CN107930643A - A kind of catalyst and its application for preparation of low carbon olefines by synthetic gas - Google Patents
A kind of catalyst and its application for preparation of low carbon olefines by synthetic gas Download PDFInfo
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- CN107930643A CN107930643A CN201711087127.1A CN201711087127A CN107930643A CN 107930643 A CN107930643 A CN 107930643A CN 201711087127 A CN201711087127 A CN 201711087127A CN 107930643 A CN107930643 A CN 107930643A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 91
- 239000003054 catalyst Substances 0.000 title claims abstract description 79
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 66
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 72
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 56
- 229910052742 iron Inorganic materials 0.000 claims abstract description 22
- 239000011572 manganese Substances 0.000 claims abstract description 20
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 19
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 15
- 239000011591 potassium Substances 0.000 claims abstract description 15
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 8
- 229910052751 metal Inorganic materials 0.000 claims abstract description 6
- 239000002184 metal Substances 0.000 claims abstract description 6
- 239000000306 component Substances 0.000 claims abstract description 3
- 239000007789 gas Substances 0.000 claims description 87
- 239000000047 product Substances 0.000 claims description 69
- 229930195733 hydrocarbon Natural products 0.000 claims description 42
- 150000002430 hydrocarbons Chemical class 0.000 claims description 41
- 239000004215 Carbon black (E152) Substances 0.000 claims description 38
- 239000007788 liquid Substances 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 230000015572 biosynthetic process Effects 0.000 claims description 22
- 239000000243 solution Substances 0.000 claims description 22
- 238000003786 synthesis reaction Methods 0.000 claims description 22
- 239000012286 potassium permanganate Substances 0.000 claims description 20
- 239000003610 charcoal Substances 0.000 claims description 19
- 239000002250 absorbent Substances 0.000 claims description 18
- 230000002745 absorbent Effects 0.000 claims description 18
- 238000013019 agitation Methods 0.000 claims description 10
- 238000001354 calcination Methods 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 239000000706 filtrate Substances 0.000 claims description 9
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 238000011065 in-situ storage Methods 0.000 claims description 7
- 230000001603 reducing effect Effects 0.000 claims description 7
- 239000006004 Quartz sand Substances 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000012298 atmosphere Substances 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 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 6
- 239000012495 reaction gas Substances 0.000 claims description 5
- 239000006227 byproduct Substances 0.000 claims description 4
- 238000006555 catalytic reaction Methods 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 239000003502 gasoline Substances 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 2
- 238000010992 reflux Methods 0.000 claims description 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 claims 2
- 150000001336 alkenes Chemical class 0.000 abstract description 20
- 230000000694 effects Effects 0.000 abstract description 16
- 239000002245 particle Substances 0.000 abstract description 10
- 239000000126 substance Substances 0.000 abstract description 9
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 7
- 230000009257 reactivity Effects 0.000 abstract description 7
- 239000006185 dispersion Substances 0.000 abstract description 5
- 230000005012 migration Effects 0.000 abstract description 4
- 238000013508 migration Methods 0.000 abstract description 4
- 238000006116 polymerization reaction Methods 0.000 abstract description 4
- 230000009467 reduction Effects 0.000 abstract description 4
- 239000003921 oil Substances 0.000 description 28
- 238000000034 method Methods 0.000 description 19
- -1 propylene, butylene Chemical group 0.000 description 18
- 150000001335 aliphatic alkanes Chemical class 0.000 description 14
- 239000000463 material Substances 0.000 description 13
- 150000001298 alcohols Chemical class 0.000 description 11
- 238000004587 chromatography analysis Methods 0.000 description 11
- 238000001514 detection method Methods 0.000 description 11
- 238000004817 gas chromatography Methods 0.000 description 11
- 238000004445 quantitative analysis Methods 0.000 description 11
- 238000001228 spectrum Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 9
- 239000002994 raw material Substances 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 7
- 238000005554 pickling Methods 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 5
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 4
- 238000005984 hydrogenation reaction Methods 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 229910017604 nitric acid Inorganic materials 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000002028 Biomass Substances 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000012065 filter cake Substances 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 3
- 238000000197 pyrolysis Methods 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 229910001567 cementite Inorganic materials 0.000 description 2
- 239000010779 crude oil Substances 0.000 description 2
- 230000009849 deactivation Effects 0.000 description 2
- 238000002242 deionisation method Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- KSOKAHYVTMZFBJ-UHFFFAOYSA-N iron;methane Chemical compound C.[Fe].[Fe].[Fe] KSOKAHYVTMZFBJ-UHFFFAOYSA-N 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 2
- RBACIKXCRWGCBB-UHFFFAOYSA-N 1,2-Epoxybutane Chemical compound CCC1CO1 RBACIKXCRWGCBB-UHFFFAOYSA-N 0.000 description 1
- OQVYMXCRDHDTTH-UHFFFAOYSA-N 4-(diethoxyphosphorylmethyl)-2-[4-(diethoxyphosphorylmethyl)pyridin-2-yl]pyridine Chemical compound CCOP(=O)(OCC)CC1=CC=NC(C=2N=CC=C(CP(=O)(OCC)OCC)C=2)=C1 OQVYMXCRDHDTTH-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- GZETWZZNDACBTQ-UHFFFAOYSA-N [Cl].C=C Chemical compound [Cl].C=C GZETWZZNDACBTQ-UHFFFAOYSA-N 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000003102 growth factor Substances 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 239000010815 organic waste Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920005594 polymer fiber Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 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
- 238000010129 solution processing Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- 230000002459 sustained effect Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 230000035899 viability Effects 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- 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
- B01J37/0201—Impregnation
- B01J37/0207—Pretreatment of the support
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
-
- 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
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/393—Metal or metal oxide crystallite size
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
- C07C1/04—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen
- C07C1/0425—Catalysts; their physical properties
- C07C1/043—Catalysts; their physical properties characterised by the composition
- C07C1/0435—Catalysts; their physical properties characterised by the composition containing a metal of group 8 or a compound thereof
- C07C1/044—Catalysts; their physical properties characterised by the composition containing a metal of group 8 or a compound thereof containing iron
-
- 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
- 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
- C10G2/332—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 iron-group
-
- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/70—Catalyst aspects
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a kind of catalyst for preparation of low carbon olefines by synthetic gas, the catalyst is using activated carbon as carrier, and using iron as active metal component, potassium and manganese are as auxiliary agent；The load capacity of the iron is 5 20wt%, and the load capacity of the potassium is 2 5wt%, and the load capacity of the manganese is 10 30wt%；Its activity of obtained catalyst mutually has higher dispersion degree and less particle diameter, with higher activity and selectivity of light olefin, stability is good, higher reactivity is still kept after when reaction 100 is small, solving conventional carbon load ferrum-based catalyst, easily generation migration polymerization causes the reduction of effective active bit quantity under the reaction condition of high temperature and pressure there are metal active particle, and the problem of accessory substance is more, and the selectivity of low-carbon alkene is relatively low, have good industrial applications prospect.
Description
Technical field：
The present invention relates to catalyst technical field, and in particular to a kind of catalyst for preparation of low carbon olefines by synthetic gas and its
Using.
Background technology：
Low-carbon alkene such as ethene, propylene, butylene are the important industrial chemicals in fossil energy, be synthetic plastic, rubber,
The Important Platform molecule of the high-molecular compounds such as staple fibre, and the chemicals of global yield maximum.Ethene be synthetic fibers,
Synthetic rubber, synthetic plastic (polyethylene and polyvinyl chloride), the basic chemical raw materials of synthesizing alcohol (alcohol), are also used for manufacture chlorine
Ethene, styrene, ethylene oxide, acetic acid, acetaldehyde, ethanol and explosive etc., can further be made tubing, film article, packaging
The products such as bag, cosmetics, high-polymer fiber, it is closely bound up with our daily life.As main fossil fuel, propylene can be with
The chemical products such as acrylonitrile, propylene oxide, acetone are used to prepare, butylene then can be used for preparing butadiene, epoxy butane, butylene
The product such as polymer and various plastics.Low-carbon alkene is one of chemical products of yield maximum in the world, is accounted in national economy
There is consequence.In the world using ethylene, propylene yield as the important symbol for weighing a national oil development of chemical industry level
One of.In recent years, with the rapid development of economy, the consumption figure of China's ethylene, propylene and yield increase year by year, according to national statistics
Office's statistics display, China's ethylene yield in 2016 is up to 17,810,000 tons, it has also become the ethylene production for being only second to the U.S. in the world is big
State.Although the ethylene yield in China, production scale and technical merit all achieve significant progress, also it is faced with the same time very big
Challenge.Such as：The proportion that China's yield accounts for Apparent con- sumption only has 92.8%, and importation dependence is higher.Larger production rule
Mould still cannot meet the needs of growing.Major technique of the crude oil pyrolysis as production low-carbon alkene, to petroleum import
Dependency degree is higher, and production efficiency is low, and environmental pollution is serious, if China is still with single crude oil pyrolysis technical limit spacing low-carbon
Alkene is obviously difficult to realize sustainable development.
China's national territorial area is wide, and biomass material derives from a wealth of sources, using biomass as raw material through pyrolysis obtain mainly into
It is divided into H2After the synthesis gas of CO, the technology path through a step Fischer-Tropsch Synthesis synthesizing low-carbon alkene, there are raw material sources to enrich,
Environmental-friendly, the less advantage of production process energy consumption.Using biomass as raw material, it is dirty that the environment caused by crop straw burning can be reduced
Dye, and agriculture and forestry organic waste material is made full use of, realize " zero " discharge of carbon dioxide.F- T synthesis is by synthesis gas (H2And CO)
Hydrocarbon oxide, including the product such as methane, gaseous state low-carbon hydro carbons and liquid hydrocarbon compound are catalytically conveted under high temperature and pressure.Often
The catalyst for being used for F- T synthesis producing light olefins is mainly ferrum-based catalyst, and traditional body phase ferrum-based catalyst exists
It is easily broken the shortcomings of service life is relatively low, the conversion ratio of unit mass iron is relatively low.Can be effective using carbon carrier supported ferric catalyst
Raising activity mutually in the degree of scatter of carrier surface, so as to improve the conversion ratio of reaction, and carbon carrier is compared to titanium dioxide
The carriers such as silicon, molecular sieve, metal oxide, what weaker activity was mutually conducive to catalyst the interaction between carrier goes back original shape
Viability phase cementite.However, conventional carbon load ferrum-based catalyst there are metal active particle high temperature and pressure reaction condition
Lower easily generation migration polymerization causes the reduction of effective active bit quantity, and accessory substance is more, and the selectivity of low-carbon alkene is relatively low.
The content of the invention：
The object of the present invention is to provide a kind of catalyst for preparation of low carbon olefines by synthetic gas and its application, obtained catalysis
Agent has higher dispersion degree and less particle diameter, has higher activity and selectivity of light olefin, stability is good, is reacting
100 it is small when after still keep higher reactivity, solving conventional carbon load ferrum-based catalyst, there are metal active particle to exist
Migration polymerization easily occurs under the reaction condition of high temperature and pressure and causes the reduction of effective active bit quantity, and accessory substance is more, low-carbon alkene
The problem of selectivity of hydrocarbon is relatively low.
The present invention is achieved by the following technical programs：
A kind of catalyst for preparation of low carbon olefines by synthetic gas, the catalyst are used as activity using activated carbon as carrier, using iron
Metal component, potassium and manganese are as auxiliary agent；The load capacity of the iron is 5-20wt%, and the load capacity of the potassium is 2-5wt%, described
The load capacity of manganese is 10-30wt%, and auxiliary agent potassium and manganese are fixed by being pre-processed to absorbent charcoal carrier potassium permanganate solution
Modified on to carrier and to surface group, active component iron is to load to processed activated carbon by equi-volume impregnating
On carrier, the load-type iron-based catalyst of permanganate pretreatment, the preparation method of the catalyst are obtained after drying, calcining
Comprise the following steps：
1) activated carbon is boiled and washed with deionized water, to remove the ash content and impurity in activated carbon, redisperse to nitre
It is heated to reflux, is washed with deionized afterwards to filtrate pH=7 in acid solution, removes remaining metal ion in activated carbon；
Through washing the activated carbon redisperse with pickling into potassium permanganate solution, the mass ratio of potassium permanganate and activated carbon is controlled to exist
Between 0.2-1.1, the magnetic agitation 20-40min at 50-100 DEG C, it is nothing that filtered afterwards and deionized water, which is washed to filtrate,
Color, is dried overnight in 120 DEG C of baking ovens, obtains pretreated absorbent charcoal carrier；
2) iron nitrate aqueous solution is prepared by the load capacity of 5-20wt%, pretreated absorbent charcoal carrier is dispersed in nitric acid
In ferrous solution, when magnetic agitation 24 is small at normal temperatures after be placed in 120 DEG C of baking ovens and be dried overnight, in nitrogen atmosphere after grinding
Under with the heating rate of 2 DEG C/min rise to 200-500 DEG C and calcine 3-5 it is small when obtain final catalyst.
Preferably, the potassium permanganate solution concentration is 0.02mol/L-0.1mol/L.
Preferably, the temperature of the potassium permanganate solution processing activated carbon is 70 DEG C.
Preferably, the load capacity of iron is 5-10wt% in the catalyst.
Preferably, calcining heat is 300 DEG C to the catalyst after load iron under nitrogen atmosphere, when calcination time is 3 small.
Preferably, the volume of iron nitrate aqueous solution is 2ml, equal to the total pore volume of activated carbon used.
The application of the present invention also protection catalyst for preparation of low carbon olefines by synthetic gas, comprises the following steps：
Above-mentioned catalyst is uniformly mixed with quartz sand, is filled in fixed bed reactors；In H2Molar ratio with CO is 1
It it is 280~360 DEG C in reaction temperature, reaction pressure is after when~3 lower 300 DEG C of normal pressure in-situ reducings 12 of synthesis gas atmosphere are small
1.0~3.0MPa, reacting gas volume space velocity are 1500~15000h-1Under conditions of, synthesis gas and fixed bed reactors are urged
Agent contacts, and generates the mainly low-carbon alkene containing C2~C4, while by-product C5+Deng gasoline segment length's chain hydrocarbon products.
Preferably, reaction temperature is 300-320 DEG C, reaction pressure 2MPa, and the molar ratio of reaction gas is H2:CO=1, instead
It is 1500~3000h to answer gas volume air speed-1。
Reaction temperature is more preferably 320 DEG C, and reacting gas volume space velocity is 3000h-1。
Beneficial effects of the present invention are as follows：
1st, catalyst of the present invention is the loaded catalyst prepared by equi-volume impregnating, and iron active particle is put down
Equal particle diameter is smaller, high in absorbent charcoal carrier Dispersion on surface degree, is conducive to greatly improve the activity of catalytic reaction；
2nd, the carrier of catalyst of the present invention is impregnated again after being pre-processed using potassium permanganate solution at 50-100 DEG C
Active phase precursor, on the one hand with activated carbon redox reaction, activated carbon used occur for potassium permanganate in processing procedure
The oxy radical of carrier surface is improved, and is conducive to the increase of surface defect position, can effectively improve point of iron presoma
The electronic effect of divergence and absorbent charcoal carrier；On the other hand auxiliary agent manganese and potassium are introduced into catalyst carrier at the same time, be conducive to
The generation of active phase and the raising of selectivity of light olefin, while there is good catalyst stability, react 100 it is small when after
Higher reactivity and the selectivity of target product low-carbon alkene are still kept, conventional carbon load ferrum-based catalyst is solved and deposits
Migration polymerization easily occurs under reaction condition of the metal active particle in high temperature and pressure and causes the reduction of effective active bit quantity, and
The problem of accessory substance is more, and the selectivity of low-carbon alkene is relatively low.
3rd, catalyst prepared by the method for the present invention, low raw-material cost, preparation method is simple and easy to control, has the conversion of higher
Rate and selectivity of light olefin, there is good industrial applications prospect.
4th, the present invention is used for the reaction system of the application proposition of the catalyst of preparation of low carbon olefines by synthetic gas at 300 DEG C of normal pressure
First be adjusted to again after in-situ reducing suitable reaction pressure and at a temperature of carry out F- T synthesis producing light olefins reaction, original position also
The induction time that former process can effectively shorten catalyst reaction initial stage, is conducive to the generation of active phase cementite.In the reaction
Under the conditions of can stably high-efficiency and continuous production low-carbon alkene, while by-product C5+Deng gasoline, diesel oil segment length's catenanes product.
Brief description of the drawings：
The reactivity that Fig. 1 is the catalyst Fe -10MnK-AC of embodiment 1 changes over time figure.
Fig. 2 is the transmission electron microscope picture after the catalyst reaction 100h in embodiment 1.
Embodiment：
It is to further explanation of the invention, rather than limitation of the present invention below.
Embodiment 1：
Comprise the following steps：
1. proper amount of active carbon is boiled and washed with deionized water, to remove the ash content and impurity in activated carbon, redisperse
Into the salpeter solution of 10wt%, under 80 DEG C of oil baths flow back 5 it is small when, be washed with deionized afterwards to filtrate pH=7, with except
Remaining metal ion in deactivation charcoal, filter cake are placed in 60 DEG C of baking ovens and are dried overnight；3g is taken through washing the activated carbon with pickling
In the potassium permanganate solution that redisperse is 0.1mol/L to concentration, the mass ratio of potassium permanganate and activated carbon is controlled in 0.2-
Between 1.1, magnetic agitation 30 minutes at 70 DEG C, it is colourless that filtered afterwards and deionized water, which is washed to filtrate, in 120 DEG C of bakings
It is dried overnight in case, the absorbent charcoal carrier pre-processed；
2. preparing iron nitrate aqueous solution by the load capacity of 10wt%, pretreated absorbent charcoal carrier is dispersed in the nitric acid
In ferrous solution, solvent is removed when magnetic agitation 24 is small at normal temperatures, iron presoma uniform adsorption is put in activated carbon surface
It is dried overnight in 120 DEG C of baking ovens, rises to 300 DEG C with the heating rate of 2 DEG C/min under nitrogen atmosphere after grinding and calcining 3 is small
When, obtained catalyst is denoted as Fe-10MnK-AC；
3. it is filled to after the catalyst obtained in step 2 and quartz sand (60-80 mesh) are mixed in fixed-bed reactor,
In H2/ CO=1:When the 1 lower 300 DEG C of normal pressure in-situ reducings 12 of synthesis gas atmosphere are small, pressure is adjusted to 2MPa (gauge pressure), temperature tune
To 320 DEG C, catalyze and synthesize gas generation Fischer-Tropsch synthesis and prepare low-carbon alkene, reacting gas volume space velocity is 3000h-1。
After stable reaction, the gas that reaction obtains is passed directly into gas-chromatography (FID, TCD) on-line checking and analyzes its group
Point, the liquid component (water phase and oil phase) reacted is cooled down by the cold-trap after being connected on fixed bed and collected, when 24 is small
Take out liquid component and weigh, hydrocarbon content is extremely low wherein in water-phase product ignores, and oil-phase product passes through offline gas phase color
Spectrum is analyzed.Key component is the alkane and alkene of below C5 in gas phase hydrocarbon product, key component in oil phase hydrocarbon product
It is the materials such as long chain alkane alkene and its isomers, the alcohols of more than C5, chromatography detection is all the external standard demarcated by standard sample
Method carries out quantitative analysis, and the Carbon balance of obtained all products and unstripped gas is maintained at more than 95%.
Embodiment 2：
Reference implementation example 1, difference are 0.05mol/L in the concentration of the potassium permanganate solution in step 1, are obtained
Catalyst is denoted as Fe-5MnK-AC；It is other same as Example 1.
After stable reaction, the gas that reaction obtains is passed directly into gas-chromatography (FID, TCD) on-line checking and analyzes its group
Point, the liquid component (water phase and oil phase) reacted is cooled down by the cold-trap after being connected on fixed bed and collected, when 24 is small
Take out liquid component and weigh, hydrocarbon content is extremely low wherein in water-phase product ignores, and oil-phase product passes through offline gas phase color
Spectrum is analyzed.Key component is the alkane and alkene of below C5 in gas phase hydrocarbon product, key component in oil phase hydrocarbon product
It is the materials such as long chain alkane alkene and its isomers, the alcohols of more than C5.Chromatography detection is all the external standard demarcated by standard sample
Method carries out quantitative analysis, and the Carbon balance of obtained all products and unstripped gas is maintained at more than 95%.
Embodiment 3：
Reference implementation example 1, difference are 0.02mol/L in the concentration of the potassium permanganate solution in step 1, are obtained
Catalyst is denoted as Fe-2MnK-AC；It is other same as Example 1.
After stable reaction, the gas that reaction obtains is passed directly into gas-chromatography (FID, TCD) on-line checking and analyzes its group
Point, the liquid component (water phase and oil phase) reacted is cooled down by the cold-trap after being connected on fixed bed and collected, when 24 is small
Take out liquid component and weigh, hydrocarbon content is extremely low wherein in water-phase product ignores, and oil-phase product passes through offline gas phase color
Spectrum is analyzed.Key component is the alkane and alkene of below C5 in gas phase hydrocarbon product, key component in oil phase hydrocarbon product
It is the materials such as long chain alkane alkene and its isomers, the alcohols of more than C5.Chromatography detection is all the external standard demarcated by standard sample
Method carries out quantitative analysis, and the Carbon balance of obtained all products and unstripped gas is maintained at more than 95%.
Embodiment 4：
Reference implementation example 1, difference in step 3 reacting gas volume space velocity be 1500h-1.Other and embodiment 1
It is identical.
After stable reaction, the gas that reaction obtains is passed directly into gas-chromatography (FID, TCD) on-line checking and analyzes its group
Point, the liquid component (water phase and oil phase) reacted is cooled down by the cold-trap after being connected on fixed bed and collected, when 24 is small
Take out liquid component and weigh, hydrocarbon content is extremely low wherein in water-phase product ignores, and oil-phase product passes through offline gas phase color
Spectrum is analyzed.Key component is the alkane and alkene of below C5 in gas phase hydrocarbon product, key component in oil phase hydrocarbon product
It is the materials such as long chain alkane alkene and its isomers, the alcohols of more than C5.Chromatography detection is all the external standard demarcated by standard sample
Method carries out quantitative analysis, and the Carbon balance of obtained all products and unstripped gas is maintained at more than 95%.
Embodiment 5：
Reference implementation example 1, difference in step 3 reacting gas volume space velocity be 9000h-1。
After stable reaction, the gas that reaction obtains is passed directly into gas-chromatography (FID, TCD) on-line checking and analyzes its group
Point, the liquid component (water phase and oil phase) reacted is cooled down by the cold-trap after being connected on fixed bed and collected, when 24 is small
Take out liquid component and weigh, hydrocarbon content is extremely low wherein in water-phase product ignores, and oil-phase product passes through offline gas phase color
Spectrum is analyzed.Key component is the alkane and alkene of below C5 in gas phase hydrocarbon product, key component in oil phase hydrocarbon product
It is the materials such as long chain alkane alkene and its isomers, the alcohols of more than C5.Chromatography detection is all the external standard demarcated by standard sample
Method carries out quantitative analysis, and the Carbon balance of obtained all products and unstripped gas is maintained at more than 95%.
Embodiment 6：
Reference implementation example 1, difference in step 3 reacting gas volume space velocity be 15000h-1。
After stable reaction, the gas that reaction obtains is passed directly into gas-chromatography (FID, TCD) on-line checking and analyzes its group
Point, the liquid component (water phase and oil phase) reacted is cooled down by the cold-trap after being connected on fixed bed and collected, when 24 is small
Take out liquid component and weigh, hydrocarbon content is extremely low wherein in water-phase product ignores, and oil-phase product passes through offline gas phase color
Spectrum is analyzed.Key component is the alkane and alkene of below C5 in gas phase hydrocarbon product, key component in oil phase hydrocarbon product
It is the materials such as long chain alkane alkene and its isomers, the alcohols of more than C5.Chromatography detection is all the external standard demarcated by standard sample
Method carries out quantitative analysis, and the Carbon balance of obtained all products and unstripped gas is maintained at more than 95%.
Embodiment 7：
Reference implementation example 1, difference in step 3 catalytic reaction temperature be adjusted to 280 DEG C, catalyze and synthesize gas occur expense
Support synthetic reaction prepares low-carbon alkene.
After stable reaction, the gas that reaction obtains is passed directly into gas-chromatography (FID, TCD) on-line checking and analyzes its group
Point, the liquid component (water phase and oil phase) reacted is cooled down by the cold-trap after being connected on fixed bed and collected, when 24 is small
Take out liquid component and weigh, hydrocarbon content is extremely low wherein in water-phase product ignores, and oil-phase product passes through offline gas phase color
Spectrum is analyzed.Key component is the alkane and alkene of below C5 in gas phase hydrocarbon product, key component in oil phase hydrocarbon product
It is the materials such as long chain alkane alkene and its isomers, the alcohols of more than C5.Chromatography detection is all the external standard demarcated by standard sample
Method carries out quantitative analysis, and the Carbon balance of obtained all products and unstripped gas is maintained at more than 95%.
Embodiment 8：
Reference implementation example 1, difference in step 3 temperature be adjusted to 360 DEG C, catalyze and synthesize gas occur F- T synthesis it is anti-
Low-carbon alkene should be prepared.
After stable reaction, the gas that reaction obtains is passed directly into gas-chromatography (FID, TCD) on-line checking and analyzes its group
Point, the liquid component (water phase and oil phase) reacted is cooled down by the cold-trap after being connected on fixed bed and collected, when 24 is small
Take out liquid component and weigh, hydrocarbon content is extremely low wherein in water-phase product ignores, and oil-phase product passes through offline gas phase color
Spectrum is analyzed.Key component is the alkane and alkene of below C5 in gas phase hydrocarbon product, key component in oil phase hydrocarbon product
It is the materials such as long chain alkane alkene and its isomers, the alcohols of more than C5.Chromatography detection is all the external standard demarcated by standard sample
Method carries out quantitative analysis, and the Carbon balance of obtained all products and unstripped gas is maintained at more than 95%.
Comparative example 1：
Reference implementation example 1, difference do not have redisperse to permanganic acid in the activated carbon through washing and pickling in step 1
Handled in aqueous solutions of potassium；
Comprise the following steps：
1. proper amount of active carbon is disperseed in deionized water, handled under 100 DEG C of oil baths 2 it is small when after filter and use deionization
Water washing, in the salpeter solution of redisperse to 10wt%, flow back under 80 DEG C of oil baths 5 it is small when, be washed with deionized afterwards to
Filtrate pH=7, filter cake are placed in 60 DEG C of baking ovens and are dried overnight, the absorbent charcoal carrier pre-processed；
2. preparing iron nitrate aqueous solution by the load capacity of 10wt%, pretreated absorbent charcoal carrier is dispersed in the nitric acid
In ferrous solution, solvent is removed when magnetic agitation 24 is small at normal temperatures, is placed in 120 DEG C of baking ovens and is dried overnight, after grinding
When rising to 300 DEG C and small calcining 3 under nitrogen atmosphere with the heating rate of 2 DEG C/min, obtained catalyst is denoted as Fe-AC；
3. it is filled to after the catalyst obtained in step 2 and quartz sand are mixed in fixed-bed reactor, in H2/ CO=
1:When the 1 lower 300 DEG C of normal pressure in-situ reducings 12 of synthesis gas atmosphere are small, pressure is adjusted to 2MPa (gauge pressure), temperature is adjusted to 320 DEG C,
Catalyze and synthesize gas generation Fischer-Tropsch synthesis and prepare low-carbon alkene, reaction gas gas volume air speed is 3000h-1。
After stable reaction, the gas that reaction obtains is passed directly into gas-chromatography (FID, TCD) on-line checking and analyzes its group
Point, the liquid component (water phase and oil phase) reacted is cooled down by the cold-trap after being connected on fixed bed and collected, when 24 is small
Take out liquid component and weigh, hydrocarbon content is extremely low wherein in water-phase product ignores, and oil-phase product passes through offline gas phase color
Spectrum is analyzed.Key component is the alkane and alkene of below C5 in gas phase hydrocarbon product, key component in oil phase hydrocarbon product
It is the materials such as long chain alkane alkene and its isomers, the alcohols of more than C5.Chromatography detection is all the external standard demarcated by standard sample
Method carries out quantitative analysis, and the Carbon balance of obtained all products and unstripped gas is maintained at more than 95%.
Comparative example 2：
Comprise the following steps：
1. proper amount of active carbon is disperseed in deionized water, handled under 100 DEG C of oil baths 2 it is small when after filter and use deionization
Water washing, in the salpeter solution of redisperse to 10wt%, flow back under 80 DEG C of oil baths 5 it is small when, be washed with deionized afterwards to
Filtrate pH=7, filter cake are placed in 60 DEG C of baking ovens and are dried overnight, the absorbent charcoal carrier pre-processed；
2. being 10wt% by the load capacity of Fe, the load capacity of K is water-soluble for the mixing of 5wt% preparation ferric nitrates and potassium nitrate
Liquid, pretreated absorbent charcoal carrier is dispersed in the solution, is removed solvent when magnetic agitation 24 is small at normal temperatures, is put
It is dried overnight in 120 DEG C of baking ovens, rises to 300 DEG C with the heating rate of 2 DEG C/min under nitrogen atmosphere after grinding and calcining 3 is small
When, obtained catalyst is denoted as Fe-10K-AC；
3. it is filled to after the catalyst obtained in step 2 and quartz sand are mixed in fixed-bed reactor, in H2/ CO=
1:When the 1 lower 300 DEG C of normal pressure in-situ reducings 12 of synthesis gas atmosphere are small, pressure is adjusted to 2MPa (gauge pressure), temperature is adjusted to 320 DEG C,
Catalyze and synthesize gas generation Fischer-Tropsch synthesis and prepare low-carbon alkene, reaction gas gas volume air speed is 3000h-1。
After stable reaction, the gas that reaction obtains is passed directly into gas-chromatography (FID, TCD) on-line checking and analyzes its group
Point, the liquid component (water phase and oil phase) reacted is cooled down by the cold-trap after being connected on fixed bed and collected, when 24 is small
Take out liquid component and weigh, hydrocarbon content is extremely low wherein in water-phase product ignores, and oil-phase product passes through offline gas phase color
Spectrum is analyzed.Key component is the alkane and alkene of below C5 in gas phase hydrocarbon product, key component in oil phase hydrocarbon product
It is the materials such as long chain alkane alkene and its isomers, the alcohols of more than C5.Chromatography detection is all the external standard demarcated by standard sample
Method carries out quantitative analysis, and the Carbon balance of obtained all products and unstripped gas is maintained at more than 95%.
Comparative example 3：
Reference implementation example 1, difference in step 1 activated carbon pass through without washing and pickling, it is and high in processing procedure
The mass ratio of potassium manganate and activated carbon is 3.2, is comprised the following steps：
1. 1g activated carbons are taken to be distributed in the potassium permanganate solution that concentration is 0.1mol/L, the magnetic agitation 30 at 70 DEG C
Minute, it is colourless that filtered afterwards and deionized water, which is washed to filtrate, is dried overnight, is pre-processed in 120 DEG C of baking ovens
Absorbent charcoal carrier；
2. preparing iron nitrate aqueous solution by the load capacity of 10wt%, pretreated absorbent charcoal carrier is dispersed in the nitric acid
In ferrous solution, solvent is removed when magnetic agitation 24 is small at normal temperatures, is placed in 120 DEG C of baking ovens and is dried overnight, after grinding
When rising to 300 DEG C and small calcining 3 under nitrogen atmosphere with the heating rate of 2 DEG C/min, obtained catalyst is denoted as Fe-30MnK-
AC；
3. it is filled to after the catalyst obtained in step 2 and quartz sand are mixed in fixed-bed reactor, in H2/ CO=
1:When the 1 lower 300 DEG C of normal pressure in-situ reducings 12 of synthesis gas atmosphere are small, pressure is adjusted to 2MPa (gauge pressure), temperature is adjusted to 320 DEG C,
Catalyze and synthesize gas generation Fischer-Tropsch synthesis and prepare low-carbon alkene, reaction gas gas volume air speed is 3000h-1。
After stable reaction, the gas that reaction obtains is passed directly into gas-chromatography (FID, TCD) on-line checking and analyzes its group
Point, the liquid component (water phase and oil phase) reacted is cooled down by the cold-trap after being connected on fixed bed and collected, when 24 is small
Take out liquid component and weigh, hydrocarbon content is extremely low wherein in water-phase product ignores, and oil-phase product passes through offline gas phase color
Spectrum is analyzed.Key component is the alkane and alkene of below C5 in gas phase hydrocarbon product, key component in oil phase hydrocarbon product
It is the materials such as long chain alkane alkene and its isomers, the alcohols of more than C5.Chromatography detection is all the external standard demarcated by standard sample
Method carries out quantitative analysis, and the Carbon balance of obtained all products and unstripped gas is maintained at more than 95%.
Table 1 is embodiment 1~8 and catalyst reaction condition of comparative example 1~3, the conversion ratio of raw material and low-carbon alkene
The comparing result of selectivity.
Table 1
It can be seen that under identical reaction conditions from embodiment 1 with the results contrast of comparative example 1 and 2, potassium is as a kind of
Base agent effectively inhibits the generation of byproduct methane, while compared to the Fe-AC of no auxiliary agent, C2-C4The ratio of alkane declines
, illustrate that potassium promoter inhibits the hydrogenation reaction of CO and low-carbon alkene active in F- T synthesis preparing low carbon olefin hydrocarbon, reduce
The selectivity of alkane.Catalyst Fe -10MnK-AC has higher CO conversion ratios in embodiment 1, illustrates to be used as common expense
Additive synthesis are held in the palm, one side manganese improves the dispersion degree of iron activity phase, improves adsorption capacity of the catalyst to CO；On the other hand
Manganese weakens the C=O double bonds in carbon monoxide molecule, makes absorption be easier to occur to dissociate and then join in the CO molecules of avtive spot
With reaction.Catalyst Fe -10MnK-AC has higher selectivity of light olefin, C in embodiment 15+Product only has 29.7%, says
Bright manganese auxiliary agent inhibits the further hydrogenation and chain growth of reaction during the reaction, passes through Anderson-Schulz-Flory
The chain growth factor that its product is calculated in model is 0.73, illustrates that the catalyst in embodiment 1 can be by the hydro carbons in product
Concentrate in C5Below.
From embodiment 1 with the results contrast of comparative example 1 and 3 can be seen that step 1 of the present invention wash, pickling and permanganic acid
Potassium processing synergistic effect, generates unexpected technique effect.Compared to comparative example 1 and comparative example 3, the conversion ratio of CO has greatly
Amplitude improves, and illustrates that activated carbon has more oxy radicals in its surface after washing, pickling and permanganate pretreatment, favorably
In the activity for improving reaction.Comparison with comparative example 3 can be seen that the content of excessive manganese and potassium and inhibit to a certain extent
The conversion ratio of CO and the selectivity of low-carbon alkene, illustrate that there are the mass ratio of a potassium permanganate and activated carbon in processing procedure
Optimized scope.
Embodiment 1~3 compared for what is prepared using the absorbent charcoal carrier that the potassium permanganate solution of various concentrations pre-processes
The mass ratio of the reaction effect of catalyst, potassium permanganate and activated carbon is between 0.2-1.1.It can be seen that from XRF characterization results
The mass ratio of iron and manganese is respectively 1 in three kinds of catalyst:3,1:2 and 1:1.It can be drawn by the CO conversion ratios for comparing reaction,
Its reactivity of the higher catalyst of manganese content is lower.Illustrate that the combination of manganese and iron causes slightly subtracting for avtive spot
It is few.It is due to manganese to H and the catalyst compared with high Mn content shows higher selectivity of light olefin2Make with competitive Adsorption
Its surface could be reduced around iron activity phase by, which being present in, only enough manganese, can participate in the H of hydrogenation reaction2Content,
So as to suppress the secondary hydrogenation of alkene.Meanwhile manganese is not the avtive spot in Fischer-Tropsch synthesis, enough manganese can be effectively
Similar avtive spot is kept apart, absorption C on adjacent active site is increased on microcosmic*Distance, make its be difficult into
One step occurs carbochain and increases.
Embodiment 1 and embodiment 4~6 compared for the reaction effect of Fe-10MnK-AC under different air speeds.It can substantially see
Go out, reduce with the increase CO conversion ratios of air speed, illustrate raw material CO and H2Shorter in the residence time of catalyst surface, reaction is more not
Completely.Contrast 1500h-1、3000h-1、9000h-1And 15000h-1Selectivity of light olefin can be seen that reaction and in air speed be
3000h-1When low-carbon alkene selective highest.
Embodiment 1 and embodiment 7~8 compared for the reaction effect of Fe-10MnK-AC under different temperatures.It is as can be seen that anti-
Should there was only 17.1% by CO conversion ratios at 280 DEG C, illustrate that the reactivity of the catalyst under low temperature is relatively low.By comparing product
The distribution of middle hydro carbons can be seen that high temperature and be conducive to product to be migrated to lower carbon number hydrocarbons direction, but excessive temperature (360 DEG C) and can be made
Into the aggravation of chain propagation reaction.
In summary embodiment, the reaction condition optimization for preparation of low carbon olefines by synthetic gas catalyst are：Temperature 320
DEG C, air speed 3000h-1, preparation condition is optimized for the Pre-Treatment of Activated high-area carbon of potassium permanganate solution using 0.1mol/L.To excellent
Catalyst Fe -10MnK-AC after change under the reaction condition of optimization during sustained response 100h (Fig. 1), catalyst it is anti-
It active should keep stablizing, CO conversion ratios maintain more than 80%, show that catalyst does not have obvious deactivation phenomenom.In embodiment 1
Catalyst reaction 100h after transmission electron microscope picture such as Fig. 2, it can be seen that iron particle still maintains preferable dispersion degree on surface,
Particle diameter distribution is concentrated mainly on 13nm or so, also illustrate that pickling and permanganate pretreatment help to improve catalyst activity position
The stability of point.C2-C4Alkene and alkane ratio (O/P) stabilization be held essentially constant in 4-5, the selectivity of low-carbon alkene
(40% or so).In short, the catalyst of the present invention for preparation of low carbon olefines by synthetic gas has preparation process simply without dirt
The advantages of dye, low in raw material price, catalyst show the reactivity of higher, the choosing of higher low-carbon alkene during the reaction
Selecting property and good stability, have good industrial applications prospect.
Claims (7)
1. a kind of catalyst for preparation of low carbon olefines by synthetic gas, it is characterised in that the catalyst is using activated carbon as carrier, with iron
As active metal component, potassium and manganese are as auxiliary agent；The load capacity of the iron is 5-20wt%, and the load capacity of the potassium is 2-
5wt%, the load capacity of the manganese is 10-30wt%, and auxiliary agent potassium and manganese are by absorbent charcoal carrier potassium permanganate solution
Pretreatment is fixed on carrier and surface group is modified, and active component iron is to load to processing by equi-volume impregnating
On the absorbent charcoal carrier crossed, the load-type iron-based catalyst of permanganate pretreatment, the catalyst are obtained after drying, calcining
Preparation method comprise the following steps：
1) activated carbon is boiled and washed with deionized water, redisperse is heated to reflux into salpeter solution, uses deionized water afterwards
To filtrate pH=7, redisperse controls the mass ratio of potassium permanganate and activated carbon in 0.2- into potassium permanganate solution for washing
Between 1.1, the magnetic agitation 20-40min at 50-100 DEG C, filtered afterwards and deionized water wash to filtrate be it is colourless,
It is dried overnight in 120 DEG C of baking ovens, obtains pretreated absorbent charcoal carrier；
2) iron nitrate aqueous solution is prepared by the load capacity of 5-20wt%, it is molten that pretreated absorbent charcoal carrier is dispersed in ferric nitrate
In liquid, when magnetic agitation 24 is small at normal temperatures after be placed in 120 DEG C of baking ovens and be dried overnight, after grinding under nitrogen atmosphere with
The heating rate of 2 DEG C/min rise to 200-500 DEG C and calcine 3-5 it is small when obtain final catalyst.
2. the catalyst according to claim 1 for preparation of low carbon olefines by synthetic gas, it is characterised in that the potassium permanganate
Concentration of aqueous solution is 0.02mol/L-0.1mol/L.
3. the catalyst according to claim 1 or 2 for preparation of low carbon olefines by synthetic gas, it is characterised in that the Gao Meng
The temperature of sour aqueous solutions of potassium processing activated carbon is 70 DEG C.
4. the catalyst according to claim 1 or 2 for preparation of low carbon olefines by synthetic gas, it is characterised in that the catalysis
The load capacity of iron is 5-10wt% in agent.
5. the catalyst according to claim 1 or 2 for preparation of low carbon olefines by synthetic gas, it is characterised in that after load iron
Catalyst under nitrogen atmosphere calcining heat be 300 DEG C, calcination time for 3 it is small when.
6. the application of the catalyst for preparation of low carbon olefines by synthetic gas in claim 1-5 described in any one claim,
It is characterised in that it includes following steps：Catalyst is uniformly mixed with quartz sand, is filled in fixed bed reactors；In H2With
It is 280~360 in reaction temperature after when the lower 300 DEG C of normal pressure in-situ reducings 12 of synthesis gas atmosphere that the molar ratio of CO is 1~3 are small
DEG C, reaction pressure is 1.0~3.0MPa, and reacting gas volume space velocity is 1500~15000h-1Under conditions of, synthesis gas and fixation
The catalyst contact of bed reactor, generates the mainly low-carbon alkene containing C2~C4, while by-product C5+Gasoline segment length's chain hydrocarbon products.
7. the application of the catalyst according to claim 6 for preparation of low carbon olefines by synthetic gas, it is characterised in that reaction temperature
Spend for 300-320 DEG C, reaction pressure 2MPa, the molar ratio of reaction gas is H2:CO=1, reacting gas volume space velocity are 1500
~3000h-1。
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| CN111659395A (en) * | 2020-05-26 | 2020-09-15 | 北京化工大学 | Preparation method and application of foamed iron-based catalyst with high all-olefin selectivity |
| CN112517034A (en) * | 2019-09-18 | 2021-03-19 | 中国科学院广州能源研究所 | Graphene-like coated iron carbide catalyst and preparation method and application thereof |
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