectivity is high only when the promoter is used in excess, and thirdly, the separation is difficult after the reaction and the catalyst component is reduced, making it difficult to reuse.
상기 내용과 같이 삼중결합을 가지는 알킨 화합물을 이중결합을 갖고 있는 알켄 화합물로 변환함에 있어 빠르고 선택적으로 알켄 화합물을 생성하면서 동시에 단일 결합 화합물의 생성을 최소화할 수 있는 사용 후에도 회수가 가능한 고체 촉매의 개발이 필요하다. 즉, 알킨 화합물을 선택적으로 수소화하여 알켄 화합물로 전환하고, 전환된 알켄 화합물은 단일결합을 가지는 알칸으로 수소화되는 반응이 가능한 일어나지 않도록 설계된 고체 촉매에 대한 요구가 증가되고 있다. 또한 이러한 촉매는 환경에 해로운 중금속을 포함하지 않으면서 동시에 사용 후에도 촉매가 변질 되지 않아야 하고 쉽게 반응물과 생성물로부터 회수할 수 있을 것을 요구하고 있다.
As described above, in the conversion of alkyne compound having a triple bond to an alkene compound having a double bond, a solid catalyst that can be recovered even after use can be generated quickly and selectively while minimizing the formation of a single bond compound. This is necessary. In other words, there is an increasing demand for a solid catalyst designed to selectively hydrogenate an alkyne compound to be converted into an alkene compound, and the converted alkene compound is hydrogenated into an alkane having a single bond. In addition, these catalysts do not contain heavy metals that are harmful to the environment and at the same time require that the catalysts not deteriorate even after use and be easily recovered from the reactants and products.
이에 본 발명자들은 상기와 같은 문제점을 해결하기 위해 노력한 결과, 팔라듐 나노 입자와 철과 구리를 기반으로 한 혼합금속 산화물 나노 입자를 다공성 실리카 구형 입자의 기공에 넣어 제조한 촉매를 개발하였고, 이러한 촉매는 수소화 반응이 알킨에서 알켄으로 매우 선택적으로 빠르게 진행되며, 또한, 초상자성 특성을 가지고 있어서 자석을 이용해서 쉽게 촉매 회수가 가능하고, 재사용해도 촉매의 활성이 크게 변하지 않음을 확인함으로써 본 발명을 완성하였다. 즉, 본 발명은 높은 선택성을 가지고 알킨을 수소화 반응시켜 알켄으로 전환시킬 수 있는 새로운 촉매의 제공에 그 목적이 있다.
Accordingly, the present inventors have made efforts to solve the above problems, and have developed a catalyst prepared by inserting palladium nanoparticles and mixed metal oxide nanoparticles based on iron and copper into pores of porous silica spherical particles. The hydrogenation reaction proceeds very quickly from alkyne to alkene, and also has superparamagnetic properties, making it easy to recover the catalyst using a magnet and completing the present invention by confirming that the activity of the catalyst does not change significantly. . That is, the present invention has an object to provide a new catalyst that can be converted to alkene by hydrogenation of alkyne with high selectivity.
본 발명은 코어-다공성 쉘 구조를 갖는 실리카 입자의 쉘 부분에 팔라듐, 및 철과 구리를 함유하는 혼합금속 산화물을 담지시킨 알킨으로부터 알켄의 선택적 수소화 반응용 촉매를 그 특징으로 한다.
The present invention is characterized by a catalyst for the selective hydrogenation of alkene from alkyne wherein palladium and a mixed metal oxide containing iron and copper are supported on a shell portion of silica particles having a core-porous shell structure.
본 발명에서 제안하는 촉매는 현재 알킨을 수소화 반응에 적용되고 있는 린들라 촉매와 대비할 때 별도의 조촉매를 사용하지 않고도 알킨 화합물이 알켄으로 전환되는 속도가 매우 빠르고 선택성이 매우 우수하다. 또한, 크기가 매우 잘 조절된 수백 나노미터의 직경을 가지며 코어-다공성 쉘 구조를 가지는 다공성 실리카를 담체로 사용함으로써, 촉매 반응에서 반응물의 확산이 매우 균일하게 이루어지고 알켄을 단일결합을 가지는 알칸으로 수소화하는 것을 방해하는 효과가 있어서 선택성이 나아지는 장점이 있다. 그리고, 본 발명의 촉매는 크기가 조절된 다공성 실리카의 기공에 자성을 가지는 철과 구리를 기반으로 한 혼합 금속 산화물 나노 입자가 담지되어 있는데, 이들 나노 입자는 초상자성 특성을 가지고 있어서 반응 후 자석을 이용해서 촉매를 쉽게 분리할 수 있으며, 또한 팔라듐 촉매의 활성을 높이는 시너지 효과를 제공한다.
The catalyst proposed in the present invention is very fast and highly selective in converting alkyne compounds to alkenes without using a separate promoter in contrast to the Lindla catalyst which is currently applied to hydrogenation of alkynes. In addition, by using a porous silica having a diameter of several hundred nanometers, which is very well sized, and having a core-porous shell structure as a carrier, the diffusion of the reactants is very uniform in the catalytic reaction, and the alkene is converted into a single bond having a single bond. There is an advantage that the selectivity is improved because there is an effect that hinders hydrogenation. In addition, the catalyst of the present invention carries mixed metal oxide nanoparticles based on iron and copper having magnetic properties in the pores of the porous silica having a size control, and these nanoparticles have superparamagnetic properties, thus providing a magnet after the reaction. The catalyst can be easily separated, and also provides a synergistic effect of increasing the activity of the palladium catalyst.
도 1은 본 발명의 코어-다공성 쉘 구조를 갖는 실리카 입자의 쉘 기공에 팔라듐(붉은 원), 및 철과 구리를 함유하는 혼합금속 산화물(푸른 사각형)이 담지된 촉매의 모식도이다.
도 2는 실시예 1에서 제조한, 코어-다공성 쉘 구조의 실리카 입자에 팔라듐/철과 구리의 혼합금속 산화물이 담지된 촉매 입자의 투과전자현미경(TEM) 사진이다.
도 3은 실시예 1에서 제조한, 코어-다공성 쉘 구조의 실리카 입자에 팔라듐/철과 구리의 혼합금속 산화물이 담지된 촉매 입자의 X-선 회절 패턴이다.
도 4는 수소화 반응 후, 코어-다공성 쉘 구조의 실리카 입자에 팔라듐/철과 구리의 혼합금속 산화물이 담지된 촉매 입자를 자석을 이용하여 분리하는 사진이다.1 is a schematic diagram of a catalyst in which shell pores of silica particles having a core-porous shell structure of the present invention are loaded with palladium (red circle) and mixed metal oxides (blue squares) containing iron and copper.
FIG. 2 is a transmission electron microscope (TEM) photograph of catalyst particles having a mixed metal oxide of palladium / iron and copper supported on silica particles having a core-porous shell structure prepared in Example 1. FIG.
3 is an X-ray diffraction pattern of catalyst particles in which a mixed metal oxide of palladium / iron and copper is supported on silica particles having a core-porous shell structure prepared in Example 1. FIG.
4 is a photograph showing separation of a catalyst particle having a mixed metal oxide of palladium / iron and copper supported on silica particles having a core-porous shell structure using a magnet after hydrogenation.
이하에서는 본 발명을 더욱 자세하게 설명하겠다.Hereinafter, the present invention will be described in more detail.
본 발명은 다공성 실리카 외각의 나노 크기의 기공 안에 팔라듐 입자와 철과 구리를 함유하는 혼합금속 산화물 입자를 넣어 제한된 공간 안에서 나노 입자 간에 근접 상호 작용(proximal interaction)을 통해서 알킨을 선별적으로 수소화 반응을 할 수 있는 촉매에 관한 것이다. 이러한 촉매는 다공성 실리카 구형 입자의 외각 기공에 촉매 활성이 뛰어난 팔라듐과 자성을 가지는 철과 구리를 함유하는 혼합금속 산화물 나노 입자들을 함유하고 있다. 생성된 알켄이 단일결합을 가지는 알칸으로 더 이상 수소화되는 반응을 억제할 수 있도록 알켄이 기공에 내장된 촉매와 접촉하는 것을 최소화할 수 있도록 나노 기공의 깊이와 크기를 조절하였고, 수소화 반응의 속도와 선택성을 높이기 위해서 팔라듐과 혼합금속 산화물 입자의 크기를 조절하였으며, 반응 후 촉매를 자석을 이용해서 간단하게 분리할 수 있도록 혼합 산화물에서 철과 다른 금속의 조성을 조절하였다.In the present invention, palladium particles and mixed metal oxide particles containing iron and copper are put in nano-sized pores of the outer surface of porous silica to selectively hydrogenate alkynes through proximal interactions between nanoparticles within a limited space. It relates to a catalyst that can be. Such a catalyst contains mixed metal oxide nanoparticles containing palladium and magnetic iron and copper having excellent catalytic activity in the outer pores of the porous silica spherical particles. The depth and size of the nanopores were adjusted to minimize the contact of alkenes with the catalysts embedded in the pores so that the resulting alkenes could no longer be hydrogenated into single-bonded alkanes. To increase the selectivity, the size of the palladium and mixed metal oxide particles were adjusted, and the composition of iron and other metals in the mixed oxide was adjusted so that the catalyst could be easily separated using a magnet after the reaction.
상기 실리카 입자는 코어-다공성 쉘의 구조를 가지며, 입자크기가 30 nm ~ 2 ㎛인 것을 사용하는 것이 비표면적을 높이는 측면에서 유리하며, 쉘의 두께가 1 ~ 500 nm 이며, 쉘의 기공크기가 1 ~ 30 nm 인 것을 사용하는 것이 좋다. 쉘의 두께와 쉘의 기공크기는 알켄의 알칸으로의 수소화 반응을 억제하기 위해 조절하며, 상기 범위의 두께 및 기공크기를 가짐으로써 알켄이 쉘 기공 안에 담지된 활성물질과 접촉하는 것을 최소화할 수 있다. 쉘의 두께는 실리카 코어-다공성 쉘 구조 합성 시 넣어주는 계면활성제의 탄소 개수(> C18)로 조절이 가능하며 쉘의 기공 크기는 암모니아를 이용한 실리카 코어-다공성 쉘 구조 합성 후 수열(hydrothermal)법이나 코어-다공성 쉘 구조 합성 시 1,3,5-트리메틸벤젠(1,3,5-trimethylbenzene, TMB)과 데켄(decene)을 첨가하는 방법으로 조절할 수 있다.The silica particles have a structure of a core-porous shell, it is advantageous to use a particle size of 30 nm ~ 2 ㎛ in terms of increasing the specific surface area, the thickness of the shell is 1 ~ 500 nm, the pore size of the shell It is better to use 1 to 30 nm. The thickness of the shell and the pore size of the shell are adjusted to suppress the hydrogenation of alkenes to alkanes, and by having the thickness and pore size in the above range, it is possible to minimize the contact of the alkene with the active material contained in the shell pores. . The thickness of the shell can be controlled by the number of carbon atoms (> C18) of the surfactant added during the synthesis of the silica core-porous shell structure, and the pore size of the shell is determined by hydrothermal method after synthesis of the silica core-porous shell structure using ammonia. The synthesis of the core-porous shell structure can be controlled by adding 1,3,5-trimethylbenzene (TMB) and decane.
이러한 코어-다공성 쉘 구조를 갖는 실리카 입자의 쉘 기공에 팔라듐과 철과 구리를 함유하는 혼합금속 산화물을 담지한다. 본 발명에서 상기 철과 구리를 함유하는 혼합금속 산화물은 바람직하게는 스피넬 구조를 가지는 혼합금속 산화물일 수 있다. 철과 구리를 함유하는 스피넬 구조의 혼합금속 산화물은 CuxFe3-xO4로 표시될 수 있으며, 소량의 Ni, Co 및 Mn 중에서 선택한 1종 이상이 첨가될 수도 있다. 산화물이 혼합형태인 경우 철산화물로는 Fe3O4, Fe2O3 또는 이들의 혼합물을 사용할 수 있고, 구리 산화물로는 CuO, Cu2O 또는 이들의 혼합물을 사용할 수 있다. 또한, 복합금속 산화물의 형태와, 개별 금속 산화물의 혼합형태를 혼성하여 적용하는 것도 가능하다. 이러한 철과 구리를 함유하는 혼합금속 산화물은 초상자성(superparamagnetic) 특성을 갖게 되어 반응 후 촉매만을 선별적으로 분리할 수 있으며, 활성물질인 팔라듐의 활성을 더욱 향상시키는 시너지 효과를 제공한다. 또한, 팔라듐과, 철과 구리를 함유하는 혼합금속 산화물의 근접 상호 작용(proximal interaction)으로 우수한 선택성을 발현시킬 수 있다.The shell pores of the silica particles having such a core-porous shell structure carry a mixed metal oxide containing palladium, iron and copper. In the present invention, the mixed metal oxide containing iron and copper may be a mixed metal oxide having a spinel structure. The mixed metal oxide of the spinel structure containing iron and copper may be represented by Cu x Fe 3-x O 4 , and one or more selected from a small amount of Ni, Co, and Mn may be added. When the oxide is in a mixed form, it may be used Fe 3 O 4 , Fe 2 O 3 or a mixture thereof as the iron oxide, CuO, Cu 2 O or a mixture thereof may be used as the copper oxide. In addition, it is also possible to mix and apply the form of a composite metal oxide and the mixed form of individual metal oxides. The mixed metal oxide containing iron and copper has a superparamagnetic property to selectively separate the catalyst after the reaction, and provides a synergy effect to further improve the activity of the active material palladium. In addition, excellent selectivity can be exhibited by the proximal interaction of palladium with a mixed metal oxide containing iron and copper.
팔라듐과 혼합금속 산화물의 입자크기는 1 ~ 30 nm 인 것이 바람직한데, 상기 범위의 입자크기를 갖는 활성 물질을 사용함으로써 수소화 반응의 속도와 선택성을 최적화할 수 있다. 팔라듐과 철과 구리를 함유하는 혼합금속 산화물의 입자크기는 소결(sintering) 방법 및 반응 온도를 통해서 조절할 수 있다.The particle size of the palladium and the mixed metal oxide is preferably 1 to 30 nm, it is possible to optimize the rate and selectivity of the hydrogenation reaction by using an active material having a particle size in the above range. The particle size of the mixed metal oxide containing palladium, iron and copper can be controlled through the sintering method and the reaction temperature.
상기 혼합금속 산화물은 구리원자와 철원자의 몰비가 1.0 : 0.5 ~ 2.9 인 것이 좋은데, 철원자의 몰비가 너무 낮을 경우 반응 후 촉매를 자석을 이용하여 분리하기 어려운 문제가 있을 수 있으며, 반대로 철원자의 몰비가 너무 높을 경우에는 구리와 팔라듐이 주는 시너지 효과를 방해하는 문제가 있을 수 있다. 또한, 실리카에 담지되어 있는 팔라듐의 양은 촉매 전체 중량 기준으로 0.01 ~ 10 중량%가 바람직하다. 팔라듐의 담지량이 0.01 중량% 미만이면 반응성이 떨어지는 문제가 있을 수 있으며, 10 중량%를 초과하면 반응성은 좋아질 수 있으나 선택도에 문제가 있을 수 있다. 또한, 실리카에 담지되는 철과 구리를 함유하는 혼합금속 산화물의 담지량 역시 촉매 전체 중량 기준 0.01 ~ 10 중량%로 맞추는 것이 촉매 회수 및 반응성과 수소화 반응의 이중 결합에 대한 선택도를 높이는 면에서 유리하다.The mixed metal oxide may have a molar ratio of copper atoms and iron atoms of 1.0: 0.5 to 2.9. If the molar ratio of iron atoms is too low, it may be difficult to separate the catalyst using a magnet after the reaction. If it is too high, there may be a problem that interferes with the synergistic effect of copper and palladium. In addition, the amount of palladium supported on the silica is preferably 0.01 to 10% by weight based on the total weight of the catalyst. If the supported amount of palladium is less than 0.01% by weight, there may be a problem that the reactivity is lowered, and when the amount of palladium exceeds 10% by weight, the reactivity may be improved but there may be a problem in selectivity. In addition, it is advantageous to adjust the amount of mixed metal oxides containing iron and copper supported on silica to 0.01 to 10% by weight based on the total weight of the catalyst in terms of increasing the catalyst recovery and the selectivity for the double bond of the reactivity and hydrogenation reaction. .
본 발명의 촉매는 알킨의 알켄으로의 수소화 반응에 적용 시 빠른 반응속도와 우수한 전환율, 높은 선택도를 나타낸다. 반응물인 알킨 화합물의 예로는 삼중결합을 가지고 있는 탄소수가 2 ~ 30 인 지방족 탄화수소 화합물 중에서 선택한 1종 이상의 것이고, 상기 지방족 탄화수소 화합물은 페닐기 또는 헤테로 고리기에 의해 치환 또는 비치환될 수도 있다. 상기 헤테로 고리기는 탄소 이외의 헤테로 원자로 O, S, N, P 등을 포함할 수 있다. 그러나, 본 발명의 촉매가 상기 알킨 화합물의 수소화 반응으로 제한되는 것은 아니다.
The catalyst of the present invention exhibits fast reaction rates, good conversion and high selectivity when applied to hydrogenation of alkynes to alkenes. Examples of the alkyne compound that is a reactant are one or more selected from aliphatic hydrocarbon compounds having 2 to 30 carbon atoms having a triple bond, and the aliphatic hydrocarbon compound may be substituted or unsubstituted by a phenyl group or a heterocyclic group. The heterocyclic group may include O, S, N, P, etc. as a hetero atom other than carbon. However, the catalyst of the present invention is not limited to the hydrogenation of the alkyne compound.
이하 본 발명을 실시예에 의거하여 더욱 상세히 설명하겠는바, 본 발명이 다음 실시예에 의해 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited by the following Examples.
[[ 실시예Example ]]
제조예 1 : 코어-다공성 쉘 구조의 실리카 입자 제조Preparation Example 1 Preparation of Silica Particles of Core-Porous Shell Structure
둥근 플라스크에 75 mL 에탄올과 10 mL 초순수 그리고 3 mL 수산화암모늄(ammonium hydroxide)을 함께 넣고 섞은 후 10분간 교반하였다. 위 용액에 테트라에톡시실란(tetraethoxysilane, 98%, Aldrich) 6 mL 를 넣어주고 격렬하게 2시간 동안 충분히 교반을 시켰다. 테트라에톡시실란 5 mL와 계면활성제인 n-옥타데실트리메톡시실란(n-octadecyltrimethoxysilane, 85%, TCI) 2 mL을 함께 섞은 용액을, 격렬하게 교반을 하는 위 혼합용액에 넣어주고 2시간 동안 교반시켰다. 합성된 코어-다공성 셀 구조의 실리카 입자는 원심분리기를 이용해 모아주고 에탄올을 이용해 여러 번 세척하고 공기 중에서 건조시키면 하얀 고체 가루를 얻었다. 얻은 하얀 고체 가루를 550℃에서 6 시간 동안 열처리를 해서 실리카 내에 남아 있는 모든 유기물들을 완전히 제거하였다.
75 mL ethanol, 10 mL ultrapure water and 3 mL ammonium hydroxide were added together in a round flask, followed by stirring for 10 minutes. 6 mL of tetraethoxysilane (98%, Aldrich) was added to the solution, followed by vigorous stirring for 2 hours. 5 mL of tetraethoxysilane and 2 mL of n-octadecyltrimethoxysilane (85%, TCI), which is a surfactant, are mixed together. Stirred. The synthesized core-porous cell structured silica particles were collected using a centrifuge, washed several times with ethanol and dried in air to obtain white solid powder. The white solid powder obtained was heat-treated at 550 ° C. for 6 hours to completely remove all organic matter remaining in the silica.
제조예 2 : 코어-다공성 쉘 구조의 실리카 입자에 팔라듐이 담지된 촉매 제조 Preparation Example 2 Preparation of Catalysts Supported with Palladium on Silica Particles of Core-Porous Shell Structure
상기 제조예 1에서 합성한 코어-다공성 셀 구조의 실리카 입자 0.2 g을 에탄올 10 mL에 완전히 분산시켰다. 위 용액에 3-아미노프로필트리에톡시실란(aminopropyltriethoxysilane, 98%+, Aldrich) 0.3 mL를 한 방울씩 넣어주고 50℃에서 6시간 동안 격렬하게 교반시켰다. 아민기로 기능화된 상기 실리카 입자를 원심분리기를 이용해 모으고 에탄올로 여러 번 세척한 후 오븐에서 건조시켰다. 이 때 건조된 분말은 흰색을 나타내었다. 충분히 건조시킨 분말을 10 mL 에탄올에 다시 분산시켰다. 위 용액을 격렬하게 교반해 주면서 K2PdCl4(98%, Aldrich) 0.0156 g 을 증류수 10 mL에 녹인 용액을 첨가하였다. 위 혼합 용액을 12시간 동안 격렬하게 교반한 후 원심분리기를 이용해 팔라듐이 부착된 코어-다공성 쉘 실리카 입자를 모으고 에탄올로 여러 번 세척한 후, 오븐에서 완전히 건조시켰다. 건조시킨 생성물은 전기로에서 500℃ 이상으로 열처리하여 팔라듐이 쉘 기공에 잘 담지되었는지를 투과전자현미경과 X-ray 분말 회절기를 통해서 확인하였다.
0.2 g of silica particles of the core-porous cell structure synthesized in Preparation Example 1 were completely dispersed in 10 mL of ethanol. 0.3 mL of 3-aminopropyltriethoxysilane (aminopropyltriethoxysilane, 98% +, Aldrich) was added dropwise to the solution and stirred vigorously at 50 ° C. for 6 hours. The silica particles functionalized with amine groups were collected using a centrifuge, washed several times with ethanol and dried in an oven. At this time, the dried powder was white. The fully dried powder was dispersed again in 10 mL ethanol. While stirring the solution vigorously, 0.0156 g of K 2 PdCl 4 (98%, Aldrich) was dissolved in 10 mL of distilled water. After stirring vigorously for 12 hours, the mixture solution was collected by using a centrifuge to collect core-porous shell silica particles attached with palladium, washed several times with ethanol, and then completely dried in an oven. The dried product was heat-treated at 500 ° C. or higher in an electric furnace to confirm that palladium was well supported in the shell pores through a transmission electron microscope and an X-ray powder diffractometer.
제조예 3 : 코어-다공성 쉘 구조의 실리카 입자에 혼합금속 산화물이 담지된 촉매 제조 Preparation Example 3 Preparation of Catalysts Supported by Mixed Metal Oxides in Silica Particles of Core-porous Shell Structure
상기 제조예 1에서 합성한 코어-다공성 셀 구조의 실리카 입자 1 g을 에탄올 10 mL에 분산시켰다. 분산시킨 용액에 Cu(NO3)2·2.5H2O(98%, Aldrich) 0.0573 g 과 Fe(NO3)3·9H2O(98%+, Aldrich) 0.1991 g을 넣어주고 구리와 철 용액이 잘 섞이도록 2 시간 이상 교반하였다. 용액이 잘 섞인 후에 20 mL의 n-옥틸에테르(TCI)와 1 mL의 계면활성제(Igepal CO-520, Aldrich)를 위에서 준비한 혼합용액에 넣어주고 1 시간 동안 초음파 처리와 교반을 실시하였다. 섞은 용액을 100℃로 가열해서 에탄올을 모두 증발시킨 후, 200℃로 온도를 올린 후 1시간 동안 유지시켰다. 이 후 300℃로 온도를 올려 3시간 동안 환류한 후에 상온까지 식혔다. 반응을 통해서 얻은 생성물을 원심분리기를 이용해서 모으고, 에탄올을 이용해서 여러 번 세척한 후 80℃ 오븐에서 완전히 건조시켰다. 건조시킨 생성물은 전기로에서 500℃ 이상에서 열처리를 하였다.
1 g of silica particles of the core-porous cell structure synthesized in Preparation Example 1 were dispersed in 10 mL of ethanol. Cu (NO 3) 2 · 2.5H 2 O (98%, Aldrich) 0.0573 g and the Fe (NO 3) 3 · 9H 2 O to put (98% +, Aldrich) 0.1991 g copper and iron in solution by dispersing solution The mixture was stirred for 2 hours or more to mix well. After the solution was well mixed, 20 mL of n-octyl ether (TCI) and 1 mL of surfactant (Igepal CO-520, Aldrich) were added to the mixed solution prepared above, followed by sonication and stirring for 1 hour. The mixed solution was heated to 100 ° C. to evaporate all of the ethanol, and then maintained at 200 ° C. for 1 hour. After raising the temperature to 300 ℃ reflux for 3 hours and then cooled to room temperature. The product obtained through the reaction was collected using a centrifuge, washed several times with ethanol and completely dried in an oven at 80 ℃. The dried product was heat-treated at 500 ° C. or higher in an electric furnace.
제조예Manufacturing example 4 : 다공성 4: porous 쉘이Shell 없고 코어만 있는 구형 실리카 입자 제조 Spherical Silica Particles Fabrication Without Cores
둥근 플라스크에 75 mL 에탄올과 10 mL 초순수 그리고 3 mL 수산화암모늄(ammonium hydroxide)을 함께 넣고 섞은 후 10분간 교반하였다. 위 용액에 테트라에톡시실란(tetraethoxysilane, 98%, Aldrich) 6 mL 를 넣어주고 격렬하게 2시간 동안 충분히 교반을 시켰다. 합성된 기공이 없는 코어 구조의 실리카 입자는 원심분리기를 이용해 모아주고 에탄올을 이용해 여러 번 세척하고 공기 중에서 건조시키면 하얀 고체 가루를 얻었다. 얻은 하얀 고체 가루를 550℃에서 6 시간 동안 열처리를 해서 실리카 내에 남아 있는 모든 유기물들을 완전히 제거하였다.
75 mL ethanol, 10 mL ultrapure water and 3 mL ammonium hydroxide were added together in a round flask, followed by stirring for 10 minutes. 6 mL of tetraethoxysilane (98%, Aldrich) was added to the solution, followed by vigorous stirring for 2 hours. Synthesized pore-free silica particles were collected using a centrifuge, washed several times with ethanol and dried in air to obtain white solid powder. The white solid powder obtained was heat-treated at 550 ° C. for 6 hours to completely remove all organic matter remaining in the silica.
제조예Manufacturing example 5 : 다공성 5: porosity 쉘이Shell 없고 코어만 있는 구형 실리카 입자에 팔라듐이 Core-spherical silica particles with no palladium 담지된Supported 촉매 제조 Catalyst preparation
상기 제조예 4 에서 합성한 기공이 없는 코어 구조의 실리카 입자 0.2 g을 에탄올 10 mL에 완전히 분산시켰다. 위 용액에 3-아미노프로필트리에톡시실란(aminopropyltriethoxysilane, 98%+, Aldrich) 0.3 mL를 한 방울씩 넣어주고 50℃에서 6시간 동안 격렬하게 교반시켰다. 아민기로 기능화된 상기 실리카 입자를 원심분리기를 이용해 모으고 에탄올로 여러 번 세척한 후 오븐에서 건조시켰다. 이 때 건조된 분말은 흰색을 나타내었다. 충분히 건조시킨 분말을 10 mL 에탄올에 다시 분산시켰다. 위 용액을 격렬하게 교반해 주면서 K2PdCl4(98%, Aldrich) 0.0156 g 을 증류수 10 mL에 녹인 용액을 첨가하였다. 위 혼합 용액을 12시간 동안 격렬하게 교반한 후 원심분리기를 이용해 팔라듐이 부착된 코어-다공성 쉘 실리카 입자를 모으고 에탄올로 여러 번 세척한 후, 오븐에서 완전히 건조시켰다.
0.2 g of the pore-free silica particles synthesized in Preparation Example 4 were completely dispersed in 10 mL of ethanol. 0.3 mL of 3-aminopropyltriethoxysilane (aminopropyltriethoxysilane, 98% +, Aldrich) was added dropwise to the solution and stirred vigorously at 50 ° C. for 6 hours. The silica particles functionalized with amine groups were collected using a centrifuge, washed several times with ethanol and dried in an oven. At this time, the dried powder was white. The fully dried powder was dispersed again in 10 mL ethanol. While stirring the solution vigorously, 0.0156 g of K 2 PdCl 4 (98%, Aldrich) was dissolved in 10 mL of distilled water. After stirring vigorously for 12 hours, the mixture solution was collected by using a centrifuge to collect core-porous shell silica particles attached with palladium, washed several times with ethanol, and then completely dried in an oven.
실시예 1 : 코어-다공성 쉘 구조의 실리카 입자에 팔라듐/혼합금속 산화물이 담지된 촉매 제조 Example 1 Preparation of Catalysts Supported with Palladium / Mixed Metal Oxide on Silica Particles of Core-porous Shell Structure
상기 제조예 3에서 합성한 혼합금속 산화물 촉매 0.2 g을 에탄올 10 mL에 완전히 분산시켰다. 위 용액에 3-아미노프로필트리에톡시실란 0.3 mL를 한 방울씩 넣어주고 50℃에서 6시간 동안 교반하였다. 표면이 아민으로 기능화된 입자를 원심분리기로 모아주고 에탄올로 세척 후 오븐에서 건조시켰다. 이 때 건조된 분말은 연한 갈색을 나타내었다. 충분히 건조시킨 분말을 10 mL 에탄올에 다시 분산시키고 격렬하게 교반을 해주면서 초순수 10 mL 에 용해시킨 0.0156 g K2PdCl4을 용액을 첨가하였다. 위 용액을 12 시간 동안 격렬하게 교반한 후 원심분리기를 이용해 팔라듐, 및 철을 함유하는 혼합금속 산화물이 담지된 실리카 입자를 모으고 에탄올로 여러 번 세척 후, 오븐에서 완전히 건조시켰다. 건조시킨 생성물은 전기로에서 500℃ 이상으로 열처리 하였다.0.2 g of the mixed metal oxide catalyst synthesized in Preparation Example 3 was completely dispersed in 10 mL of ethanol. 0.3 mL of 3-aminopropyltriethoxysilane was added dropwise to the solution and stirred at 50 ° C. for 6 hours. Particles functionalized with amines were collected in a centrifuge, washed with ethanol and dried in an oven. At this time, the dried powder was light brown. The sufficiently dried powder was dispersed again in 10 mL ethanol and stirred with vigorous stirring, and a solution of 0.0156 g K 2 PdCl 4 dissolved in 10 mL of ultrapure water was added. The solution was stirred vigorously for 12 hours, and then collected by using a centrifuge to collect silica particles loaded with a mixed metal oxide containing palladium and iron, washed several times with ethanol, and dried completely in an oven. The dried product was heat treated at 500 ° C. or higher in an electric furnace.
도 2는 제조된 코어-다공성 쉘 구조의 실리카 입자에 팔라듐/혼합금속 산화물이 담지된 촉매입자의 투과전자현미경(TEM) 사진이다. 사진에서 확인할 수 있듯이, 금속 성분들이 모두 외각의 기공안에 잘 부착되어져 있음을 알 수 있다. 팔라듐 나노 입자와 철을 함유하는 혼합금속 산화물 나노 입자는 입자의 크기는 수 나노미터 정도로 작아서 X-선 분말 회절로는 존재의 유무를 판별하기 어려우나 TEM 장비를 이용해서 원소 분포(elemental distribution mapping)를 해 보면 금속 성분이 존재함을 명확하게 알 수 있다. 500℃ 이상의 고온에서 실리카 입자를 열처리하면 팔라듐 나노 입자 및 철을 함유하는 혼합금속 산화물 나노 입자의 크기가 커져서 X-선 분말 회절로 분석이 가능하다. 이렇게 열처리한 시료를 분석해 보면 도 3의 X-선 회절 패턴과 같이, 팔라듐과 철을 함유하는 혼합금속 산화물이 실리카 입자 안에 담지되어 있음을 확인할 수 있다.
FIG. 2 is a transmission electron microscope (TEM) photograph of a catalyst particle having palladium / mixed metal oxide supported on silica particles having a core-porous shell structure. As can be seen from the photograph, it can be seen that all the metal components are well adhered to the pores of the outer shell. The mixed metal oxide nanoparticles containing palladium nanoparticles and iron are small in particle size of several nanometers, so it is difficult to determine the presence or absence by X-ray powder diffraction.However, elemental distribution mapping can be performed using TEM equipment. It is clear that the metal component exists. When the silica particles are heat-treated at a high temperature of 500 ° C. or higher, the size of the mixed metal oxide nanoparticles containing palladium nanoparticles and iron can be increased and analyzed by X-ray powder diffraction. Analysis of the heat-treated sample shows that the mixed metal oxide containing palladium and iron is supported in the silica particles as in the X-ray diffraction pattern of FIG. 3.
실시예 2 : 코어-다공성 쉘 구조의 실리카 입자에 팔라듐/혼합금속 산화물이 담지된 촉매를 이용한 페닐 아세틸렌의 수소화 반응Example 2 Hydrogenation of Phenyl Acetylene with Catalyst Supported with Palladium / Mixed Metal Oxide on Silica Particles with Core-porous Shell Structure
상기 실시예 1에서 합성한, 코어-다공성 쉘 구조의 실리카 입자에 팔라듐/혼합금속 산화물이 담지된 촉매 10 mg 을 헥산 2 mL에 분산시켰다. 반응 전에 반응기 안에 있는 공기를 모두 제거해준 후에 수소 풍선을 이용해서 수소를 공급해 주었다. 촉매가 분산된 용액에 0.1 mL의 페닐 아세틸렌 용액을 넣어주고 수소화 반응을 진행하였다. 생성물인 스티렌은 1H NMR 과 GC 로 확인하였다. 2 시간 이후에 생성물인 스티렌의 전환율 과 선택도는 각각 98% 이상이었다. 1H NMR (400 MHz, CDCl3, 25 C): δ = 7.40-7.60 (m, 5H), 6.63(m, 1H), 5.61(m, 1H), 5.18(m, 1H).
10 mg of a catalyst in which palladium / mixed metal oxides were supported on silica particles having a core-porous shell structure synthesized in Example 1 was dispersed in 2 mL of hexane. Before the reaction, all the air in the reactor was removed and hydrogen was supplied using a hydrogen balloon. 0.1 mL of phenyl acetylene solution was added to the solution in which the catalyst was dispersed, and then hydrogenated. The product styrene was confirmed by 1 H NMR and GC. After 2 hours the conversion and selectivity of the product styrene were more than 98%, respectively. 1 H NMR (400 MHz, CDCl 3 , 25 C): δ = 7.40-7.60 (m, 5H), 6.63 (m, 1H), 5.61 (m, 1H), 5.18 (m, 1H).
비교예 1 : 팔라듐 촉매를 이용한 페닐 아세틸렌의 수소화 반응Comparative Example 1 Hydrogenation of Phenyl Acetylene with Palladium Catalyst
상기 실시예 2와 반응 조건은 모두 동일하며, 촉매만 상기 제조예 2에서 제조한, 코어-다공성 쉘 구조의 실리카 입자에 팔라듐이 담지된 촉매를 이용하였다. 생성물인 스티렌은 1H NMR 과 GC 로 확인하였다. 40 시간 이후에 생성물인 스티렌의 전환율은 40% 이상, 그리고 선택도는 97% 이상이었다. 1H NMR (400 MHz, CDCl3, 25 C): δ = 7.40-7.60 (m, 5H), 6.63(m, 1H), 5.61(m, 1H), 5.18(m, 1H).
Example 2 and the reaction conditions are the same, only the catalyst was prepared in Preparation Example 2, a catalyst in which the palladium is supported on the silica particles of the core-porous shell structure was used. The product styrene was confirmed by 1 H NMR and GC. After 40 hours, the product had a conversion of styrene of at least 40% and selectivity of at least 97%. 1 H NMR (400 MHz, CDCl 3 , 25 C): δ = 7.40-7.60 (m, 5H), 6.63 (m, 1H), 5.61 (m, 1H), 5.18 (m, 1H).
비교예 2: 혼합금속 산화물 촉매를 이용한 페닐 아세틸렌의 수소화 반응Comparative Example 2: Hydrogenation of Phenyl Acetylene with Mixed Metal Oxide Catalyst
상기 실시예 2와 반응 조건은 모두 동일하며, 촉매만 상기 제조예 3에서 제조한, 코어-다공성 쉘 구조의 실리카 입자에 혼합금속 산화물이 담지된 촉매를 사용하였다. 실험결과 페닐 아세틸렌의 수소화 반응은 진행되지 않았다.
Example 2 and the reaction conditions are the same, only the catalyst was prepared in Preparation Example 3, a catalyst in which a mixed metal oxide is supported on the silica particles of the core-porous shell structure was used. As a result, the hydrogenation of phenyl acetylene did not proceed.
비교예Comparative example 3 : 3: LindlarLindlar 촉매를 이용한 With catalyst 페닐Phenyl 아세틸렌의 수소화 반응 Hydrogenation of Acetylene
상기 실시예 2와 반응 조건은 모두 동일하며 촉매는 시중에서 구입할 수 있는 린들라 촉매(~5 % Pd/Pb/CaCO3, Aldrich)를 사용하였다. 린들라 촉매는 알킨에서 알켄까지 부분 수소화 반응에 사용되며, CaCO3을 담체로 사용하고 5 중량% 의 Pd 와 독(Poison)으로 Pd 의 활성을 낮추는 역할을 하는 Pb 가 담체에 담지된다. 이 촉매 10 mg을 사용하여 2시간 반응한 결과, 생성물인 스티렌의 전환율은 98% 이상, 그리고 선택도는 85% 정도였으며. 이는 본 발명에 의한 선택성에 비하여 현저하게 낮음을 보여준다. 1H NMR (400 MHz, CDCl3, 25 C): δ = 7.40-7.60 (m, 5H), 6.63(m, 1H), 5.61(m, 1H), 5.18(m, 1H).
The reaction conditions are the same as in Example 2, and the catalyst was a commercially available Lindla catalyst (˜5% Pd / Pb / CaCO 3 , Aldrich). Lin Raise catalyst is used for the partial hydrogenation of alkynes to alkenes in, Pb is used, which serves as a carrier and the CaCO 3 to lower the activity of the Pd and Pd poison (Poison) of 5% by weight is supported on a support. The reaction was carried out using 10 mg of this catalyst for 2 hours. The conversion of styrene as a product was more than 98% and the selectivity was about 85%. This shows that it is significantly lower compared to the selectivity according to the present invention. 1 H NMR (400 MHz, CDCl 3 , 25 C): δ = 7.40-7.60 (m, 5H), 6.63 (m, 1H), 5.61 (m, 1H), 5.18 (m, 1H).
비교예 4 : 실리카(SiOComparative Example 4: Silica (SiO 22 )에 담지된 팔라듐 촉매를 이용한 페닐 아세틸렌의 수소화 반응Hydrogenation of Phenyl Acetylene Using Palladium Catalyst Supported on
상기 실시예 2와 반응 조건은 모두 동일하며, 촉매만 상기 제조예 5에서 제조한 다공성 쉘이 없는 구형 실리카 표면에 팔라듐이 담지된 촉매를 사용하였다. 10 시간 반응 후 전환율은 97%, 그리고 선택도는 85% 를 얻었다.
Example 2 and the reaction conditions are the same, only the catalyst was used a catalyst in which palladium is supported on the surface of the spherical silica without the porous shell prepared in Preparation Example 5. The conversion was 97% and the selectivity 85% after 10 hours of reaction.
이상의 결과를 하기 표 1에 요약하였다.The above results are summarized in Table 1 below.
생성물 분석 : 1H NMR 및 GCReaction conditions: 0.1 mL of phenyl acetate, 10 mg of catalyst, 2 mL of hexane, H 2 Balloon (1 atm)
Product analysis: 1 H NMR and GC
실시예Example 3 : 코어-다공성 쉘 구조의 실리카 입자에 팔라듐/혼합금속 산화물이 3: Palladium / Mixed Metal Oxide in Silica Particles of Core-porous Shell Structure 담지Support 된 촉매의 회수 및 재사용Recovery and reuse of spent catalyst
상기 실시예 2와 반응 조건은 모두 동일하며, 실시예 1에서 제조한 코어-다공성 쉘 구조의 실리카 입자에 팔라듐/혼합금속 산화물이 담지된 촉매를 사용한 후 자석으로 촉매를 분리하고, 별도의 과정 없이 촉매를 5회 재사용 하였다. 촉매 반응 결과 촉매의 활성 및 선택성이 5회 까지 이상 없이 유지됨을 확인하였다. 도 4는 자석을 이용하여 촉매를 분리하는 사진이다.
The reaction conditions are the same as in Example 2, using a catalyst in which the palladium / mixed metal oxide is supported on the silica particles of the core-porous shell structure prepared in Example 1, and then the catalyst is separated by a magnet, without any additional process. The catalyst was reused five times. As a result of the catalytic reaction, it was confirmed that the activity and selectivity of the catalyst were maintained at least five times. 4 is a photograph of separating a catalyst using a magnet.
실시예Example 4 ~ 7 : 코어-다공성 쉘 구조의 실리카 입자에 팔라듐/혼합금속 산화물이 담지된 촉매를 이용한 4 to 7: Palladium / Mixed Metal Oxide Supported Catalysts in Silica Particles of Core-porous Shell Structures 페닐Phenyl 아세틸렌의 수소화 반응의 용매 효과 Solvent Effect of Hydrogenation of Acetylene
상기 실시예 2와 반응 조건은 모두 동일하되, 용매를 변경하여 수소화 반응을 수행하였다. 사용용매, 반응시간, 스티렌에 대한 전환율 및 선택도는 하기 표 2와 같다.Example 2 and the reaction conditions are the same, but the hydrogenation reaction was performed by changing the solvent. Solvent, reaction time, conversion rate and selectivity for styrene are shown in Table 2 below.
생성물 분석 : 1H NMR 및 GCReaction conditions: 0.1 mL of phenyl acetate, 10 mg of catalyst, 2 mL of solvent, H 2 Balloon (1 atm)
Product analysis: 1 H NMR and GC
실시예 8: 코어-다공성 쉘 구조의 실리카 입자에 팔라듐/혼합금속 산화물이 담지된 촉매를 이용한 4-메틸 페닐 아세틸렌의 수소화 반응Example 8: Hydrogenation of 4-methyl phenyl acetylene using a catalyst having palladium / mixed metal oxides supported on silica particles having a core-porous shell structure
상기 실시예 2와 동일하게 실시하되, 반응물로 4-메틸 페닐 아세틸렌을 사용하였다. 1-메틸-4-비닐벤젠에 대한 전환율이 99%, 선택도가 73%를 보이는데 2 시간이 걸렸다. 1H NMR (400 MHz, CDCl3, 25 C): δ = 7.00-7.40 (m, 4H), 6.64(m, 1H), 5.65(m, 1H), 5.21(m, 1H), 2.34(s, 3H)
In the same manner as in Example 2, 4-methyl phenyl acetylene was used as the reactant. It took 2 hours for the conversion to 1-methyl-4-vinylbenzene to show 99% and selectivity 73%. 1 H NMR (400 MHz, CDCl 3 , 25 C): δ = 7.00-7.40 (m, 4H), 6.64 (m, 1H), 5.65 (m, 1H), 5.21 (m, 1H), 2.34 (s, 3H)
실시예 9 : 코어-다공성 쉘 구조의 실리카 입자에 팔라듐/혼합금속 산화물이 담지된 촉매를 이용한 4-플루오로 페닐 아세틸렌의 수소화 반응Example 9: Hydrogenation of 4-fluorophenyl acetylene using a catalyst having palladium / mixed metal oxides supported on silica particles having a core-porous shell structure
상기 실시예 5와 동일하게 실시하되, 반응물로 4-플루오로 페닐 아세틸렌을 사용하였다. 1-플루오로-4-비닐벤젠에 대한 전환율이 99%, 선택도가 98%를 보이는데 1 시간이 걸렸다. 1H NMR (400 MHz, CDCl3, 25 C): δ = 7.19-7.60 (m, 4H), 6.63(m, 1H), 5.61(m, 1H), 5.18(m, 1H).
In the same manner as in Example 5, 4-fluoro phenyl acetylene was used as a reactant. It took 1 hour for 99% conversion and 98% selectivity for 1-fluoro-4-vinylbenzene. 1 H NMR (400 MHz, CDCl 3 , 25 C): δ = 7.19-7.60 (m, 4H), 6.63 (m, 1H), 5.61 (m, 1H), 5.18 (m, 1H).
이상의 결과를 표 3에 요약하였다.The above results are summarized in Table 3.
생성물 분석 : 1H NMR 및 GCReaction conditions: 0.1 mL of reactant, 10 mg of catalyst, 2 mL of solvent, H 2 Balloon (1 atm)
Product analysis: 1 H NMR and GC
Claims (9)
A catalyst for the selective hydrogenation of alkenes from alkyne wherein palladium and mixed metal oxides containing iron and copper are supported in shell pores of silica particles having a core-porous shell structure.
The selective hydrogenation of alkenes from alkyne according to claim 1, wherein the silica particles have a particle size of 30 nm to 2 μm, a shell thickness of 1 to 500 nm, and a pore size of the shell of 1 to 30 nm. Reaction catalyst.
The catalyst for selective hydrogenation of alkene from alkynes according to claim 1, wherein the mixed metal oxide containing palladium, iron and copper has a particle size of 1 to 30 nm.
The mixed metal oxide of claim 1, wherein the mixed metal oxide containing iron and copper is a mixed metal oxide of iron and copper, or a mixture of iron oxide and copper oxide, or a mixed metal oxide of iron and copper, iron oxide. And a catalyst for the selective hydrogenation of alkenes from alkynes, characterized in that a mixture of copper oxides.
5. The catalyst for selective hydrogenation of alkene from alkynes according to claim 4, wherein the mixed metal oxide of the spinel structure is further added with at least one selected from Ni, Co and Mn.
2. The catalyst for selective hydrogenation of alkene from alkynes according to claim 1, wherein the mixed metal oxide containing iron and copper has a molar ratio of copper atoms and iron atoms of 1.0: 0.5 to 2.9.
The catalyst for selective hydrogenation of alkene from alkyne according to claim 1, wherein the supported amount of palladium is 0.01 to 10% by weight based on the total weight of the catalyst.
The catalyst for selective hydrogenation of alkene from alkyne according to claim 1, wherein the supported amount of the mixed metal oxide containing iron and copper is 0.01 to 10% by weight based on the total weight of the catalyst.
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| US20230372906A1 (en) | 2021-07-19 | 2023-11-23 | Lg Chem, Ltd. | Catalyst for hydrogenation reaction and manufacturing method therefor |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US20100029993A1 (en) | 2008-07-31 | 2010-02-04 | Johnston Victor J | Direct and selective production of acetaldehyde from acetic acid utilizing a supported metal catalyst |
| KR20120021570A (en) * | 2010-08-09 | 2012-03-09 | 서강대학교산학협력단 | Mesoporous microspheres having catalytic and superparamagnetic characters and producing method of the same |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100029993A1 (en) | 2008-07-31 | 2010-02-04 | Johnston Victor J | Direct and selective production of acetaldehyde from acetic acid utilizing a supported metal catalyst |
| KR20120021570A (en) * | 2010-08-09 | 2012-03-09 | 서강대학교산학협력단 | Mesoporous microspheres having catalytic and superparamagnetic characters and producing method of the same |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104226331A (en) * | 2013-06-17 | 2014-12-24 | 中国石油化工股份有限公司 | Selective hydrogenation copper catalyst with core-shell structure and preparation method thereof |
| CN104226331B (en) * | 2013-06-17 | 2016-08-17 | 中国石油化工股份有限公司 | A kind of selection hydrogenation copper catalyst with nucleocapsid structure and preparation method |
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| KR20120117252A (en) | 2012-10-24 |
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