KR101251388B1 - Sulfate ion impregnated nickel-alumina solid oxide catalysts, Preparing method thereof and Preparing method of butene using the same - Google Patents
Sulfate ion impregnated nickel-alumina solid oxide catalysts, Preparing method thereof and Preparing method of butene using the same Download PDFInfo
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- nickel
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- alumina
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- 239000003054 catalyst Substances 0.000 title claims abstract description 136
- 239000007787 solid Substances 0.000 title claims abstract description 111
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 67
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 title claims abstract description 50
- 238000000034 method Methods 0.000 title claims abstract description 30
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 title claims abstract description 15
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 title claims abstract description 12
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 55
- 239000005977 Ethylene Substances 0.000 claims abstract description 55
- 238000006471 dimerization reaction Methods 0.000 claims abstract description 40
- 238000004519 manufacturing process Methods 0.000 claims abstract description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 80
- 229910052759 nickel Inorganic materials 0.000 claims description 31
- 238000000975 co-precipitation Methods 0.000 claims description 25
- 239000002243 precursor Substances 0.000 claims description 22
- 229910052782 aluminium Inorganic materials 0.000 claims description 21
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 21
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 19
- 239000000243 solution Substances 0.000 claims description 16
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 claims description 11
- 239000007864 aqueous solution Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 239000012153 distilled water Substances 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- 229910000288 alkali metal carbonate Inorganic materials 0.000 claims description 2
- 150000008041 alkali metal carbonates Chemical class 0.000 claims description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims 1
- 230000000694 effects Effects 0.000 description 43
- 238000006243 chemical reaction Methods 0.000 description 39
- 238000002441 X-ray diffraction Methods 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 16
- 238000010438 heat treatment Methods 0.000 description 15
- 230000035484 reaction time Effects 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 238000002360 preparation method Methods 0.000 description 9
- 230000008569 process Effects 0.000 description 9
- 239000011148 porous material Substances 0.000 description 7
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 4
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 4
- 235000011130 ammonium sulphate Nutrition 0.000 description 4
- 239000005416 organic matter Substances 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 239000002638 heterogeneous catalyst Substances 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- 229910000943 NiAl Inorganic materials 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- -1 alkaline earth metal salts Chemical class 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000002815 homogeneous catalyst Substances 0.000 description 2
- 229910000480 nickel oxide Inorganic materials 0.000 description 2
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 2
- 229920001083 polybutene Polymers 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical class C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 1
- 241000640882 Condea Species 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 229910052936 alkali metal sulfate Inorganic materials 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- XVGWRGSSPBULLR-UHFFFAOYSA-L aluminum;nickel(2+);sulfate Chemical compound [Al+3].[Ni+2].[O-]S([O-])(=O)=O XVGWRGSSPBULLR-UHFFFAOYSA-L 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 239000003637 basic solution Substances 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 229920005549 butyl rubber Polymers 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- IAQRGUVFOMOMEM-ARJAWSKDSA-N cis-but-2-ene Chemical compound C\C=C/C IAQRGUVFOMOMEM-ARJAWSKDSA-N 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 230000000447 dimerizing effect Effects 0.000 description 1
- GDQXQVWVCVMMIE-UHFFFAOYSA-N dinitrooxyalumanyl nitrate hexahydrate Chemical compound O.O.O.O.O.O.[Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GDQXQVWVCVMMIE-UHFFFAOYSA-N 0.000 description 1
- 238000000895 extractive distillation Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 150000003840 hydrochlorides Chemical class 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 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
- VDJVKLUWBYHLOA-UHFFFAOYSA-N nickel sulfuric acid Chemical compound [Ni].S(O)(O)(=O)=O.[Ni] VDJVKLUWBYHLOA-UHFFFAOYSA-N 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- IAQRGUVFOMOMEM-ONEGZZNKSA-N trans-but-2-ene Chemical compound C\C=C\C IAQRGUVFOMOMEM-ONEGZZNKSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 239000010457 zeolite Substances 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/053—Sulfates
-
- 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
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C11/00—Aliphatic unsaturated hydrocarbons
- C07C11/02—Alkenes
- C07C11/08—Alkenes with four carbon atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
- C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
- C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
- C07C2/08—Catalytic processes
- C07C2/10—Catalytic processes with metal oxides
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- Chemical Kinetics & Catalysis (AREA)
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Abstract
본 발명은 에틸렌의 이량화 반응(dimerization)에 사용되는 황산이온(SO4 2-)이 담지 된 니켈-알루미나 고체 산화물 촉매 및 이의 제조방법, 그리고 이 촉매를 이용하여 에틸렌의 이량화 반응을 수행하여 부텐(n-butene)을 제조하는 방법에 관한 것이다. The present invention provides a nickel-alumina solid oxide catalyst having a sulfate ion (SO 4 2- ) used in the dimerization of ethylene and a method for preparing the same, and a dimerization reaction of ethylene using the catalyst. It relates to a process for preparing butene ( n- butene).
Description
본 발명은 황산이온(SO4 2-)이 담지 된 니켈-알루미나 고체 산화물 촉매 및 이 촉매의 제조방법, 그리고 이 촉매를 이용하여 에틸렌의 이량화 반응(dimerization)을 수행하여 부텐을 제조하는 방법에 관한 것이다.
The present invention relates to a nickel-alumina solid oxide catalyst loaded with sulfate ion (SO 4 2- ), a method for preparing the catalyst, and a method for preparing butene by performing dimerization of ethylene using the catalyst. It is about.
석유화학공업에서 화학원료로 많이 사용하고 있는 부텐은 1-부텐(1-Butene), 시스 2-부텐(cis 2-butene), 트랜스 2-부텐(trans 2-butene), 이소부텐(iso-butene) 등의 4가지 이성질체를 가진다. 부텐은 주로 옥탄(octane), 1,3-부타디엔을 만드는 공정에서 원료로 사용되며, 그 이성질체는 메타크릴산메틸(Methyl methacrylate), 메타크릴로니트릴(Methacrylonitrile)을 제조하는 공정, 또는 각종 폴리부텐(Polybutene), 부틸고무(Butyl rubber)와 같은 합성고무 제조하는 공정에서 원료로 이용된다. Butenes, which are widely used as chemical raw materials in the petrochemical industry, are 1-butene, cis 2-butene, trans 2-butene, and iso -butene. ) And four isomers. Butene is mainly used as a raw material in the process of making octane, 1,3-butadiene, and the isomer is a process for producing methyl methacrylate, methacrylonitrile, or various polybutenes. It is used as a raw material in the process of manufacturing synthetic rubber such as polybutene and butyl rubber.
일반적으로 부텐은 대부분 납사 분해설비(Naphtha Cracking Center)에서 납사 열분해 공정을 거쳐 얻어진 C4 잔사유(Raffinate)로부터 추출증류 공정을 통해 생산되며, 일부는 부탄의 탈수소화 공정을 통해 생산된다. 최근에는 에틸렌의 이량화를 통해 부반응이 최소화되고 선택도가 높은 부텐의 새로운 제조방법이 개발되었다. In general, butene is mostly produced by extractive distillation from C 4 Raffinate obtained through naphtha pyrolysis at Naphtha Cracking Center, and partly through dehydrogenation of butane. Recently, a new method for producing butenes with high selectivity through the dimerization of ethylene has been developed.
에틸렌의 이량화 반응은 주로 고압조건에서 진행되며, 유기 금속에 흡착된 두 개의 에틸렌이 서로 결합하여 부텐을 생성하는 반응 메커니즘으로 진행된다. 에틸렌의 이량화 반응용 촉매로는 주로 지글러-나타(Ziegler-Natta) 계열 및 메탈로센 계열의 균일계 촉매[미국특허 제4,101,600(1978년), 미국특허 제4,115,469(1978년), 미국특허 제5,037,997(1991년), 미국특허 제5,030,790(1991년), 미국특허 제5,227,562(1993년), 미국특허 제5,414,178(1994년), R.F. de Souza, K. Bernardo-Gusmao, G.A. Cunha, C. Loup, F. Leca, R. Reau, J. Catal., 226, 235(2004)]를 사용한다. 또한, 에틸렌의 이량화 반응용 촉매로서 텅스텐-지르코니아[J.R. Sohn, S.Y. Lee, Appl. Catal. A: Gen., 164, 127(1997)], 황산 처리된 지르코니아[J.R. Sohn, D.C. Shin, J. Catal., 160, 314(1996), J.R. Sohn, W.C. Park, Appl. Catal. A: Gen., 230, 11(2002)], 니켈-실리카계[A. Bruckner, U. Bentrup, H. Zanthoff, D. Maschmeyer, J. Catal., 266, 120(2009)] 그리고 전이금속이 이온 교환된 제올라이트[미국특허 제5,449,849(1995년), J. Michalik, H. Lee, L. Kevan, J. Phys. Chem., 89, 4282(1985), A.K. Ghosh, L. Kevan, J. Phys. Chem., 94, 3117(1990)] 등의 고체 금속산화물 또는 고체 촉매가 개발된 바도 있다.The dimerization reaction of ethylene proceeds mainly under high pressure conditions, and proceeds to a reaction mechanism in which two ethylene adsorbed on the organic metal are bonded to each other to generate butene. Catalysts for the dimerization reaction of ethylene are mainly Ziegler-Natta series and metallocene series homogeneous catalysts [US Patent No. 4,101,600 (1978), US Patent No. 4,115,469 (1978), US Patent No. 5,037,997 (1991), U.S. Patent 5,030,790 (1991), U.S. Patent 5,227,562 (1993), U.S. Patent 5,414,178 (1994), RF de Souza, K. Bernardo-Gusmao, G.A. Cunha, C. Loup, F. Leca, R. Reau, J. Catal., 226, 235 (2004). Further, tungsten-zirconia [J.R. Sohn, S.Y. Lee, Appl. Catal. A: Gen., 164, 127 (1997)], sulfuric acid treated zirconia [J.R. Sohn, D.C. Shin, J. Catal., 160, 314 (1996), J.R. Sohn, W.C. Park, Appl. Catal. A: Gen., 230, 11 (2002)], nickel-silica based [A. Bruckner, U. Bentrup, H. Zanthoff, D. Maschmeyer, J. Catal., 266, 120 (2009) and zeolites ion-exchanged with transition metals (US Pat. No. 5,449,849 (1995), J. Michalik, H. Lee, L. Kevan, J. Phys. Chem., 89, 4282 (1985), A.K. Ghosh, L. Kevan, J. Phys. Chem., 94, 3117 (1990), and the like have been developed solid metal oxides or solid catalysts.
그러나 상기 지글러-나타(Ziegler-Natta)계와 메탈로센 계열의 유기금속 촉매는 에틸렌 이량화 반응에 사용되어 촉매 당 부텐의 선택성과 생산성이 높아 상용 운전이 가능하다는 장점이 있지만, 균일계 촉매로서 반응물과 촉매가 균일한 상을 이루고 있으므로 촉매를 1회 사용 후 폐기해야 하기 때문에 반응 후 촉매와 반응 중 사용되는 용매 및 반응매체를 분리해야 한다. 따라서 이를 위해 추가적인 분리 설비가 필요하고, 촉매 폐기 시 추가처리로 인한 비용이 소요된다는 문제점이 있다.However, the Ziegler-Natta-based and metallocene-based organometallic catalysts are used in ethylene dimerization reaction, but the advantage of high selectivity and productivity of butenes per catalyst is possible for commercial operation. Since the reactants and the catalyst form a uniform phase, the catalyst must be discarded after one use, and thus the catalyst and the solvent and the medium used during the reaction must be separated. Therefore, this requires an additional separation facility, there is a problem in that the cost of the additional treatment when the catalyst is discarded.
이에 본 발명자들은 상기와 같은 종래 기술들의 문제점을 극복하기 위해서 연구한 결과, 반응물과 촉매의 상이 다른 불균일계 촉매로서 반응 후 촉매와 생성물간의 추가적인 분리가 필요하지 않고, 촉매 교체 없이 연속 사용이 가능하도록 하는 새로운 고체 산화물 촉매를 개발하였다.
Therefore, the present inventors have studied to overcome the problems of the prior art as a result, as a heterogeneous catalyst having a different phase of the reactant and the catalyst does not require additional separation between the catalyst and the product after the reaction, so that it can be used continuously without changing the catalyst Developed a new solid oxide catalyst.
본 발명은 에틸렌의 이량화 반응에 의해 부텐을 제조하는 반응에 적용되는, 불균일계 고체 산화물 촉매를 제공하는 것을 목적으로 한다.An object of the present invention is to provide a heterogeneous solid oxide catalyst which is applied to a reaction for producing butene by dimerization of ethylene.
또한, 본 발명은 상기한 고체 산화물 촉매를 이용하여 에틸렌의 이량화 반응을 수행하여 부텐을 제조하는 방법을 제공하는 것을 다른 목적으로 한다.Another object of the present invention is to provide a method for preparing butene by performing a dimerization reaction of ethylene using the solid oxide catalyst described above.
상기 기술적 과제를 달성하기 위하여, 본 발명은 니켈(Ni)/알루미늄(Al)의 몰 비가 0.1 내지 1 범위를 이루는 니켈-알루미나 고체 산화물담지 체에, 황산이온(SO4 2-)이 3 내지 15 중량% 담지 되어 있는 에틸렌의 이량화 반응용 고체 산화물 촉매를 그 특징으로 한다.In order to achieve the above technical problem, the present invention is a nickel-alumina solid oxide carrier having a molar ratio of nickel (Ni) / aluminum (Al) of 0.1 to 1, the sulfate ion (SO 4 2- ) is 3 to 15 It is characterized by the solid oxide catalyst for dimerization reaction of ethylene carried by weight%.
또한 본 발명은 하기의 제조단계를 포함하는 에틸렌의 이량화 반응용 고체 산화물 촉매의 제조방법을 그 특징으로 한다. 니켈/알루미늄의 몰 비가 0.1 내지 1 범위를 이루도록 니켈 전구체 및 알루미늄 전구체를 증류수에 용해시켜 니켈-알루미늄 혼합용액을 제조하는 단계; 상기 니켈-알루미늄 혼합용액에 공침제를 첨가하여 pH를 7.5 내지 8.5로 조절한 후, 교반 및 공침시켜 공침용액을 제조하는 단계; 상기 공침용액을 여과 및 세척한 후, 70 내지 140 ℃에서 건조하고, 400 내지 600 ℃에서 열처리하여 니켈-알루미나 고체 산화물 담지 체를 얻는 단계; 상기 니켈-알루미나 고체 산화물 담지 체를 황산 전구체가 녹아있는 수용액에 첨가하고 감압 증류하여 황산이온이 3 내지 15 중량% 담지 된 고체 시료를 얻는 단계; 및 상기 황산이온이 담지 된 니켈-알루미나 고체 시료를 100 내지 120 ℃에서 건조시키고, 400 내지 600 ℃에서 열처리하여 황산이온이 담지 된 니켈-알루미나 고체 산화물 촉매를 얻는 단계.In another aspect, the present invention is characterized by a method for producing a solid oxide catalyst for dimerization reaction of ethylene comprising the following steps. Preparing a nickel-aluminum mixed solution by dissolving the nickel precursor and the aluminum precursor in distilled water such that the molar ratio of nickel / aluminum is in the range of 0.1 to 1; Preparing a coprecipitation solution by adding a coprecipitation agent to the nickel-aluminum mixed solution to adjust pH to 7.5 to 8.5, followed by stirring and coprecipitation; Filtering and washing the coprecipitation solution, drying at 70 to 140 ° C., and heat treating at 400 to 600 ° C. to obtain a nickel-alumina solid oxide carrier; Adding the nickel-alumina solid oxide carrier to an aqueous solution in which a sulfuric acid precursor is dissolved and distilling under reduced pressure to obtain a solid sample having 3 to 15 wt% of sulfate ion; And drying the nickel-alumina solid sample loaded with sulfate ion at 100 to 120 ° C. and heat-treating at 400 to 600 ° C. to obtain a nickel-alumina solid oxide catalyst loaded with sulfate ion.
또한, 본 발명은 상기 고체 산화물 촉매를 이용하여 에틸렌의 이량화 반응을 수행하여 부텐을 제조하는 방법을 그 특징으로 한다.
In addition, the present invention is characterized by a method for producing butene by performing a dimerization reaction of ethylene using the solid oxide catalyst.
본 발명의 고체 산화물 촉매는 불균일계 촉매로서, 기존의 부텐 제조용 균일계 촉매와는 달리 생성물과 촉매 분리를 위한 추가 공정이 필요치 않으며, 촉매의 연속 사용이 가능하므로 촉매의 교체 없이 연속 운전이 가능하여 공정의 운전비용이 감소하므로 경제적인 면에서 우수하다는 장점이 있다.Solid oxide catalyst of the present invention is a heterogeneous catalyst, unlike the conventional homogeneous catalyst for the production of butenes, no additional process for product and catalyst separation is required, and the continuous use of the catalyst enables continuous operation without replacement of the catalyst. The operating cost of the process is reduced, so it is advantageous in terms of economics.
본 발명의 고체 산화물 촉매는 에틸렌의 이량화 반응에 대한 활성이 높고 부텐에 대한 선택도가 우수하다는 장점이 있다.
The solid oxide catalyst of the present invention has the advantage of high activity for dimerization of ethylene and excellent selectivity for butene.
도 1은 본 발명의 고체 산화물 촉매 제조를 위한 공정도이다.
도 2는 니켈-알루미나 고체 산화물 담지 체의 X-선 회절패턴 결과이다.
도 3은 황산이온 담지 된 니켈-알루미나 고체 산화물 촉매의 X-선 회절패턴 결과이다.
도 4는 황산이온 담지 니켈-알루미나 고체 산화물 촉매의 열처리 온도에 따른 X-선 회절패턴 결과이다.
도 5는 비교예 1의 공침온도 70 ℃에서 제조한 니켈-알루미나 고체 산화물 담지체 및 비교예 2에서 제조한 황산이온과 니켈이 담지 된 알루미나 촉매의 X-선 회절패턴 결과이다.
도 6은 S(6)NA(0.20) 촉매를 이용하여 실험예 2의 방법으로 에틸렌의 이량화 반응을 수행하였을 때, 반응시간에 따른 반응활성 실험 결과를 나타낸 그래프이다. 1 is a process chart for preparing a solid oxide catalyst of the present invention.
2 is an X-ray diffraction pattern of the nickel-alumina solid oxide support.
3 is an X-ray diffraction pattern of the sulfate-supported nickel-alumina solid oxide catalyst.
4 is an X-ray diffraction pattern of the sulfate-supported nickel-alumina solid oxide catalyst according to the heat treatment temperature.
5 is an X-ray diffraction pattern of the nickel-alumina solid oxide support prepared at the coprecipitation temperature of 70 ° C. of Comparative Example 1 and the alumina catalyst loaded with the sulfate ion and nickel prepared in Comparative Example 2. FIG.
Figure 6 is a graph showing the reaction activity test results according to the reaction time when the dimerization of ethylene by the method of Experimental Example 2 using the S (6) NA (0.20) catalyst.
본 발명은 에틸렌의 이량화 반응에 이용되는 황산이온이 담지 된 니켈-알루미나 고체 산화물 촉매에 관한 것이다. 본 발명의 고체 산화물 촉매는 니켈-알루미나 고체 산화물 담지체 85 내지 97 중량%에 황산이온 3 내지 15 중량%가 담지 되어 있는 불균일계 촉매이다. The present invention relates to a nickel-alumina solid oxide catalyst loaded with sulfate ions used in the dimerization reaction of ethylene. The solid oxide catalyst of the present invention is a heterogeneous catalyst in which 3 to 15 wt% of sulfate ion is supported on 85 to 97 wt% of the nickel-alumina solid oxide support.
본 발명의 촉매 제조에 사용되는 니켈-알루미나 고체 산화물 담지체는 비표면적이 170 m2/g 이상, 바람직하기로는 비표면적이 170 내지 250 m2/g 범위이다. 상기한 니켈-알루미나 고체 산화물 담지체는 촉매성분을 담지 시키는 담지체로서의 역할은 물론이고, 에틸렌의 이량화 반응에서 촉매 활성점 역할을 하게 된다. 본 발명에서는 담지 체를 구성하는 니켈/알루미늄의 몰 비 조절을 통해 촉매의 산 특성을 변화시켰다. 본 발명에 의하면 담지 체를 구성하는 니켈/알루미늄의 몰 비, 즉 [Ni]/[Al]가 0.1 내지 1 범위, 바람직하기로는 [Ni]/[Al]가 1.0 내지 0.5 범위를 유지하는 것이 에틸렌의 이량화 반응에서 우수한 촉매활성을 나타낼 수 있다.The nickel-alumina solid oxide support used in the preparation of the catalyst of the invention has a specific surface area of at least 170 m 2 / g, preferably in the range of 170 to 250 m 2 / g. The nickel-alumina solid oxide support described above serves as a support for supporting the catalyst component as well as a catalyst active point in the dimerization reaction of ethylene. In the present invention, the acid properties of the catalyst were changed by controlling the molar ratio of nickel / aluminum constituting the support. According to the present invention, the molar ratio of nickel / aluminum constituting the carrier, that is, [Ni] / [Al] in the range of 0.1 to 1, preferably [Ni] / [Al] in the range of 1.0 to 0.5, is ethylene. It can exhibit excellent catalytic activity in the dimerization reaction of.
상기한 본 발명의 고체 산화물 촉매 제조방법은 도 1의 공정도에 의거하여 구체적으로 설명하면 다음과 같다.The solid oxide catalyst manufacturing method of the present invention described above will be described in detail based on the process chart of FIG. 1.
제 1단계는, 니켈 전구체와 알루미늄 전구체를 증류수에 용해시켜 니켈-알루미늄 혼합용액을 제조하는 단계이다.The first step is to prepare a nickel-aluminum mixed solution by dissolving the nickel precursor and the aluminum precursor in distilled water.
이때, 니켈 전구체와 알루미늄 전구체는 니켈/알루미늄의 몰 비([Ni]/[Al])가 0.1 내지 1 범위를 유지할 수 있도록 칭량한다. 상기 니켈 전구체와 알루미늄 전구체는 촉매 제조분야에서 통상적으로 사용되는 금속화합물로, 산화물, 수산화물, 염화물, 염산염, 질산염, 아세트산염, 아세틸아세토네이트염 등이 사용될 수 있다. 본 발명의 실시예에서는 니켈 전구체로서 염화니켈, 질산니켈을 사용하고, 알루미늄 전구체로서 염화알루미늄, 질산알루미늄을 대표적으로 사용하고 있으나, 본 발명은 이들 전구체의 선택에 특별한 제한을 두고 있지 않는다. 전구체 용액을 제조할 때 용액은 상온 주변의 온도를 유지하는 것이 좋은 바, 구체적으로는 20 내지 30 ℃를 유지하며, 바람직하게는 25 ℃를 유지한다. At this time, the nickel precursor and the aluminum precursor are weighed so that the molar ratio ([Ni] / [Al]) of nickel / aluminum can be maintained in the range of 0.1 to 1. The nickel precursor and the aluminum precursor are metal compounds commonly used in the field of catalyst production, and oxides, hydroxides, chlorides, hydrochlorides, nitrates, acetates, acetylacetonate salts, and the like may be used. In the embodiment of the present invention, nickel chloride and nickel nitrate are used as nickel precursors, and aluminum chloride and aluminum nitrate are representatively used as aluminum precursors, but the present invention does not particularly limit the selection of these precursors. When preparing the precursor solution, the solution is preferably maintained at a temperature around room temperature, specifically 20 to 30 ℃, preferably 25 ℃.
제 2단계는, 상기 니켈-알루미늄 혼합용액에 공침제를 첨가하여 공침용액을 제조하는 단계이다.In the second step, a coprecipitation solution is prepared by adding a coprecipitation agent to the nickel-aluminum mixed solution.
상기 공침제는 당 업계에서 pH 조절을 위해 사용하는 염기성 용액으로, 예를 들면 암모니아수, 알칼리금속 수산화물 수용액, 알칼리금속 탄산염 수용액을 사용할 수 있다. 상기한 공침제를 구체적으로 예시하면, 수산화나트륨 수용액, 수산화칼륨 수용액, 탄산나트륨 수용액, 탄산칼륨 수용액, 암모니아수를 사용할 수 있다. 상기 니켈-알루미늄 혼합용액에 공침제를 첨가하여 pH를 7.5 내지 8.5, 바람직하게는 pH를 7.8 내지 8.2, 더욱 바람직하게는 pH를 7.9 내지 8.1로 조절한다. pH가 너무 낮거나 높으면 담지체 내 활성에 참여하는 물질의 상이 생성되지 않는 문제가 있을 수 있으므로 상기 범위의 pH를 유지하는 것이 바람직하다.The coprecipitation agent is a basic solution used for adjusting pH in the art, for example, may be used ammonia water, aqueous alkali metal hydroxide solution, aqueous alkali metal carbonate solution. Specific examples of the co-precipitation agent, sodium hydroxide aqueous solution, potassium hydroxide aqueous solution, sodium carbonate aqueous solution, potassium carbonate aqueous solution, ammonia water can be used. The co-precipitation agent is added to the nickel-aluminum mixed solution to adjust the pH to 7.5 to 8.5, preferably pH to 7.8 to 8.2, more preferably pH to 7.9 to 8.1. If the pH is too low or too high, there may be a problem that the phase of the material participating in the activity in the carrier is not generated, it is preferable to maintain the pH in the above range.
제 3단계는, 상기 공침용액을 건조 및 열처리하여 니켈-알루미나 고체 산화물 담지체를 얻는 단계이다.The third step is to obtain a nickel-alumina solid oxide carrier by drying and heat treating the coprecipitation solution.
상기 공침용액은 감압 여과기를 통해 충분히 여과 및 세척하여 고체 시료를 얻는다. 그리고, 얻어진 고체 시료는 70 내지 140 ℃, 바람직하게는 100 내지 120 ℃에서 24시간 정도 충분히 건조한다. 그리고, 건조된 고체 시료를 전기로에서 400 내지 600 ℃ 온도로 열처리하여 니켈-알루미나 고체 산화물 담지체를 제조한다. 이때 열처리 온도가 400 ℃ 미만이면 미 반응 유기물 및 원하는 결정을 얻지 못하는 문제가 있을 수 있으며, 600 ℃를 초과하면 촉매 자체 또는 구성성분 일부가 녹아 고융체를 형성하는 문제가 있을 수 있으므로, 상기 범위 내의 온도를 유지하는 것이 바람직하다.The coprecipitation solution is sufficiently filtered and washed through a vacuum filter to obtain a solid sample. The obtained solid sample is sufficiently dried at 70 to 140 ° C., preferably at 100 to 120 ° C. for about 24 hours. Then, the dried solid sample is heat-treated at 400 to 600 ° C. in an electric furnace to prepare a nickel-alumina solid oxide support. At this time, if the heat treatment temperature is less than 400 ℃ there may be a problem that can not obtain the unreacted organic matter and the desired crystals, if it exceeds 600 ℃ may have a problem of melting the catalyst itself or a part of the components to form a high melt, within the above range It is desirable to maintain the temperature.
제 4단계는, 상기 니켈-알루미나 고체 산화물 담지체에 황산이온을 담지시키는 단계이다.The fourth step is a step of supporting sulfate ion on the nickel-alumina solid oxide support.
황산 전구체는 황산이온이 3 내지 15 중량% 담지되도록 칭량한 후에 증류수에 용해시켜 황산 수용액을 제조한다. 본 발명에서 사용되는 황산 전구체는 당 업계에서 통상적으로 사용되는 것으로, 이의 선택에 특별히 제한을 두지 않는다, 황산 전구체로는 구체적으로 황산 암모늄염, 황산 알칼리금속염, 황산 알칼리 토금속염이 사용될 수 있다. 그리고, 황산 수용액에 상기 니켈-알루미나 고체 산화물 담지체를 첨가하고 충분히 담지 되도록 1 내지 4시간, 바람직하게는 2 내지 3시간 정도 교반시켜 니켈-알루미나 고체 산화물 담지체에 황산이온을 담지 시킨다. 그런 다음, 50 내지 70 ℃에서 감압 증류하여 황산이온이 담지 된 니켈-알루미나 고체 시료를 얻는다.The sulfuric acid precursor is weighed to carry 3 to 15% by weight of sulfate ions and dissolved in distilled water to prepare an aqueous sulfuric acid solution. Sulfuric acid precursors used in the present invention are commonly used in the art, and there is no particular limitation on the selection thereof. Specifically, sulfuric acid precursors may include ammonium sulfate, alkali metal sulfate, and alkaline earth metal salts. Then, the nickel-alumina solid oxide support is added to the aqueous sulfuric acid solution, and stirred for 1 to 4 hours, preferably 2 to 3 hours, so that the sulfate-ion is supported on the nickel-alumina solid oxide support. Then, distillation under reduced pressure at 50 to 70 ℃ to obtain a nickel-alumina solid sample loaded with sulfate ion.
제 5단계는, 상기 황산이온이 담지 된 니켈-알루미나 고체 시료를 건조 및 열처리하여 본 발명이 목적하는 고체 산화물 촉매를 얻는 단계이다.The fifth step is a step of obtaining a solid oxide catalyst of the present invention by drying and heat-treating the nickel-alumina solid sample loaded with the sulfate ion.
상기 황산이온이 담지 된 니켈-알루미나 고체 시료는 70 내지 140 ℃, 바람직하게는 100 내지 120 ℃에서 24시간 정도 충분히 건조시켜 건조된 촉매를 얻는다. 상기 건조된 촉매를 전기로에서 400 내지 600 ℃에서 열처리하여 황산이온이 담지 된 니켈-알루미나 고체 산화물 촉매를 얻다. 이때, 열처리 온도가 400℃ 미만이면 황산 전구체의 유기물이 제거되지 않는 문제가 있고, 600 ℃를 초과하면 황산이온이 분해되어 촉매 활성에 문제가 있을 수 있으므로, 상기 범위 내의 온도를 유지하는 것이 바람직하다. The nickel-alumina solid sample loaded with sulfate ion is sufficiently dried at 70 to 140 ° C., preferably at 100 to 120 ° C. for about 24 hours to obtain a dried catalyst. The dried catalyst is heat-treated at 400 to 600 ° C. in an electric furnace to obtain a nickel-alumina solid oxide catalyst loaded with sulfate ion. At this time, if the heat treatment temperature is less than 400 ℃ there is a problem that the organic matter of the sulfuric acid precursor is not removed, and if it exceeds 600 ℃, the sulfate ion may be decomposed and there may be a problem in the catalytic activity, it is preferable to maintain the temperature within the above range .
이상에서 설명한 본 발명의 고체 산화물 촉매는 에틸렌의 이량화 반응용 촉매로서 유용하다. 이량화 반응을 수행하기에 앞서, 고체 산화물 촉매는 250 내지 400 ℃ 온도에서 1 내지 5시간 동안 전처리한다. 상기 전처리된 고체 산화물 촉매는 에틸렌 분압 0.5 내지 1 atm, 반응온도 15 내지 40 ℃ 조건에서 에틸렌을 이량화하여 부텐을 제조하게 된다.The solid oxide catalyst of the present invention described above is useful as a catalyst for ethylene dimerization reaction. Prior to performing the dimerization reaction, the solid oxide catalyst is pretreated for 1-5 hours at a temperature of 250-400 ° C. The pretreated solid oxide catalyst is produced by dimerizing ethylene under conditions of ethylene partial pressure of 0.5 to 1 atm, reaction temperature of 15 to 40 ℃.
이와 같은 본 발명은 하기의 실시예에 의거하여 더욱 자세히 설명하겠는 바, 본 발명이 이들 실시예에 의해 한정되는 것은 아니다.
Such a present invention will be described in more detail based on the following examples, but the present invention is not limited to these examples.
[실시예]
[Example]
실시예 1. 니켈-알루미나 고체 산화물 담지체의 제조Example 1 Preparation of Nickel-Alumina Solid Oxide Supports
도 1에 나타낸 공정도에 의거하여 고체 산화물 담지체를 제조하였다.Based on the process diagram shown in FIG. 1, a solid oxide support was prepared.
먼저, 질산알루미늄 9수화물(Al(NO3)3ㆍ9H2O, SAMCHUN, 98%) 104.1 g을 증류수 360 g에 넣어 교반한 후, 질산니켈 6수화물(Ni(NO3)2ㆍ6H2O, SAMCHUN, 98%) 84.8 g을 첨가하고 교반하여, 니켈/알루미늄의 몰 비가 1.0인 니켈-알루미늄 혼합 수용액을 제조하였다. 상온에서 암모니아수(NH4OH, SAMCHUN, 28~30%)를 pH 8.0이 될 때까지 니켈-알루미늄 혼합 수용액에 첨가하면서 교반하여 Ni(OH)2-Al(OH)3의 공침용액을 제조하였다. 공침용액은 상온에서 12시간 동안 교반하였다. 공침된 고체 산화물을 세척하여 여과한 후 120 ℃에서 24시간 동안 건조하고, 소성로에서 500 ℃에서 4시간 동안 열처리하여 니켈-알루미나 고체 산화물 담지체를 제조하였다.
First, 104.1 g of aluminum nitrate hexahydrate (Al (NO 3 ) 3 .9H 2 O, SAMCHUN, 98%) was added to 360 g of distilled water and stirred, followed by nickel nitrate hexahydrate (Ni (NO 3 ) 2 .6H 2 O. , SAMCHUN, 98%) was added and stirred to prepare a nickel-aluminum mixed aqueous solution having a molar ratio of nickel / aluminum of 1.0. At room temperature, ammonia water (NH 4 OH, SAMCHUN, 28 to 30%) was added to the nickel-aluminum mixed aqueous solution until the pH was 8.0, while stirring to prepare a coprecipitation solution of Ni (OH) 2 -Al (OH) 3 . The coprecipitation solution was stirred at room temperature for 12 hours. The co-precipitated solid oxide was washed, filtered, dried at 120 ° C. for 24 hours, and heat-treated at 500 ° C. for 4 hours in a kiln to prepare a nickel-alumina solid oxide support.
상기 실시예 1의 방법으로 니켈-알루미나 고체 산화물 담지체를 제조하였으며, 각 제조된 담지체의 X-선 회절패턴을 도 2에 나타내었다. X-선 회절패턴은 CuKα와 니켈 필터를 사용하는 X-선 회절분석기(XRD, XPMAC)로 100 kV와 40 mA 조건에서 X-선 회절 패턴을 그렸다. The nickel-alumina solid oxide carrier was prepared by the method of Example 1, and the X-ray diffraction patterns of the prepared carriers are shown in FIG. 2. X-ray diffraction pattern was X-ray diffraction pattern (XRD, XPMAC) using CuKα and nickel filter to draw an X-ray diffraction pattern at 100 kV and 40 mA.
도 2에서는 본 실시예 1에서 제조한 담지체를 'NA'로 표기하였고, 니켈/알루미늄의 몰 비를 괄호안의 숫자로 표기하였다. 예컨대 [Ni]/[Al]의 몰 비가 1인 니켈-알루미나 고체 산화물 담지체는 'NA(1.0)'으로 표기하였다.In FIG. 2, the carrier prepared in Example 1 was expressed as 'NA', and the molar ratio of nickel / aluminum was indicated by the numbers in parentheses. For example, the nickel-alumina solid oxide support having a molar ratio of [Ni] / [Al] of 1 is designated as 'NA (1.0)'.
도 2에 나타낸 X-선 회절패턴은 문헌 [C. Otero Arean, M. Penarroya Mentruit, A.J. Lopez Lopez, J.B. Parra, Colloid Surface A., 180, 253(2001), A. Al-ubaid, E.E. Wolf, Appl. Catal., 40, 73(1988), A.V. Ghule, K. Ghule, T. Punde, J.-Y. Liu, S.-H. Tzing, J.-Y. Chang, H. Chang, Y.-C. Ling, Mater. Chem. Phys., 119, 86(2010)]에 보고된 것처럼 회절각(2θ) 37°, 45° 등에서 니켈-알루미나(NiAl2O4) 구조와 관련된 회절피크가 관측되었다. [Ni]/[Al]의 몰 비가 0.1에서 1.0으로 증가할수록 회절각(2θ)의 피크 위치가 이동하여 37.2°, 43.3° 등에서 산화니켈(NiO)에 관련된 회절피크가 관측되었다.
The X-ray diffraction pattern shown in FIG. 2 is described in C. Otero Arean, M. Penarroya Mentruit, AJ Lopez Lopez, JB Parra, Colloid Surface A., 180, 253 (2001), A. Al-ubaid, EE Wolf, Appl. Catal., 40, 73 (1988), AV Ghule, K. Ghule, T. Punde, J.-Y. Liu, S.-H. Tzing, J.-Y. Chang, H. Chang, Y.-C. Ling, Mater. Chem. Phys., 119, 86 (2010)], diffraction peaks related to nickel-alumina (NiAl 2 O 4 ) structures were observed at diffraction angles ( 2θ ) 37 °, 45 ° and the like. As the molar ratio of [Ni] / [Al] increased from 0.1 to 1.0, the peak position of the diffraction angle ( 2θ ) shifted and diffraction peaks related to nickel oxide (NiO) were observed at 37.2 ° and 43.3 °.
실시예 2. 황산이온이 담지 된 니켈-알루미나 고체 산화물 촉매의 제조Example 2 Preparation of Nickel-Alumina Solid Oxide Catalyst Supported with Sulfate Ion
도 1에 나타낸 공정도에 의거하여, 상기 실시예 1에서 제조한 니켈-알루미나 고체 산화물 담지체에 황산이온을 담지하여 고체 산화물 촉매를 제조하였다. Based on the process diagram shown in FIG. 1, a sulfate oxide was supported on the nickel-alumina solid oxide support prepared in Example 1 to prepare a solid oxide catalyst.
즉, 황산암모늄((NH4)2SO4, SAMCHUN, 99%) 0.88 g을 증류수 50 g에 넣어 교반한 후 니켈-알루미나 고체 산화물 담지체 10 g을 가하여 25 ℃에서 2시간 동안 교반하면서 담지시켰다. 이어 감압증발기를 이용하여 70 ℃에서 감압 증류하여 고체 시료를 얻고, 상기 고체 시료를 120 ℃에서 24시간 동안 건조하고, 소성로에서 500 ℃, 4시간 동안 소성하여 황산이온이 담지 된 니켈-알루미나 고체 금속 산화물 촉매를 제조하였다.
That is, 0.88 g of ammonium sulfate ((NH 4 ) 2 SO 4 , SAMCHUN, 99%) was added to 50 g of distilled water, followed by stirring. Then, 10 g of a nickel-alumina solid oxide support was added thereto, followed by stirring at 25 ° C. for 2 hours. . Subsequently, a solid sample was obtained by distillation under reduced pressure at 70 ° C. using a reduced pressure evaporator. The solid sample was dried at 120 ° C. for 24 hours, and calcined at 500 ° C. for 4 hours in a kiln to carry nickel sulfate-aluminum solid metal. Oxide catalysts were prepared.
상기 실시예 2에서 황산암모늄의 양을 조절하여 황산이온의 담지량을 조절하였다.In Example 2, the amount of ammonium sulfate was adjusted by adjusting the amount of ammonium sulfate.
도 3에는 [Ni]/[Al]의 몰 비가 0.2인 니켈-알루미나 고체 산화물 담지체 NA(0.20)에 황산이온을 3, 6, 8, 10, 13, 15 중량% 담지량으로 담지시켜 제조된 금속 산화물 촉매의 X-선 회절패턴을 나타내었다. X-선 회절패턴은 CuKα와 니켈 필터를 사용하는 X-선 회절분석기(XRD, XPMAC)로 100 kV와 40 mA조건에서 X-선 회절 패턴을 그렸다. FIG. 3 shows a metal prepared by loading 3, 6, 8, 10, 13, 15 wt% of sulfate ions on a nickel-alumina solid oxide carrier NA (0.20) having a molar ratio of [Ni] / [Al] of 0.2. The X-ray diffraction pattern of the oxide catalyst is shown. The X-ray diffraction pattern was an X-ray diffraction pattern (XRD, XPMAC) using a CuKα and nickel filter to draw an X-ray diffraction pattern at 100 kV and 40 mA.
도 3에서는 상기 실시예 2에서 제조한 고체 산화물 촉매에 담지 된 황산이온의 담지량을 황산이온의 약자(S)뒤 괄호 안에 중량% 단위로 기재하였다. 예컨대 [Ni]/[Al]의 몰 비가 0.2인 니켈-알루미나 고체 산화물 담지체에, 황산이온이 10 중량% 담지 된 고체 산화물 촉매는 'S(10)NA(0.20)'으로 표기하였다. 도 3에 의하면, 황산이온의 담지량에 관계없이 상기 실시예 1에 나타낸 문헌에 보고된 니켈-알루미나(NiAl2O4)의 구조와 일치하는 회절피크가 관측되었다.
In FIG. 3, the amount of sulfate ions supported on the solid oxide catalyst prepared in Example 2 is described in weight percent in parentheses after the abbreviation (S) of sulfate ion. For example, a solid oxide catalyst having 10% by weight of sulfate ion supported on a nickel-alumina solid oxide support having a molar ratio of [Ni] / [Al] of 0.2 is designated as 'S (10) NA (0.20)'. 3, a diffraction peak consistent with the structure of nickel-alumina (NiAl 2 O 4 ) reported in the literature shown in Example 1 was observed regardless of the amount of sulfate ion supported.
실시예 3. 황산이온이 담지 된 니켈-알루미나 고체 산화물 촉매 제조: 열처리 온도의 영향Example 3 Preparation of Nickel-Alumina Solid Oxide Catalysts Supported with Sulfate Ion: Effect of Heat Treatment Temperature
상기 실시예 2와 동일한 방법으로 [Ni]/[Al]의 몰 비가 0.2인 니켈-알루미나 고체 산화물 담지체에, 황산이온이 10 중량% 담지 된 고체 산화물 촉매 즉, S(10)NA(0.2) 촉매를 제조하였다. 다만, 황산이온 담지시킨 후의 열처리 온도를 각각 400 ℃, 450 ℃, 500 ℃, 550 ℃, 600 ℃로 변화시키면서 'S(10)NA(0.2)' 촉매를 제조하였다.
In the same manner as in Example 2, S (10) NA (0.2), a solid oxide catalyst in which 10% by weight of sulfate ion was supported on a nickel-alumina solid oxide support having a molar ratio of [Ni] / [Al] of 0.2 Catalyst was prepared. However, 'S (10) NA (0.2)' catalyst was prepared while changing the heat treatment temperature after supporting sulfate ion to 400 ° C., 450 ° C., 500 ° C., 550 ° C. and 600 ° C., respectively.
도 4에는 열처리 온도를 달리하여 제조된 S(10)NA(0.2) 촉매의 X-선 회절패턴을 나타내었다.Figure 4 shows the X-ray diffraction pattern of the S (10) NA (0.2) catalyst prepared by varying the heat treatment temperature.
도 4에 의하면, 상기 실시예 1에 나타낸 문헌에 보고된 니켈-알루미나의 회절 패턴과 잘 일치하였으며, 열처리 온도가 증가할수록 촉매의 결정화도는 증가하였다.
According to FIG. 4, the diffraction pattern of the nickel-alumina reported in the literature shown in Example 1 was in good agreement, and the crystallinity of the catalyst increased with increasing heat treatment temperature.
비교예 1. 황산이온 담지 니켈-알루미나 고체 산화물 촉매 제조: 공침온도의 영향Comparative Example 1. Preparation of Sulfate-Ioned Nickel-Alumina Solid Oxide Catalysts: Effect of Coprecipitation Temperature
상기 실시예 1의 방법으로 [Ni]/[Al]의 몰 비가 0.2인 니켈-알루미나 고체 산화물 담지체를 제조하되, 다만 공침시 용액의 온도를 상온을 유지하는 대신에 70 ℃로 가열하였다. 또한, 제조된 'NA(0.20)_70 ℃'의 니켈-알루미나 고체 산화물 담지체에 상기 실시예 2의 방법으로 황산이온을 10 중량% 담지량으로 담지시켜 'S(10)NA(0.20)_70 ℃'의 고체 산화물 촉매를 제조하였다.
The nickel-alumina solid oxide carrier having a molar ratio of [Ni] / [Al] of 0.2 was prepared by the method of Example 1, but was heated to 70 ° C. instead of maintaining the temperature of the solution at the time of coprecipitation. In addition, on the prepared 'NA (0.20) _ 70 ℃' nickel-alumina solid oxide support by the method of Example 2 by supporting the sulfate ion in a 10% by weight loading amount 'S (10) NA (0.20) _ 70 ℃' The solid oxide catalyst of was prepared.
도 5에는 상기 비교예 1의 70 ℃ 온도에서 공침하여 제조한 담지체 NA(0.20)_70℃의 X-선 회절패턴을 나타내었다. 도 5에 의하면, 공침온도를 70 ℃로 유지하더라도 상기 실시예 1에 나타낸 문헌에 보고된 니켈-알루미나의 회절 패턴과 잘 일치하였으며, 결정화도도 비슷하였다.
5 shows an X-ray diffraction pattern of a carrier NA (0.20) _70 ° C. prepared by coprecipitation at 70 ° C. of Comparative Example 1. FIG. According to FIG. 5, even when the coprecipitation temperature was maintained at 70 ° C., the diffraction pattern of the nickel-alumina reported in the literature shown in Example 1 was well matched, and the degree of crystallinity was similar.
비교예 2. 알루미나 담지체에 니켈과 황산이온을 담지한 촉매 제조Comparative Example 2. Preparation of Catalyst Supported with Nickel and Sulfate Ion on Alumina Supporting Body
상기 실시예 2에서 제조한 S(10)NA(0.20)의 고체 산화물 촉매와 비교하기 위해서, 알루미나 고체 산화물 담지체에 니켈과 황산이온을 차례로 담지한 고체 산화물 촉매를 제조하였다.In order to compare the solid oxide catalyst of S (10) NA (0.20) prepared in Example 2, a solid oxide catalyst in which nickel and sulfate ions were sequentially supported on an alumina solid oxide carrier was prepared.
먼저, 알루미나 고체 산화물 담지체에 니켈을 담지시키기 위하여 질산니켈 6수화물(Ni(NO3)2ㆍ6H2O, SAMCHUN, 98%) 5.9 g을 증류수 100 g에 넣어 교반한 후, 니켈/알루미늄 몰 비가 0.20이 되도록 γ-알루미나(γ-Al2O3, CONDEA)를 5.1 g 가하여 25℃에서 2시간 동안 교반하였다. 이어 감압증발기를 이용하여 70℃에서 감압 증류하여 고체 시료를 얻고, 상기 고체 시료를 120 ℃에서 24시간 동안 건조하고, 소성로에서 500 ℃, 4시간 동안 열처리하여 니켈 담지 된 γ-알루미나 고체 산화물 담지체를 만들었다. First, 5.9 g of nickel nitrate hexahydrate (Ni (NO 3 ) 2 · 6H 2 O, SAMCHUN, 98%) was added to 100 g of distilled water to stir nickel on the alumina solid oxide support, followed by stirring. Γ -alumina ( γ- Al 2 O 3 , CONDEA) was added in a ratio of 0.20 and stirred at 25 ° C. for 2 hours. Followed by distillation under reduced pressure at 70 ℃ using a reduced pressure evaporator to obtain a solid sample, the γ The solid sample was dried at 120 ℃ for 24 hours, and heat treated for 500 ℃ in a firing furnace for 4 hours, a nickel-supported alumina solid oxide carrier Made.
그런 다음, 황산이온을 담지시키기 위하여 상기 실시예 2와 동일한 방법으로 10 중량%의 담지량으로 황산이온을 담지하여 니켈-황산/알루미나 고체 산화물 촉매 즉, 'S(10)-Ni/γ-Al2O3(0.20)'의 고체 산화물 촉매를 제조하였다.
Then, in order to support the sulfate ion, in the same manner as in Example 2, the sulfuric acid ion was supported at a supported amount of 10% by weight to form a nickel-sulfuric acid / alumina solid oxide catalyst, that is, 'S (10) -Ni / γ- Al 2 A solid oxide catalyst of O 3 (0.20) 'was prepared.
도 5에는 상기 비교예 2에서 제조한 S(10)-Ni/γ-Al2O3(0.20) 고체 산화물 촉매의 X-선 회절패턴을 나타내었다. 도 5에 의하면, S(10)NA(0.20)의 고체 산화물 촉매의 X-선 회절 분석결과 다른 특정 피크는 나타나지 않았으며, 문헌[S.M. Park, J.W. Park, H.-P. Ha, H.-S. Han, G. Seo, J. Mol. Catal. A: Chem., 273, 64(2007)]에 보고된 γ-알루미나에 관련된 회절 패턴만 확인 할 수 있었다.
FIG. 5 shows an X-ray diffraction pattern of the S (10) -Ni / γ- Al 2 O 3 (0.20) solid oxide catalyst prepared in Comparative Example 2. According to FIG. 5, X-ray diffraction analysis of the solid oxide catalyst of S (10) NA (0.20) showed no other specific peaks. SM Park, JW Park, H.-P. Ha, H.-S. Han, G. Seo, J. Mol. Catal. A: Chem., 273, 64 (2007)] can only confirm the diffraction pattern related to γ -alumina.
[실험예]
Experimental Example
실험예 1. 촉매의 비표면적 및 평균 세공크기 측정Experimental Example 1. Measurement of specific surface area and average pore size of catalyst
하기 표 1에는 상기 실시예 2의 방법으로 제조된 황산이온 담지 니켈-알루미나 고체 산화물 촉매의 비표면적과 평균 세공크기를 측정하여 나타내었다.Table 1 below shows the specific surface area and average pore size of the sulfate-ion-supported nickel-alumina solid oxide catalyst prepared by the method of Example 2.
질소흡착법으로 측정하였으며, 질소흡착은 부피식 흡착장치(Mirae SI, NanoPorosity-XQ)로 질소 흡착등온선을 그렸다. 300 ℃에서 5시간 배기한 후 액체질소 온도(-196 ℃)에서 질소를 흡착시켰다. 비표면적은 BET 식을 이용하여 계산하였고, 평균 세공크기는 BJH 방법을 이용하여 계산하였다.Nitrogen adsorption was measured by nitrogen adsorption method, and nitrogen adsorption isotherms were drawn using a volumetric adsorption device (Mirae SI, NanoPorosity-XQ). After exhausting at 300 ° C. for 5 hours, nitrogen was adsorbed at a liquid nitrogen temperature (−196 ° C.). The specific surface area was calculated using the BET equation, and the average pore size was calculated using the BJH method.
(m2/g)BET surface area
(m 2 / g)
(Å)Average pore size
(A)
실시예 2
Example 2
상기 표 1에 의하면, 비표면적은 니켈/알루미나 몰 비에 따라 차이가 있지만 대부분이 비표면적이 170 m2/g 이상이었으며, 평균 세공크기도 36 내지 45 Å 정도였다. 황산이온의 담지량이 증가함에 따라 그리고 열처리 온도가 증가함에 따라 비표면적은 증가하다가 감소하였다. According to Table 1, the specific surface area is different depending on the nickel / alumina mole ratio, but most of the specific surface area was 170 m 2 / g or more, the average pore size was about 36 to 45 Å. The specific surface area increased and then decreased as the amount of sulfate ion increased and as the heat treatment temperature increased.
비교예 1은 공침온도 70 ℃에서 제조된 담체 또는 고체 산화물 촉매로서, 비표면적과 평균 세공크기는 실시예 2의 고체 산화물 촉매와 거의 비슷한 수준이었다.Comparative Example 1 was a carrier or solid oxide catalyst prepared at a coprecipitation temperature of 70 ° C., and the specific surface area and average pore size were almost the same as those of the solid oxide catalyst of Example 2.
그러나, 비교예 2는 알루미나 담지체에 황산이온과 니켈을 담지시켜 제조한 고체 산화물 촉매로서, 실시예 2의 고체 산화물 촉매와 비교할 때 비표면적이 매우 낮고 평균 세공크기가 상대적으로 매우 큰 경향을 나타내었다.
However, Comparative Example 2 is a solid oxide catalyst prepared by supporting sulfate and nickel on an alumina carrier, and has a relatively low specific surface area and a relatively large average pore size when compared to the solid oxide catalyst of Example 2. It was.
실험예 2. 에틸렌의 이량화 반응 : 촉매 및 반응조건 선정Experimental Example 2 Dimerization of Ethylene: Selection of Catalysts and Reaction Conditions
상기 실시예 2 및 비교예 1, 2에 의해 제조된 촉매들의 반응성 평가는 통상적인 Batch식 반응기에서 촉매 활성을 평가하였다. Evaluation of the reactivity of the catalysts prepared in Example 2 and Comparative Examples 1 and 2 evaluated the catalytic activity in a conventional batch reactor.
촉매를 수분 보정 후 0.3 g씩 정확히 측정하여 3/8″스테인리스 반응기에 넣고, 진공상태에서 350 ℃로 2시간 동안 전 처리하였다. 반응기 온도를 20 ℃로 유지 후 반응기 내 에틸렌의 분압이 0.7 atm일 때 반응을 시작하여 2시간 동안 반응을 진행하였으며, 소모되는 에틸렌 양은 반응시간에 따른 에틸렌 분압의 변화를 측정하여 반응활성을 계산하였다.After calibrating the water, the catalyst was accurately measured in 0.3 g increments and placed in a 3/8 "stainless steel reactor, and pretreated for 2 hours at 350 ° C in a vacuum. After the reactor temperature was maintained at 20 ℃, the reaction was started when the partial pressure of ethylene in the reactor was 0.7 atm, and the reaction proceeded for 2 hours. The amount of ethylene consumed was calculated by measuring the change in the partial pressure of ethylene according to the reaction time. .
하기 비교실험에 얻은 반응활성은 하기 수학식 1에 의해 계산하였다.The reaction activity obtained in the following comparative experiment was calculated by the following equation.
[수학식 1][Equation 1]
1) 담지체를 구성하는 니켈/알루미늄 몰 비에 따른 촉매 활성 비교1) Comparison of catalyst activity according to the nickel / aluminum mole ratio constituting the support
하기 표 2에는 고체 산화물 촉매 제조에 사용된 니켈-알루미나 담지체의 니켈/알루미늄 몰 비 변화에 따른 반응활성 정도를 비교하여 나타내었다.Table 2 below shows a comparison of the degree of reaction activity according to the change in the nickel / aluminum mole ratio of the nickel-alumina support used to prepare the solid oxide catalyst.
전처리 온도: 300 ℃, 전처리 시간: 2시간
[에틸렌의 이량화 반응조건]
반응온도: 20 ℃, 반응시간: 2시간, 에틸렌 분압: 0.7 atm[Catalyst Pretreatment Conditions]
Pretreatment temperature: 300 ℃, Pretreatment time: 2 hours
[Ethylene Dimerization Reaction Conditions]
Reaction temperature: 20 DEG C, reaction time: 2 hours, ethylene partial pressure: 0.7 atm
상기 표 2에 나타낸 것처럼, 본 발명의 황산이온 담지 니켈-알루미나 고체 산화물 촉매는 담지체를 구성하는 니켈/알루미늄의 몰 비에 따라 촉매 활성에 차이를 보였으며, 특히 니켈/알루미늄의 몰 비가 0.2인 S(6.0)NA(0.2) 고체 산화물 촉매의 반응활성이 1.98 mmol/g로 가장 높았다.
As shown in Table 2, the sulfate-ion-supported nickel-alumina solid oxide catalyst of the present invention showed a difference in catalyst activity depending on the molar ratio of nickel / aluminum constituting the carrier, in particular, the molar ratio of nickel / aluminum is 0.2. The reaction activity of the S (6.0) NA (0.2) solid oxide catalyst was the highest at 1.98 mmol / g.
2) 황산이온의 담지량에 따른 촉매 활성 비교2) Comparison of Catalyst Activity According to the Amount of Sulfate Ion
하기 표 3에는 상기 실험예 2의 방법으로 에틸렌의 이량화 반응을 수행할 때, 니켈-알루미나 담지체에 담지되는 황산이온의 담지량에 따른 반응활성 정도를 비교하여 나타내었다.Table 3 below shows the degree of reaction activity according to the amount of sulfate ion supported on the nickel-alumina support when the dimerization reaction of ethylene was carried out by the method of Experimental Example 2.
전처리 온도: 350 ℃, 전처리 시간: 2시간
[에틸렌의 이량화 반응조건]
반응온도: 20 ℃, 반응시간: 2시간, 에틸렌 분압: 0.7 atm[Catalyst Pretreatment Conditions]
Pretreatment temperature: 350 ° C, Pretreatment time: 2 hours
[Ethylene Dimerization Reaction Conditions]
Reaction temperature: 20 DEG C, reaction time: 2 hours, ethylene partial pressure: 0.7 atm
에틸렌 이량화 반응은 산 촉매 반응이기 때문에 고체산 역할을 하는 황산이온 담지량에 따라 반응활성에 차이가 있다. 상기 표 3에 나타낸 것처럼 황산이온 담지량이 증가할수록 반응 활성은 증가하여 황산이온 함량이 10 중량%인 S(10)NA(0.20) 고체 산화물 촉매에서 반응활성이 3.45 mmol/g으로 가장 높았다. 하지만, 황산이온의 담지량이 너무 많으면 반응활성이 감소하였다. 또한 공침 온도를 높여서 제조한 고체 산화물 촉매(비교예 1) 또는 기존 γ-알루미나 담지체에 니켈과 황산이온을 담지하여 제조한 고체 산화물 촉매(비교예 2)에 비교하여, 본 발명의 황산이온 담지 니켈-알루미나 고체 산화물 촉매는 보다 반응활성이 높아 에틸렌 이량화 반응에 우수한 촉매임을 확인 할 수 있다.
Since the ethylene dimerization reaction is an acid catalyzed reaction, there is a difference in reaction activity depending on the amount of sulfate ion serving as a solid acid. As shown in Table 3 above, as the amount of sulfate ion supported increased, the reaction activity increased to the highest at 3.45 mmol / g in the S (10) NA (0.20) solid oxide catalyst having a sulfate ion content of 10% by weight. However, if the amount of sulfate ion supported was too large, the reaction activity decreased. In addition, compared to the solid oxide catalyst prepared by raising the coprecipitation temperature (Comparative Example 1) or the solid oxide catalyst prepared by supporting nickel and sulfate ions in the existing γ -alumina support (Comparative Example 2), the sulfate ion supported of the present invention Nickel-alumina solid oxide catalysts can be confirmed that the higher the catalytic activity is excellent catalyst for ethylene dimerization reaction.
3) 촉매의 열처리 온도에 따른 촉매 활성 비교3) Comparison of Catalyst Activity According to Heat Treatment Temperature of Catalyst
하기 표 4에는 상기 실험예 2의 방법으로 에틸렌의 이량화 반응을 수행할 때, S(6)NA(0.20) 고체 산화물 촉매 제조를 위한 열처리 온도 조건에 따른 반응활성 정도를 비교하여 나타내었다.Table 4 below shows the degree of reaction activity according to the heat treatment temperature conditions for the preparation of S (6) NA (0.20) solid oxide catalyst when performing the dimerization reaction of ethylene by the method of Experimental Example 2.
촉매: S(10)NA(0.20), 전처리 온도: 350 ℃, 전처리 시간: 2시간
[에틸렌의 이량화 반응조건]
반응온도: 20 ℃, 반응시간: 2시간, 에틸렌 분압: 0.7 atm[Catalyst Pretreatment Conditions]
Catalyst: S (10) NA (0.20), Pretreatment temperature: 350 ° C., Pretreatment time: 2 hours
[Ethylene Dimerization Reaction Conditions]
Reaction temperature: 20 DEG C, reaction time: 2 hours, ethylene partial pressure: 0.7 atm
상기 표 4에 의하면, 촉매 제조 시 남아 있는 유기물 제거와 황산이온의 활성에 영향을 주는 열처리 온도에 대해 반응 활성 평가 결과 큰 차이를 보였으며, 500 ℃에서 열처리 하였을 때 최고의 촉매활성을 나타내었다. 상기 결과에 의하면, 열처리 온도가 400 ℃로 낮으면 촉매 제조 후 남아있는 유기물의 제거가 완벽하게 되지 않고, 황산이온이 활성화 되지 않아 반응 활성이 2.28 mmol/g으로 낮았고, 열처리 온도가 600 ℃로 너무 높으면 담지 된 황산이온이 일부 제거되어 반응 활성이 2.88 mmol/g으로 낮아졌다.
According to Table 4, the reaction activity evaluation results showed a great difference with respect to the heat treatment temperature affecting the removal of organic matter remaining in the catalyst preparation and the activity of sulfate ions, and showed the best catalytic activity when the heat treatment at 500 ℃. According to the results, when the heat treatment temperature is low at 400 ℃, the removal of the organic matter remaining after the preparation of the catalyst is not perfect, the sulfate ion is not activated, the reaction activity was low to 2.28 mmol / g, and the heat treatment temperature is too high at 600 ℃ At higher levels, some of the supported sulfate ions were removed, lowering the reaction activity to 2.88 mmol / g.
4) 촉매의 전처리 시간에 따른 촉매 활성 비교4) Comparison of Catalyst Activity According to Pretreatment Time of Catalyst
하기 표 5에는 S(6)NA(0.20) 고체 산화물 촉매를 이용하여 상기 실험예 2의 방법으로 에틸렌의 이량화 반응을 수행할 때, 상기 촉매를 300 ℃에서 전처리하는 시간에 따른 반응활성 정도를 정리하여 나타내었다.Table 5 shows the degree of reaction activity according to the time of pretreatment of the catalyst at 300 ° C. when the dimerization reaction of ethylene was carried out by the method of Experimental Example 2 using the S (6) NA (0.20) solid oxide catalyst. In summary.
촉매: S(6.0)NA(0.20), 전처리 온도: 300 ℃
[에틸렌의 이량화 반응조건]
반응온도: 20 ℃, 반응시간: 2시간, 에틸렌 분압: 0.7 atm[Catalyst Pretreatment Conditions]
Catalyst: S (6.0) NA (0.20), Pretreatment temperature: 300 ° C
[Ethylene Dimerization Reaction Conditions]
Reaction temperature: 20 DEG C, reaction time: 2 hours, ethylene partial pressure: 0.7 atm
5) 촉매의 전처리 온도에 따른 촉매 활성 비교5) Comparison of Catalyst Activity According to Pretreatment Temperature of Catalyst
하기 표 6에는 S(6)NA(0.20) 고체 산화물 촉매를 이용하여 상기 실험예 2의 방법으로 에틸렌의 이량화 반응을 수행할 때, 상기 촉매를 2시간 동안 전처리하여 사용하였으며 이때 촉매의 전처리 온도에 따른 반응활성 정도를 비교하여 나타내었다.In Table 6, when the dimerization reaction of ethylene was carried out using the S (6) NA (0.20) solid oxide catalyst by the method of Experimental Example 2, the catalyst was pretreated for 2 hours and the pretreatment temperature of the catalyst was used. The degree of reaction activity was compared.
촉매: S(6.0)NA(0.20), 전처리 시간: 2시간
[에틸렌의 이량화 반응조건]
반응온도: 20 ℃, 반응시간: 2시간, 에틸렌 분압: 0.7 atm[Catalyst Pretreatment Conditions]
Catalyst: S (6.0) NA (0.20), Pretreatment time: 2 hours
[Ethylene Dimerization Reaction Conditions]
Reaction temperature: 20 DEG C, reaction time: 2 hours, ethylene partial pressure: 0.7 atm
6) 에틸렌 분압에 따른 촉매 활성 비교6) Comparison of Catalyst Activity According to Ethylene Partial Pressure
하기 표 7에는 S(6)NA(0.20) 고체 산화물 촉매를 이용하여 상기 실험예 2의 방법으로 에틸렌의 이량화 반응을 수행할 때, 에틸렌 분압에 따른 반응활성 정도를 비교하여 나타내었다.Table 7 shows a comparison of the degree of reaction activity according to the ethylene partial pressure when the dimerization reaction of ethylene was carried out by the method of Experimental Example 2 using S (6) NA (0.20) solid oxide catalyst.
촉매: S(6.0)NA(0.20), 전처리 온도: 300 ℃, 전처리 시간: 2시간
[에틸렌의 이량화 반응조건]
반응온도: 20 ℃, 반응시간: 2시간[Catalyst Pretreatment Conditions]
Catalyst: S (6.0) NA (0.20), Pretreatment temperature: 300 ° C., Pretreatment time: 2 hours
[Ethylene Dimerization Reaction Conditions]
Reaction temperature: 20 ℃, Reaction time: 2 hours
7) 이량화 반응시간에 따른 촉매 활성 비교7) Comparison of Catalyst Activity According to Dimerization Reaction Time
도 6에는 S(6)NA(0.20) 고체 산화물 촉매를 이용하여 상기 실험예 2의 방법으로 에틸렌의 이량화 반응을 수행하였을 때, 반응시간에 따른 반응활성을 나타낸 그래프이다. 도 6에 의하면, 반응시간이 경과할수록 반응활성 정도는 향상되었으며, 120분이 경과되어도 반응활성은 지속적으로 증가됨을 확인할 수 있었다.
Figure 6 is a graph showing the reaction activity according to the reaction time when the dimerization of ethylene by the method of Experiment 2 using the S (6) NA (0.20) solid oxide catalyst. According to Figure 6, as the reaction time elapsed the degree of reaction activity was improved, even after 120 minutes it was confirmed that the reaction activity continuously increased.
상기한 실험결과로부터, 본 발명의 황산이온 담지 니켈-알루미나 고체 산화물 촉매를 사용하여 에틸렌의 이량화 반응을 수행함에 있어, 촉매의 전처리 온도, 전처리 시간 및 에틸렌 분압 등 최적의 반응조건을 선정할 수 있었다.From the above experimental results, in carrying out the ethylene dimerization reaction using the sulfate-ion-supported nickel-alumina solid oxide catalyst of the present invention, it is possible to select optimum reaction conditions such as pretreatment temperature, pretreatment time and ethylene partial pressure of the catalyst. there was.
Claims (6)
That it is a solid oxide carrier of alumina in 85 to 97% by weight, a sulfate ion (SO 4 2-) is 3 to 15% by weight supported-nickel (Ni) / aluminum (Al) molar ratio of 0.1 to the nickel constituting the first ranges of Solid oxide catalyst for dimerization reaction of ethylene.
상기 니켈-알루미나 고체 산화물 담지체는 비표면적이 170 내지 250 m2/g 범위인 것을 특징으로 하는 에틸렌의 이량화 반응용 고체 산화물 촉매.
The method of claim 1,
The nickel-alumina solid oxide support has a specific surface area in the range of 170 to 250 m 2 / g solid oxide catalyst for dimerization reaction of ethylene.
상기 니켈-알루미늄 혼합용액에 공침제를 첨가하여 pH를 7.5 내지 8.5로 조절한 후, 교반 및 공침시켜 공침용액을 제조하는 단계;
상기 공침용액을 여과 및 세척한 후, 70 내지 140 ℃에서 건조하고, 400 내지 600 ℃에서 열처리하여 니켈-알루미나 고체 산화물 담지체를 얻는 단계;
상기 니켈-알루미나 고체 산화물 담지체를 황산 전구체가 녹아있는 수용액에 첨가하고 감압 증류하여, 상기 니켈-알루미나 고체 산화물 담지체 85 내지 97 중량%에 황산이온이 3 내지 15 중량% 담지 된 고체 시료를 얻는 단계; 및
상기 황산이온이 담지 된 니켈-알루미나 고체 시료를 100 내지 120 ℃에서 건조시키고, 400 내지 600 ℃에서 열처리하여 황산이온이 담지 된 니켈-알루미나 고체 산화물 촉매를 얻는 단계;
를 포함하는 것을 특징으로 하는 에틸렌의 이량화 반응용 고체 산화물 촉매의 제조방법.
Preparing a nickel-aluminum mixed solution by dissolving the nickel precursor and the aluminum precursor in distilled water such that the molar ratio of nickel (Ni) / aluminum (Al) is 0.1 to 1;
Preparing a coprecipitation solution by adding a coprecipitation agent to the nickel-aluminum mixed solution to adjust pH to 7.5 to 8.5, followed by stirring and coprecipitation;
Filtering and washing the coprecipitation solution, drying at 70 to 140 ° C., and heat treating at 400 to 600 ° C. to obtain a nickel-alumina solid oxide support;
The nickel-alumina solid oxide support was added to an aqueous solution in which a sulfuric acid precursor was dissolved and distilled under reduced pressure to obtain a solid sample in which 3 to 15 wt% of sulfate ion was supported on 85 to 97 wt% of the nickel-alumina solid oxide support. step; And
Drying the nickel-alumina solid sample loaded with sulfate ion at 100 to 120 ° C. and heat-treating at 400 to 600 ° C. to obtain a nickel-alumina solid oxide catalyst loaded with sulfate ion;
Method for producing a solid oxide catalyst for the dimerization reaction of ethylene comprising a.
The amount of ethylene according to claim 3, wherein at least one selected from nickel nitrate and nickel chloride is used as the nickel precursor, and at least one selected from aluminum nitrate and aluminum chloride is used as the aluminum precursor. Method for producing a solid oxide catalyst for the oxidation reaction.
The method of claim 3, wherein the coprecipitation agent is selected from the group consisting of ammonia water, an alkali metal carbonate aqueous solution, and an alkali metal hydroxide aqueous solution.
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