WO2015161700A1 - 一种用于合成气生产α-烯烃的结构化铁基催化剂及制备方法和应用 - Google Patents
一种用于合成气生产α-烯烃的结构化铁基催化剂及制备方法和应用 Download PDFInfo
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- WO2015161700A1 WO2015161700A1 PCT/CN2015/072400 CN2015072400W WO2015161700A1 WO 2015161700 A1 WO2015161700 A1 WO 2015161700A1 CN 2015072400 W CN2015072400 W CN 2015072400W WO 2015161700 A1 WO2015161700 A1 WO 2015161700A1
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- Prior art keywords
- iron
- based catalyst
- auxiliary agent
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 122
- 239000003054 catalyst Substances 0.000 title claims abstract description 66
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 65
- 239000004711 α-olefin Substances 0.000 title claims abstract description 35
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 22
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 28
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 11
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 11
- 239000002245 particle Substances 0.000 claims abstract description 11
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 11
- 239000002243 precursor Substances 0.000 claims abstract description 5
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 5
- 150000003624 transition metals Chemical class 0.000 claims abstract description 5
- 229910000314 transition metal oxide Inorganic materials 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 31
- 230000009467 reduction Effects 0.000 claims description 22
- KBPLFHHGFOOTCA-UHFFFAOYSA-N caprylic alcohol Natural products CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims description 20
- 239000007789 gas Substances 0.000 claims description 15
- 238000004519 manufacturing process Methods 0.000 claims description 15
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 13
- 239000001257 hydrogen Substances 0.000 claims description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 11
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 229910002651 NO3 Inorganic materials 0.000 claims description 9
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 9
- 239000002002 slurry Substances 0.000 claims description 8
- 239000012018 catalyst precursor Substances 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 5
- 239000006185 dispersion Substances 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 3
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 230000032683 aging Effects 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 238000007598 dipping method Methods 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 239000000395 magnesium oxide Substances 0.000 claims description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 claims description 2
- 229910001950 potassium oxide Inorganic materials 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims 3
- 229910000420 cerium oxide Inorganic materials 0.000 claims 2
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims 2
- 229910052746 lanthanum Inorganic materials 0.000 claims 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims 1
- 229910001928 zirconium oxide Inorganic materials 0.000 claims 1
- 235000012239 silicon dioxide Nutrition 0.000 abstract 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 12
- 229910004298 SiO 2 Inorganic materials 0.000 description 9
- 150000001336 alkenes Chemical class 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 6
- 239000005977 Ethylene Substances 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 229940057995 liquid paraffin Drugs 0.000 description 5
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 4
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 4
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 4
- 238000005336 cracking Methods 0.000 description 4
- 238000005984 hydrogenation reaction Methods 0.000 description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 4
- 238000006384 oligomerization reaction Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
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- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 3
- 229910021193 La 2 O 3 Inorganic materials 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 239000004014 plasticizer Substances 0.000 description 3
- 229920013639 polyalphaolefin Polymers 0.000 description 3
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 229920001903 high density polyethylene Polymers 0.000 description 2
- 239000004700 high-density polyethylene Substances 0.000 description 2
- 229920000092 linear low density polyethylene Polymers 0.000 description 2
- 239000004707 linear low-density polyethylene Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- -1 polyethylene Polymers 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 2
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- AWFYPPSBLUWMFQ-UHFFFAOYSA-N 2-[5-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-1,3,4-oxadiazol-2-yl]-1-(1,4,6,7-tetrahydropyrazolo[4,3-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1=NN=C(O1)CC(=O)N1CC2=C(CC1)NN=C2 AWFYPPSBLUWMFQ-UHFFFAOYSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000002199 base oil Substances 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 239000000675 fabric finishing Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000009962 finishing (textile) Methods 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
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- 235000010446 mineral oil Nutrition 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 150000005673 monoalkenes Chemical class 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
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- 238000005245 sintering Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 1
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- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
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- C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
- C10G2/33—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used
- C10G2/331—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals
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- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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- C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
- C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
- C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
- C10G2/33—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used
- C10G2/331—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals
- C10G2/333—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals of the platinum-group
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G5/00—Recovery of liquid hydrocarbon mixtures from gases, e.g. natural gas
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/20—C2-C4 olefins
Definitions
- the invention belongs to the field of catalysts and their preparation and application, and in particular relates to a structured iron-based catalyst for syngas production of ⁇ -olefins, a preparation method and application thereof.
- the long-chain ⁇ -olefin refers to a monoolefin or a mixed olefin having an unsaturated bond at a carbon terminal position of a chain hydrocarbon terminal or more and a carbon number of 16 or less. Since the molecule contains an active site (ethylenic bond), the ⁇ -olefin is easily incorporated into various functional groups and derivatized into alcohol, acid, ester and other compounds, and is widely used in the production of fine chemicals such as surfactants and plasticizers. At present, ⁇ -olefins are mainly used as comonomers for the production of polyethylene, accounting for 44.1% of the total consumption.
- comonomers The most widely used varieties for comonomers are C 4 (1-butene), C 6 (1-hexene) and C 8 (1-octene) in the production of high density polyethylene and linear low density polyethylene.
- the use of these comonomers in (HDPE/LLDPE) improves PE density and increases tear and tensile strength.
- ⁇ -olefins are also used to produce high-carbon alcohols.
- the final products are plasticizers and detergents, accounting for 19.6% of the total consumption.
- High-carbon alcohol is the basic raw material for surfactants and plasticizers, and the annual consumption in the world has reached about 10 million tons.
- Octanol is mainly used in the preparation of various esters, with annual sales of more than $1 billion worldwide.
- Heptanol can be used to prepare perfumes and flavors with high value.
- ⁇ -olefins are also used to produce polyalphaolefins (PAO), which accounts for 16.6% of the total consumption.
- PAO is a raw material for high-end lubricant base oils. The viscosity index is high and the price is 2-3 times that of mineral oil.
- ⁇ -olefins are also used as raw materials for emulsifiers, leather treatment agents, lubricating oil additives, rust inhibitors, fabric finishing agents, and papers for chemicals and the like.
- the total production capacity of foreign alpha-olefins is about 2.12 million tons, and the domestic production capacity is 260,000 tons. Moreover, domestic lack of ability to produce long-chain alpha-olefins, 1-octene and 1-hexene are almost completely dependent on imports.
- paraffin cracking or ethylene oligomerization.
- the paraffin cracking method is generally used as a raw material for deoiling and refining wax.
- the raw material wax is preheated and mixed with steam, and the reaction is carried out in a tubular cracking furnace at about 550 °C.
- the ethylene oligomerization reaction is carried out under the action of a triethylaluminum catalyst, and ethylene undergoes a controlled chain growth reaction to polymerize into a chain length olefin. Specifically, it can be divided into a two-step method, a one-step method, and a SHOP process.
- the Chinese Patent of Publication No. 101265151 discloses a process for producing light olefins from methanol or dimethyl ether.
- the methanol or dimethyl ether feed is fed to the reaction zone of the reactor through a feed distributor and contacted with the molecular sieve catalyst to form a mixture comprising light olefins, diolefins, oxygenates, and carbon tetrahydrocarbons.
- the Chinese invention patent represented by Publication Nos. 101265149 and 1537674 discloses an iron/activated carbon catalyst which directly reacts ethylene, propylene and butene from synthesis gas, and is characterized by the specific chemical composition of the self-made catalyst.
- the Chinese invention patent represented by Publication No. 1284898A, 1515359A discloses a method of producing self-supporting precipitated iron-based catalyst particles for use in a Fischer-Tropsch slurry bed process.
- a structured iron-based catalyst for syngas production of ⁇ -olefins of the present invention comprises an active component, an auxiliary agent and a carrier, the active component of which is iron; and the auxiliary agent includes the first auxiliary VIB , Group VIIB or Group VIII transition metal ruthenium, platinum, copper, cobalt, zinc, second auxiliary metal oxide: ruthenium oxide, ruthenium oxide, magnesium oxide, aluminum oxide, silicon oxide, potassium oxide, manganese oxide, zirconia
- the weight percentage of the catalyst is: active component iron: 50.0 to 99.8%, first auxiliary transition metal or transition metal oxide content: 0 to 5.0%; second auxiliary metal oxide: 0 to 10%, balance
- the carrier silica; the active component iron, the first auxiliary agent, and the carrier silica are formed into monodisperse particles by a heat dispersion method, and then impregnated with a second auxiliary solution.
- the content of the first auxiliary agent is selected from 0 to 2%; the content of the second auxiliary metal oxide is selected from 2 to 6%, and the content of the active component is selected from 60 to 97%.
- the carrier has a silica content of 1 to 40%, a first auxiliary agent content of 1 to 2%, a second auxiliary metal oxide content of 2 to 6%, and a balance of the active component of iron.
- a method for preparing a structured iron-based catalyst the steps are as follows:
- the iron nitrate of the decrystallization water and the nitrate of the first auxiliary agent and the amorphous silica are added to n-octanol according to the weight ratio thereof, and the total weight of each substance accounts for 3-20% of the mixed solution, and the mixture is stirred.
- the salt is dissolved, heated to 140-180 ° C, and kept at a constant temperature for 4 h. After cooling, it is filtered and dried to obtain a black solid. After grinding for 20 to 40 minutes by planetary grinding, it is placed in a muffle furnace at 400-600 ° C for 5 h to obtain a catalyst.
- Precursor A
- the weight percentage of each component of the structured iron-based catalyst is: carrier silica content: 1 to 40%, first additive content is selected from 1 to 2%; second additive metal oxide content is selected from 2 to 6%.
- the balance is that the active component is iron.
- the method for preparing the structured iron-based catalyst the step 1) mixing the ferric nitrate of the decrystallized water and the nitrate of the first auxiliary agent and the amorphous silica into the n-octanol according to the weight ratio thereof, respectively
- the total weight of the substance is 5 to 15% of the mixed liquid.
- the catalyst precursor A has a particle size of 50 to 60 nm and is spherical and has a monodisperse distribution.
- the invention has the following advantages:
- the catalyst of the invention uses the thermal decomposition method to prepare the main active component of the catalyst, and the powder obtained by the invention has the characteristics of regular shape and uniform pore size, and the catalytic material finally prepared has a unique shape. Appearance and microstructure.
- the method of the present invention can obtain an iron phase in which the particles are uniform and spherical, having a particle size of about 70 nm and a monodisperse structure. This structure makes the iron catalytically active center more consistent and facilitates the construction of the active center. At the same time, the powder with uniform morphology is more likely to form an ideal pore structure.
- the catalyst of the invention has a high degree of reduction and degree of carbonization due to the reasonable blending of the strength between the iron and the auxiliary agent.
- the adjustment of the amount and the use of the auxiliary agent the interaction between the active component of the catalyst and the carrier is reasonable, that is, the sintering of the iron component is prevented, and the occurrence of the difficult-reducing component is avoided, and the catalyst is Has excellent chemical properties.
- the synergistic effect of both structural and chemical factors allows the catalyst to have higher long-chain alpha-olefin selectivity and activity.
- the catalyst can be formed from powder tableting or spray drying, and has good mechanical properties.
- the present invention provides a novel process for the production of alpha-olefins which utilizes syngas as a feedstock to directly synthesize alpha-olefins under the action of the catalyst of the present invention.
- the present invention is different in raw materials, target products, technical routes, catalyst manufacturing methods, and the like, thereby forming a new technology which is distinct from the prior art and has outstanding innovation in producing ⁇ -olefins.
- the monodisperse structure of the present invention and suitable metal-support chemistry allow the catalyst to produce an active center suitable for alpha-olefin formation and thus have excellent selectivity.
- Figure 1 is a TEM photograph of the structure of an iron catalyst prepared by thermal decomposition.
- Example 1 53%Fe 1% La 2 O 3
- Example 2 75% Fe 2% K 2 O 1% MnO
- Example 3 60% Fe 10%Co 2% CuO
- Example 4 54%Fe 5% Co 4% ZrO 2
- Example 5 90%Fe 6% Al 2 O 3
- Example 6 80%Fe 3%Cr 2 O 3 0.5%
- K 2 O Example 7
- Example 8 70% Fe 2% CeO 2 0.3% CuO
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Abstract
Description
编号 | Fe含量 | 助剂1含量 | 助剂2含量 |
实施例1 | 53%Fe | 1%La2O3 | |
实施例2 | 75%Fe | 2%K2O | 1%MnO |
实施例3 | 60%Fe | 10%Co | 2%CuO |
实施例4 | 54%Fe | 5%Co | 4%ZrO2 |
实施例5 | 90%Fe | 6%Al2O3 | |
实施例6 | 80%Fe | 3%Cr2O3 | 0.5%K2O |
实施例7 | 95%Fe | 1%ZnO | 0.2%K2O |
实施例8 | 70%Fe | 2%CeO2 | 0.3%CuO |
实施例9 | 68%Fe | 2%TiO2 | 0.1%Ru |
实施例10 | 98%Fe | 1%Al2O3 | 0.2%K2O |
Claims (10)
- 一种用于合成气生产α-烯烃的结构化铁基催化剂,包括活性组分、助剂和载体,其特征在于:活性组分为铁;助剂包括第一助剂VIB、VIIB族或VIII族的过渡金属钌、铂、铜、钴、锌,第二助剂金属氧化物:氧化镧、氧化铈、氧化镁、氧化铝、氧化硅、氧化钾、氧化锰、氧化锆;催化剂的重量百分比为:活性组分铁:50.0~99.8%,第一助剂过渡金属或过渡金属氧化物含量:0~5.0%;第二助剂金属氧化物:0~10%,余量为载体二氧化硅;将活性组分铁、第一助剂、载体二氧化硅用热分散法制成单分散颗粒后,用第二助剂溶液浸渍。
- 根据权利要求1所述的用于合成气生产α-烯烃的结构化铁基催化剂,其特征在于:第一助剂含量选0~2%;第二助剂金属氧化物含量选2~6%,活性组分铁含量选60~97%。
- 根据权利要求1所述的用于合成气生产α-烯烃的结构化铁基催化剂,其特征在于:载体二氧化硅含量:1~40%、第一助剂含量选1~2%;第二助剂金属氧化物含量选2~6%,余量为活性组分为铁。
- 一种权利要求1~3之一的结构化铁基催化剂的制备方法,步骤如下:1)用热分散法制备单分散颗粒催化剂前驱体A:将去结晶水的硝酸铁和第一助剂的硝酸盐以及无定形二氧化硅按其重量比要求加入到正辛醇中混合,各物质总重量占混合液的3~20%,搅拌,硝酸盐溶解,升温到140~180℃度后,恒温4h,冷却后抽滤烘干,得到黑色固体,经行星磨研磨20~40分钟后置于马弗炉中400-600℃焙烧5h,得到催化剂前驱体A;2)将第二助剂按重量比溶于水或乙醇,用配制好的第二助剂的溶液干法浸渍上述催化剂前驱体A,老化12~24小时,然后于100~130℃干燥,于300~1200℃焙烧4~10小时,压片,筛分,制得结构化铁基催化剂。
- 根据权利要求4所述的结构化铁基催化剂的制备方法,其特征在于:各成分重量百分比为:载体二氧化硅含量:1~40%、第一助剂含量选1~2%;第二助剂金属氧化物含量选2~6%,余量为活性组分为铁。
- 根据权利要求4或5所述的结构化铁基催化剂的制备方法,其特征在于:步骤1)将去结晶水的硝酸铁和第一助剂的硝酸盐以及无定形二氧化硅按其重量比要求加入到正辛醇中混合,各物质总重量占混合液的5~15%。
- 根据权利要求4或5所述的结构化铁基催化剂的制备方法,其特征在于:催化剂前驱体A的粒度为50~60nm,且为球形,呈单分散分布。
- 根据权利要求6所述的结构化铁基催化剂的制备方法,其特征在于:催化剂前驱体A的粒度为50~60nm,且为球形,呈单分散分布。
- 一种权利要求4~8之一方法制备的结构化铁基催化剂的应用,用于合成气生产α-烯烃在固定床进行费托合成反应的作条件为:还原条件为:300~500℃,0.2~1.2MPa,400~1500h-1(V/V),6~18h,纯氢气氛;合成气反应条件为:190~360℃,0.5~5.0MPa,400~20000h-1(V/V),H2/CO=1/1~3/1。
- 一种权利要求4~8之一方法制备的结构化铁基催化剂的应用,用于合成气生产α-烯烃在浆态床中进行费托合成反应的作条件为:还原条件为:300~500℃,0.2~1.2MPa,400~1400rpm,400~1500h-1(V/V),6~18h,纯氢气氛;合成气反应条件为:190~360℃,0.5~5.0MPa,400~20000h-1(V/V),400~1400rpm,H2/CO=1/1~3/1。
Priority Applications (7)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP15782614.0A EP3135371A4 (en) | 2014-04-21 | 2015-02-06 | Structured iron-based catalyst for producing a-olefin from synthesis gas and preparation method and use |
RU2016145065A RU2659067C2 (ru) | 2014-04-21 | 2015-02-06 | СТРУКТУРИРОВАННЫЙ КАТАЛИЗАТОР НА ОСНОВЕ ЖЕЛЕЗА ДЛЯ ПРОИЗВОДСТВА α-ОЛЕФИНА ИЗ СИНТЕЗ-ГАЗА И СПОСОБ ЕГО ИЗГОТОВЛЕНИЯ И ПРИМЕНЕНИЕ |
AU2015251402A AU2015251402B2 (en) | 2014-04-21 | 2015-02-06 | Structured iron-based catalyst for producing alpha-olefin from synthesis gas and preparation method and use |
JP2016563184A JP6403797B2 (ja) | 2014-04-21 | 2015-02-06 | 合成ガスからのα−オレフィン製造用構造化鉄系触媒の調製方法並びに使用方法 |
CA2946450A CA2946450A1 (en) | 2014-04-21 | 2015-02-06 | Structured iron-based catalyst for producing a-olefin from synthesis gas and preparation method and use |
KR1020167032466A KR102000821B1 (ko) | 2014-04-21 | 2015-02-06 | 합성 가스로부터 알파-올레핀 생산용 구조적인 철-기반 촉매, 이의 제조 방법 및 이의 사용 |
US15/299,441 US10266776B2 (en) | 2014-04-21 | 2016-10-20 | Iron-based catalyst, method for preparing the same, and method for producing alpha-olefins using the same |
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CN103949262A (zh) * | 2014-04-21 | 2014-07-30 | 武汉凯迪工程技术研究总院有限公司 | 一种用于合成气生产α-烯烃的结构化铁基催化剂及制备方法和应用 |
CN105363458B (zh) * | 2014-08-27 | 2017-12-15 | 中国石油化工股份有限公司 | 合成轻质烃的催化剂及其制备方法 |
CN105363464B (zh) * | 2014-08-27 | 2018-01-09 | 中国石油化工股份有限公司 | 合成气直接制轻质烃的催化剂及其制备方法 |
CN105435803B (zh) * | 2014-08-27 | 2018-04-06 | 中国石油化工股份有限公司 | 微球状合成气制低碳烃的催化剂及其制备方法 |
CN105363463B (zh) * | 2014-08-27 | 2017-12-15 | 中国石油化工股份有限公司 | 合成气制轻质烃的催化剂及其制备方法 |
CN104492452A (zh) * | 2014-12-03 | 2015-04-08 | 中国石油大学(北京) | 合成气直接制低碳烯烃联产α-烯烃的催化剂及工艺 |
CN106582698B (zh) * | 2015-10-20 | 2019-05-21 | 中国石油化工股份有限公司 | 一种负载型催化剂及其制备方法和应用以及由合成气制备α-烯烃的方法 |
CN106590720B (zh) * | 2015-10-20 | 2018-07-31 | 中国石油化工股份有限公司 | 一种以煤和炼厂干气为原料制α-烯烃的方法 |
CN106391016B (zh) * | 2016-08-31 | 2019-03-19 | 武汉凯迪工程技术研究总院有限公司 | 费托合成单分散铁基催化剂及其制备方法和应用 |
CN107243347B (zh) * | 2017-07-06 | 2020-08-07 | 中国科学院上海高等研究院 | 一种合成气制烯烃的铁基催化剂及其制备方法和用途 |
CN107285972A (zh) * | 2017-07-11 | 2017-10-24 | 江南大学 | 一种从合成气生产芳香族化合物的连续反应工艺 |
CN112533697A (zh) * | 2018-06-05 | 2021-03-19 | 沙特基础全球技术有限公司 | 铁-镁二氧化硅负载的催化剂、其制备方法及其用途 |
CN111036282B (zh) * | 2018-10-15 | 2022-09-27 | 中国石油化工股份有限公司 | 负载型催化剂及其制备方法以及由合成气制备α-烯烃的方法 |
CN111068705B (zh) * | 2018-10-19 | 2022-09-23 | 中国石油化工股份有限公司 | 负载型催化剂前体及其制备方法以及α-烯烃的生产方法 |
CN111068745B (zh) * | 2018-10-19 | 2023-02-17 | 中国石油化工股份有限公司 | α-烯烃的生产方法 |
CN112569947B (zh) * | 2020-12-29 | 2022-02-15 | 中国科学院山西煤炭化学研究所 | 一种形貌可控的均匀棒状结构铁/石墨烯催化剂及其制备方法和应用 |
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KR20160147871A (ko) | 2016-12-23 |
RU2016145065A3 (zh) | 2018-05-21 |
EP3135371A4 (en) | 2018-01-17 |
RU2016145065A (ru) | 2018-05-21 |
CN103949262A (zh) | 2014-07-30 |
JP2017518170A (ja) | 2017-07-06 |
RU2659067C2 (ru) | 2018-06-28 |
EP3135371A1 (en) | 2017-03-01 |
US10266776B2 (en) | 2019-04-23 |
US20170037321A1 (en) | 2017-02-09 |
AU2015251402B2 (en) | 2017-09-14 |
CA2946450A1 (en) | 2015-10-29 |
JP6403797B2 (ja) | 2018-10-10 |
AU2015251402A1 (en) | 2016-12-01 |
KR102000821B1 (ko) | 2019-07-16 |
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