CN106040257B - Fischer-tropsch synthetic catalyst and preparation method thereof and catalyst and Fischer-Tropsch synthesis method - Google Patents
Fischer-tropsch synthetic catalyst and preparation method thereof and catalyst and Fischer-Tropsch synthesis method Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 136
- 238000002360 preparation method Methods 0.000 title claims abstract description 38
- 238000001308 synthesis method Methods 0.000 title abstract description 4
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 48
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 48
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 40
- 229910052702 rhenium Inorganic materials 0.000 claims abstract description 38
- 229910052751 metal Inorganic materials 0.000 claims abstract description 20
- 239000002184 metal Substances 0.000 claims abstract description 20
- 230000003197 catalytic effect Effects 0.000 claims abstract description 9
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 78
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 30
- 239000002243 precursor Substances 0.000 claims description 30
- 238000001035 drying Methods 0.000 claims description 29
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 26
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 25
- 229910052593 corundum Inorganic materials 0.000 claims description 25
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 25
- 239000003795 chemical substances by application Substances 0.000 claims description 23
- 229910017052 cobalt Inorganic materials 0.000 claims description 20
- 239000010941 cobalt Substances 0.000 claims description 20
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 20
- 239000000377 silicon dioxide Substances 0.000 claims description 17
- 239000011148 porous material Substances 0.000 claims description 16
- 229910052681 coesite Inorganic materials 0.000 claims description 15
- 229910052906 cristobalite Inorganic materials 0.000 claims description 15
- 229910052682 stishovite Inorganic materials 0.000 claims description 15
- 229910052905 tridymite Inorganic materials 0.000 claims description 15
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims description 13
- 230000004048 modification Effects 0.000 claims description 11
- 238000012986 modification Methods 0.000 claims description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 10
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 10
- NWAHZABTSDUXMJ-UHFFFAOYSA-N platinum(2+);dinitrate Chemical compound [Pt+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O NWAHZABTSDUXMJ-UHFFFAOYSA-N 0.000 claims description 9
- 229910021634 Rhenium(III) chloride Inorganic materials 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 8
- LOIHSHVELSAXQN-UHFFFAOYSA-K trirhenium nonachloride Chemical compound Cl[Re](Cl)Cl LOIHSHVELSAXQN-UHFFFAOYSA-K 0.000 claims description 8
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 5
- 229910052746 lanthanum Inorganic materials 0.000 claims description 5
- QSHYGLAZPRJAEZ-UHFFFAOYSA-N 4-(chloromethyl)-2-(2-methylphenyl)-1,3-thiazole Chemical compound CC1=CC=CC=C1C1=NC(CCl)=CS1 QSHYGLAZPRJAEZ-UHFFFAOYSA-N 0.000 claims description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 239000012752 auxiliary agent Substances 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 claims 1
- 230000003647 oxidation Effects 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 claims 1
- 229930195733 hydrocarbon Natural products 0.000 abstract description 21
- 150000002430 hydrocarbons Chemical class 0.000 abstract description 21
- 239000004215 Carbon black (E152) Substances 0.000 abstract description 20
- 230000009467 reduction Effects 0.000 abstract description 10
- 238000007598 dipping method Methods 0.000 description 36
- 238000002803 maceration Methods 0.000 description 24
- 238000003756 stirring Methods 0.000 description 20
- 239000000243 solution Substances 0.000 description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 15
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 15
- 239000008367 deionised water Substances 0.000 description 14
- 229910021641 deionized water Inorganic materials 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 12
- 239000007789 gas Substances 0.000 description 12
- 238000010792 warming Methods 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 8
- 230000004913 activation Effects 0.000 description 7
- 239000011159 matrix material Substances 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 239000007788 liquid Substances 0.000 description 6
- 229910000510 noble metal Inorganic materials 0.000 description 6
- 239000003245 coal Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 5
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 5
- 239000010953 base metal Substances 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- 239000000446 fuel Substances 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 229910004369 ThO2 Inorganic materials 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 230000008676 import Effects 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000005660 chlorination reaction Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- BYFGZMCJNACEKR-UHFFFAOYSA-N Al2O Inorganic materials [Al]O[Al] BYFGZMCJNACEKR-UHFFFAOYSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000004868 gas analysis Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 239000011799 hole material Substances 0.000 description 1
- 235000003642 hunger Nutrition 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 1
- 239000006193 liquid solution Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- XZWYZXLIPXDOLR-UHFFFAOYSA-N metformin Chemical compound CN(C)C(=N)NC(N)=N XZWYZXLIPXDOLR-UHFFFAOYSA-N 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 238000013215 result calculation Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 230000037351 starvation Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- ZCUFMDLYAMJYST-UHFFFAOYSA-N thorium dioxide Chemical compound O=[Th]=O ZCUFMDLYAMJYST-UHFFFAOYSA-N 0.000 description 1
- ZSDSQXJSNMTJDA-UHFFFAOYSA-N trifluralin Chemical compound CCCN(CCC)C1=C([N+]([O-])=O)C=C(C(F)(F)F)C=C1[N+]([O-])=O ZSDSQXJSNMTJDA-UHFFFAOYSA-N 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8986—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with manganese, technetium or rhenium
-
- B01J35/613—
-
- B01J35/615—
-
- 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
- C10G2/333—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
-
- 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
Abstract
The present invention relates to F- T synthesis field, a kind of fischer-tropsch synthetic catalyst and preparation method thereof and catalyst and Fischer-Tropsch synthesis method are disclosed.The load type cobalt-base fischer-tropsch synthetic catalyst includes the Co and metal promoter of carrier and load on the carrier, wherein the metal promoter contains Pt and Re simultaneously.Load type cobalt-base fischer-tropsch synthetic catalyst provided by the invention not only catalytic activity with higher after reduction, but also to C5+Long-chain heavy hydrocarbon also has good selectivity, and is highly suitable for producing C5+Long-chain heavy hydrocarbon.
Description
Technical field
The present invention relates to F- T synthesis fields, and in particular, to a kind of load type cobalt-base fischer-tropsch synthetic catalyst, a kind of negative
The preparation method of load type Co based Fischer-Tropsch synthesis catalyst, a kind of load type cobalt-base fischer-tropsch synthetic catalyst and the above-mentioned load of use
The method of type Co based Fischer-Tropsch synthesis catalyst progress F- T synthesis.
Background technique
Energy resource structure total feature in China's is " rich coal, oil starvation, few gas ", produces synthesis gas by raw material of coal, passes through again later
It is one of the important channel for solving liquid fuel insufficient supply that Fischer-Tropsch synthesis, which generates liquefied hydrocarbon, to guarantee national energy peace
Entirely, promote that social economy is sustainable, scientific development has important strategic importance.F- T synthesis refers to synthesis gas (CO+H2)
The reaction of liquid hydrocarbon fuel is catalyzed and synthesized in the presence of fischer-tropsch synthetic catalyst.Gasoline made from F- T synthesis is no sulphur, nothing
The impurity such as lead and the high-quality clean fuel with higher octane, this is low for helping China to improve atmospheric conditions, realization green
Carbon will play an important role.
The fischer-tropsch synthetic catalyst generally includes iron-base fischer-tropsch synthesis catalyst, Co based Fischer-Tropsch synthesis catalyst and ruthenium base
Fischer-tropsch synthetic catalyst.Wherein, Co based Fischer-Tropsch synthesis catalyst has high activity, high linear saturation heavy hydrocarbon-selective and low
The features such as water-gas reacting condition and it is great have industrial application value, be that high-quality liquid fuel is most appropriate urges for the synthesis of coal base
One of agent.
CN101269336A discloses a kind of multilevel hole material load cobalt catalyst, the weight percent composition of the catalyst
Are as follows: metallic cobalt 5-40%, noble metal 0-2.0%, base metal 0-2%, silica 56-95%, the noble metal be Ir,
Ru, Rh, Pt or Pd, the base metal are La, Ce, Mg, Ca, Zr, Mn or Re.The catalyst is abundant micro- since carrier has
Pore structure can provide enough surface areas for reaction, to help to obtain the cobalt-base catalyst of high dispersive, make it suitable for
F- T synthesis high temperature hydrothermal condition has high thermal stability and hydrothermal stability.
US4568663 discloses one kind with ThO2Carrier is improved while being urged by the Fischer-Tropsch synthesis cobalt-based of auxiliary agent of Re
Agent, the catalyst contain the Co of 2-25 weight %, preferably 5-15 weight %, 0.1-10 weight %, preferably 0.5-5 weight %'s
ThO2, the weight ratio of Re and Co are (0.025-0.1): 1, Co and ThO2Weight ratio be (20-1): 1, carrier TiO2, carrier
In rutile and anatase ratio be greater than 2:3.Studies have shown that the catalyst is to C10+Alkane and alkene choosing with higher
Selecting property.
US5733839 discloses one kind using Pt as auxiliary agent and with Al2O3For the Fischer-Tropsch synthesis cobalt-based catalyst of carrier, this is urged
The weight ratio of Pt and Co is (0.00005-0.1) in agent: 1.Studies have shown that catalyst catalytic activity with higher.
Summary of the invention
The object of the present invention is to provide a kind of new load type cobalt-base fischer-tropsch synthetic catalysts, a kind of load type cobalt-base Fischer-Tropsch
The preparation method of synthetic catalyst, a kind of load type cobalt-base fischer-tropsch synthetic catalyst and the above-mentioned load type cobalt-base Fischer-Tropsch of use close
The method for carrying out F- T synthesis at catalyst.
Although CN101269336A, which is referred in Co based Fischer-Tropsch synthesis catalyst, can contain noble metal and base metal,
It is the thermostabilization that the catalyst is intended to improve catalyst by using a kind of silica supports with mesoporous and macropore grade
Property and hydrothermal stability, and noble metal and base metal are not necessary component but optional component, and disclosed in it
Noble metal and non-noble metal type are more, disclose any embodiment for containing platinum (Pt) and rhenium (Re) simultaneously or
Embodiment, it can be seen that its inventor is not implied by or finds Pt and Re to the synergistic effect of catalyst performance.
The present inventor is after further investigation it was unexpectedly observed that when being used as co-based fischer-tropsch to synthesize simultaneously Pt and Re
When at least part or whole of the metal promoter of catalyst, the two can play good synergistic effect, so as to significant
Improve the activity of catalyst, to C5+The selectivity of long-chain heavy hydrocarbon and the service life for extending catalyst.Based on above-mentioned unexpected
Technical effect and have been surprisingly found that, complete the present invention.
Specifically, the present invention provides a kind of load type cobalt-base fischer-tropsch synthetic catalyst, the catalyst include carrier and
The catalytic active component Co and metal promoter of load on the carrier, wherein the metal promoter contains Pt and Re simultaneously.
The present invention also provides a kind of preparation method of load type cobalt-base fischer-tropsch synthetic catalyst, this method includes that will be catalyzed
Active component Co and metal promoter are supported on carrier, wherein the metal promoter contains Pt and Re simultaneously.
The present invention also provides by above-mentioned load type cobalt-base fischer-tropsch synthetic catalyst or prepared by the above method
Load type cobalt-base fischer-tropsch synthetic catalyst is through restoring obtained load type cobalt-base F- T synthesis activated catalyst.
In addition, this method includes urging synthesis gas in F- T synthesis the present invention also provides a kind of method of F- T synthesis
It is reacted in the presence of agent, wherein the fischer-tropsch synthetic catalyst is above-mentioned load type cobalt-base F- T synthesis activating catalytic
Agent.
Load type cobalt-base fischer-tropsch synthetic catalyst provided by the invention after reduction activation catalytic activity with higher with
And to C5+The selectivity of long-chain heavy hydrocarbon simultaneously has longer service life, great prospects for commercial application.
A preferred embodiment of the invention, as Pt and Re in the load type cobalt-base fischer-tropsch synthetic catalyst
Weight ratio is (0.01-2): when 1, or when the load in the load type cobalt-base fischer-tropsch synthetic catalyst relative to 100 parts by weight
Body, Co content be 15-50 parts by weight, when the content of Pt is 0.01-0.1 parts by weight, the content of Re is 0.05-1 parts by weight, phase
The catalyst answered is to C5+Long-chain heavy hydrocarbon also has higher selectivity, is highly suitable for preparation C5+Long-chain heavy hydrocarbon.
Other features and advantages of the present invention will the following detailed description will be given in the detailed implementation section.
Specific embodiment
Detailed description of the preferred embodiments below.It should be understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or
Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively
It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more
New numberical range, these numberical ranges should be considered as specific open herein.
Load type cobalt-base fischer-tropsch synthetic catalyst provided by the invention includes the Co of carrier and load on the carrier
And metal promoter, wherein the metal promoter contains Pt and Re simultaneously.
The load type cobalt-base fischer-tropsch synthetic catalyst provided according to the present invention, it is preferable that the weight ratio of Pt and Re is
(0.01-2): 1, more preferably (0.02-1.5): 1, most preferably (0.03-1): 1, the catalyst enabled in this way is through also
To C after original activation5+Long-chain heavy hydrocarbon has higher selectivity, is particularly suited for preparation C5+Long-chain heavy hydrocarbon.
According to the present invention, in the load type cobalt-base fischer-tropsch synthetic catalyst, it is preferable that relative to 100 parts by weight
Carrier, the content of Co are 15-50 parts by weight, and the content of Pt is 0.01-0.1 parts by weight, and the content of Re is 0.05-1 parts by weight；More
Preferably, the carrier relative to 100 parts by weight, the content of Co are 20-45 parts by weight, and the content of Pt is 0.015-0.075 weight
Part, the content of Re is 0.1-0.9 parts by weight；Most preferably, the carrier relative to 100 parts by weight, the content of Co are 20-40 weight
Part, the content of Pt is 0.02-0.05 parts by weight, and the content of Re is 0.2-0.8 parts by weight.It is closed when by the load type cobalt-base Fischer-Tropsch
When controlling in above-mentioned preferred range at the content of each component in catalyst, obtained catalyst is through reduction activation later to C5+
Long-chain heavy hydrocarbon has higher selectivity.
The present invention is not particularly limited the type of the carrier, various can be used as co-based fischer-tropsch to be existing
The carrier of synthetic catalyst, for example, can be unmodified porous oxide, or modified porous oxide, also
It can be the two mixture.Wherein, the example of the unmodified porous oxide includes but is not limited to SiO2、
Al2O3、TiO2And ZrO2At least one of.And the example of the modified component in the modified porous oxide includes but
It is not limited to selected from least one of Si, Al, Ti, Ce, La and Zr, the example of porous oxide includes but is not limited to SiO2、
Al2O3、TiO2And ZrO2At least one of, specific method of modifying can be existing conventional selection, to this those skilled in the art
Member can know that therefore not to repeat here.In addition, on the basis of the total weight of the modified porous oxide, it is therein to change
The content of property component can be 0.5-15 weight %, preferably 1-10 weight %.
Preferably, the carrier further contains support modification agent, it is highly preferred that the support modification agent includes SiO2、
TiO2、CeO2And La2O3At least one of, and carrier and support modification agent be not identical, and most preferably, the use of support modification agent
Amount is the 0.5-10% of vehicle weight.
The present invention is not particularly limited the specific surface area and pore volume of the carrier, for example, the specific surface area can
Think 20-400m2/ g, pore volume can be 0.2-2mL/g.In the present invention, the specific surface area and pore volume are low according to BET
Warm nitrogen adsorption method is measured.
The preparation method of load type cobalt-base fischer-tropsch synthetic catalyst provided by the invention includes loading Co and metal promoter
On carrier, wherein the metal promoter contains Pt and Re simultaneously.
The preparation method of the load type cobalt-base fischer-tropsch synthetic catalyst provided according to the present invention, it is preferable that in the load
In type Co based Fischer-Tropsch synthesis catalyst, the weight ratio of Pt and Re are (0.01-2): 1, more preferably (0.02-1.5): 1, most preferably
For (0.03-1): 1, the catalyst enabled in this way is after restoring to C5+Long-chain heavy hydrocarbon has higher selectivity, more
Suitable for preparation C5+Long-chain heavy hydrocarbon.
According to the present invention, in the load type cobalt-base fischer-tropsch synthetic catalyst, it is preferable that relative to 100 parts by weight
Carrier, the content of Co are 15-50 parts by weight, and the content of Pt is 0.01-0.1 parts by weight, and the content of Re is 0.05-1 parts by weight；More
Preferably, the carrier relative to 100 parts by weight, the content of Co are 20-45 parts by weight, and the content of Pt is 0.015-0.075 weight
Part, the content of Re is 0.1-0.9 parts by weight；Most preferably, the carrier relative to 100 parts by weight, the content of Co are 20-40 weight
Part, the content of Pt is 0.02-0.05 parts by weight, and the content of Re is 0.2-0.8 parts by weight.It is closed when by the load type cobalt-base Fischer-Tropsch
It is controlled in above-mentioned preferred range at the content of each component in catalyst, obtained catalyst is through reduction activation later to C5+It is long
Chain heavy hydrocarbon has higher selectivity.
The specific type and its specific surface area and pore volume of the carrier have been described herein above, and do not go to live in the household of one's in-laws on getting married herein
It states.
According to the present invention, the method for Co and metal promoter load on the carrier is generally included will be before cobalt precursors, platinum
Body and the load of rhenium precursor on the carrier, are then dried and roast.Wherein, cobalt precursors, platinum precursor and rhenium precursor are born
The mode carried on the carrier can be carried out using existing various modes, for example, above-mentioned three kinds of precursors can be made into molten
It is sprayed on the carrier after liquid；The carrier can be successively immersed in cobalt precursors solution, platinum precursor solution and rhenium precursor
In solution；The carrier can be first immersed in the mixed solution containing any the two in cobalt precursors, platinum precursor and rhenium precursor
In, then be immersed in a kind of remaining solution of precursor, the impregnation sequence of the two can be interchanged；The carrier impregnation can also be existed
In mixed solution simultaneously containing cobalt precursors, platinum precursor and rhenium precursor；It can also will be before cobalt precursors solution, platinum precursor solution and rhenium
Maceration extract of the liquid solution in batches as the carrier is impregnated, and is specifically known to the skilled person, is not gone to live in the household of one's in-laws on getting married herein
It states.
The present invention is not particularly limited the type of the cobalt precursors, platinum precursor and rhenium precursor, can be existing each
Soluble-salt of the kind in the oxide of the oxide and rhenium for the oxide, platinum that can be converted into cobalt after drying and roasting.
Specifically, the example of cobalt precursors includes but is not limited at least one of nitrate, carbonate, sulfate and hydrochloride of cobalt.
The example of the platinum precursor includes but is not limited to the nitrate of platinum and its complex and chloroplatinic acid, chloroplatinate and its matches
At least one of position compound.The example of the rhenium precursor includes but is not limited in perrhenic acid, ammonium perrhenate and rhenium trichloride
At least one.
The present invention is not particularly limited the condition of the drying, for example, generally including drying temperature can be 55-
130 DEG C, drying pressure can be 0-1bar, and drying time can be 30min-1h.
In the present invention, the pressure refers both to gauge pressure.
The present invention is not particularly limited the condition of the roasting, for example, generally including maturing temperature can be 180-
450 DEG C, calcining time can be 1-10h.
The present invention also provides by above-mentioned load type cobalt-base fischer-tropsch synthetic catalyst or prepared by the above method
Load type cobalt-base fischer-tropsch synthetic catalyst is through restoring obtained load type cobalt-base F- T synthesis activated catalyst.
The present invention is not particularly limited the method for the reduction activation, can carry out according to existing various modes,
For example, above-mentioned load type cobalt-base fischer-tropsch synthetic catalyst can be carried out reduction activation in a hydrogen atmosphere, wherein reduction temperature
It can be 320-450 DEG C, reduction pressure can be 1-15bar, and the recovery time can be 4-50 hours, hydrogen in reduction process
Air speed can be 1000-15000h-1。
In the present invention, the air speed refers to that (unit is for unit time (unit is hour), per volume of catalyst
Rise) gas flow (unit be rise) under the standard state of processing.
Load type cobalt-base fischer-tropsch synthetic catalyst provided by the invention can be used for coal, biomass, coal bed gas, natural gas and
Trans-utilization of the feedstock hydrocarbons such as shale gas through synthesis gas.
In addition, this method includes urging synthesis gas in F- T synthesis the present invention also provides a kind of method of F- T synthesis
It is reacted in the presence of agent, wherein the fischer-tropsch synthetic catalyst is above-mentioned load type cobalt-base F- T synthesis activating catalytic
Agent.
Theing improvement is that for Fischer-Tropsch synthesis method provided by the invention uses a kind of new fischer-tropsch synthetic catalyst, and
Other conditions can be same as the prior art, can know to this those skilled in the art, therefore not to repeat here.
The present invention will be described in detail by way of examples below.
In following embodiment, room temperature is 25 DEG C, and normal pressure refers both to standard atmospheric pressure.
In following embodiment and comparative example, Co based Fischer-Tropsch synthesis catalyst performance measures in accordance with the following methods:
(1) it element species and content analysis: is measured using Xray fluorescence spectrometer (XRF), model ZSX
Primus II (Rigaku), Upside Radiation x ray generator, 4kW Rh target, test elements class scope are F-
U, test zone diameter are 30mm, and test method is full element semi-quantitative method.
(2) specific surface area and pore volume: the TriStar II3020 physics produced using Micrometrics company of the U.S.
Adsorption instrument is measured, wherein the analyst coverage of equipment is: the test scope of material specific surface area is 0.01m2/ g is to supreme
It limits, relative pressure (P/Po=0.01-1) used in test.
Embodiment 1
The embodiment is for illustrating load type cobalt-base fischer-tropsch synthetic catalyst provided by the invention and preparation method thereof.
It weighs cobalt nitrate hexahydrate 35.5g and tri-chlorination platinum 0.0155g, is added 35.12g deionized water stirring and dissolving, then plus
The perrhenic acid aqueous solution 1.7411g for entering 77.5 weight % concentration, stirs and evenly mixs, maceration extract is prepared.With commercially available TiO2For
Carrier, the TiO2Carrier is the TiO for being P25 by the trade mark of Evonik Degussa Corp.'s production2Powder is sized mixing, and in inlet temperature 250
DEG C, spray drying forming under conditions of 120 DEG C of outlet temperature, obtained after then being roasted 1 hour at 500 DEG C, the TiO2Carrier
Specific surface area be 50m2/ g, pore volume 0.6mL/g.Weigh the above-mentioned TiO of 100g2Carrier at normal temperatures and pressures adds maceration extract
Enter onto the carrier, stir evenly, and is kept for 10 minutes at normal temperatures and pressures.Impregnated just wet carrier is put into forced air drying
In case, after 3 hours dry at 70 DEG C, 0.8bar, it be then placed in Muffle furnace and roasted 1 hour at 450 DEG C, is prepared
Load type cobalt-base fischer-tropsch synthetic catalyst, is denoted as C1.TiO in catalyst C1, relative to 100 parts by weight2Carrier, Co's
Content is 15 parts by weight, and the content of Pt is 0.01 parts by weight, and the content of Re is 1.0 parts by weight.
Embodiment 2
The embodiment is for illustrating load type cobalt-base fischer-tropsch synthetic catalyst provided by the invention and preparation method thereof.
It weighs cobalt nitrate hexahydrate 98.8g and tri-chlorination platinum 0.0618g, is added 15.73g deionized water stirring and dissolving, then plus
The perrhenic acid aqueous solution 0.5223g for entering 77.5 weight % concentration, stirs and evenly mixs, maceration extract is prepared.With commercially available Al2O3For
Carrier, the Al2O3Carrier is the carrier that the trade mark of SASOL company production is Puralox Scca 5/150, the specific surface of the carrier
Product is 150m2/ g, pore volume 0.5mL/g.It weighs the above-mentioned carrier of 100g to be put into Rotary Evaporators evaporative flask, is evacuated to and is
System pressure is 0.8bar, using negative pressure by maceration extract through in Rotary Evaporators liquid-feeding tube sucking evaporative flask, Stirring is uniform, so
It is impregnated 5 hours under room temperature 0.8bar pressure afterwards.After dipping, 80 DEG C are warming up to using Rotary Evaporators, is pressed in 0.8bar
It is 2 hours dry under power, the sample after drying is put into Muffle furnace and is roasted 5 hours at 300 DEG C, supported cobalt is prepared
Base fischer-tropsch synthetic catalyst, is denoted as C2.Al in catalyst C2, relative to 100 parts by weight2O3Carrier, the content of Co are 20
Parts by weight, the content of Pt are 0.04 parts by weight, and the content of Re is 0.3 parts by weight.
Embodiment 3
The embodiment is for illustrating load type cobalt-base fischer-tropsch synthetic catalyst provided by the invention and preparation method thereof.
Cobalt nitrate hexahydrate 123.5g, chloroplatinic acid 0.0531g and rhenium trichloride 1.2569g are weighed, 69.68g deionization is added
Water stirring and dissolving, is prepared maceration extract.With commercially available porous SiO2For carrier, the SiO2Carrier is Davis Co., Ltd's production
The trade mark is the carrier of Davisil 62, and the specific surface area of the carrier is 303m2/ g, pore volume 1.1mL/g.Weigh 100g carrier
And be heated to 70 DEG C, maceration extract is heated to 70 DEG C and is uniformly sprayed on carrier, after being kept for 30 minutes at 70 DEG C, it will impregnate
Good carrier is put into the drying box of nitrogen atmosphere protection, after 0.5 hour dry at 90 DEG C, 0.8bar, is placed in nitrogen gas
Muffle furnace under atmosphere roasts 10 hours at 200 DEG C later, load type cobalt-base fischer-tropsch synthetic catalyst is prepared, is denoted as C3.
Porous SiO in catalyst C3, relative to 100 parts by weight2The content of carrier, Co is 25 parts by weight, and the content of Pt is
0.02 parts by weight, the content of Re are 0.8 parts by weight.
Embodiment 4
The embodiment is for illustrating load type cobalt-base fischer-tropsch synthetic catalyst provided by the invention and preparation method thereof.
Weigh cobalt nitrate hexahydrate 148.2g, 65.02g deionized water stirring and dissolving be added, be prepared impregnate for the first time it is molten
Liquid.Chloroplatinic acid 0.1858g and rhenium trichloride 0.3142g are separately weighed, 96g deionized water stirring and dissolving is added, is prepared second
Secondary dipping solution.Contain SiO with commercially available2Al2O3For carrier (SiO2Content: 1 weight %), which is the production of SASOL company
The trade mark be Siralox Scca 1/270 carrier, the group of the carrier becomes 1 weight %SiO2With 99 weight %Al2O3, the load
The specific surface area of body is 226m2/ g, pore volume 0.6mL/g.The above-mentioned carrier of 100g is weighed to be put into Rotary Evaporators evaporative flask,
And carrier is heated to 60 DEG C, first time maceration extract is heated to pour into above-mentioned carrier after 60 DEG C, it is small to impregnate 1 under normal pressure
When.After dipping, 120 DEG C are warming up to using Rotary Evaporators, is dried 4 hours under normal pressure, dipping preparation for the first time is completed；
Continue would be heated to 60 DEG C of second of maceration extract to pour into the carrier for completing dipping preparation for the first time, be soaked at 60 DEG C of normal pressure
Stain 1 hour, after dipping, 120 DEG C are warming up to using Rotary Evaporators, is dried 4 hours under normal pressure, second is completed and impregnates
Preparation.Drying sample after double-steeping is put into Muffle furnace, is roasted 4 hours at 350 DEG C, load type cobalt-base expense is prepared
Tropsch synthesis catalyst is denoted as C4.In catalyst C4, contain SiO relative to 100 parts by weight2Al2O3Carrier, the content of Co
For 30 parts by weight, the content of Pt is 0.07 parts by weight, and the content of Re is 0.2 parts by weight.
Embodiment 5
The embodiment is for illustrating load type cobalt-base fischer-tropsch synthetic catalyst provided by the invention and preparation method thereof.
Weigh cobalt nitrate hexahydrate 51.9g, 140.76g deionized water stirring and dissolving be added, be prepared impregnate for the first time it is molten
Liquid.Cobalt nitrate hexahydrate 121.0g, platinum nitrate 0.0654g and ammonium perrhenate 0.7202g are separately weighed, 83.1g deionized water is added and stirs
Dissolution is mixed, second of dipping solution is prepared.Contain TiO with commercially available2Al2O3For carrier (TiO2Content: 1 weight %), it should
Carrier is the Al for being Puralox Scca 20/200 with the trade mark that SASOL company produces2O3Carrier is matrix, on the matrix with
Tetrabutyl titanate is titanium source, impregnates the TiO of upper 1 weight %2And it is made after being roasted 2 hours at 500 DEG C；The group of the carrier becomes
1 weight %TiO2With 99 weight %Al2O3, the specific surface area of the carrier is 172m2/ g, pore volume 0.8mL/g.Weigh 100g
Above-mentioned carrier is put into Rotary Evaporators evaporative flask, and carrier is heated to 55 DEG C, after first time maceration extract is heated to 55 DEG C
It pours into above-mentioned carrier, impregnates 2 hours under normal pressure.After dipping, be warming up to 75 DEG C using Rotary Evaporators, in normal pressure and
Nitrogen purging is lower 6 hours dry, and the drying sample after first time is impregnated is put into Muffle furnace, in the case where 250 DEG C of nitrogen atmospheres are protected
Roast the dipping preparation for the first time of completion in 4 hours；Continue to would be heated to 55 DEG C of second of maceration extract and pour into complete and soaks for the first time
In the carrier of stain preparation, is impregnated 2 hours at 55 DEG C of normal pressure, after dipping, 75 DEG C are warming up to using Rotary Evaporators, normal
It is 6 hours dry under pressure and nitrogen purging, complete second of impregnation drying.Drying sample is put into Muffle furnace, is roasted at 250 DEG C
8 hours, load type cobalt-base fischer-tropsch synthetic catalyst is prepared, is denoted as C5.In catalyst C5, relative to 100 parts by weight
Contain TiO2Al2O carrier, the content of Co are 35 parts by weight, and the content of Pt is 0.04 parts by weight, and the content of Re is 0.5 weight
Part.
Embodiment 6
The embodiment is for illustrating load type cobalt-base fischer-tropsch synthetic catalyst provided by the invention and preparation method thereof.
Cobalt nitrate hexahydrate 98.8g, platinum nitrate 0.0246g and ammonium perrhenate 0.5042g are weighed, 143.3g deionized water is added
First time dipping solution is prepared in stirring and dissolving；Separately weigh cobalt nitrate hexahydrate 98.8g, platinum nitrate 0.0246g and ammonium perrhenate
0.5042g is added 107.3g deionized water stirring and dissolving, second of dipping solution is prepared.Contain CeO with commercially available2's
Al2O3For carrier (CeO2Content: 5 weight %), it is Puralox Scca 20/ which, which is with the trade mark that SASOL company produces,
200 Al2O3Carrier is matrix, using cerous nitrate as cerium source on the matrix, impregnates the CeO of upper 5 weight %2And it is roasted at 500 DEG C
It is made after burning 2 hours；The group of the carrier becomes 5 weight %CeO2With 95 weight %Al2O3, the specific surface area of the carrier is
200m2/ g, pore volume 0.9mL/g.It weighs the above-mentioned carrier of 100g to be put into Rotary Evaporators evaporative flask, and carrier is heated to
50 DEG C, being evacuated to system pressure is 0.02bar, after first time maceration extract is heated to 50 DEG C, is passed through maceration extract using negative pressure
Rotary Evaporators catheter is added in carrier, impregnates 3 hours at pressure 0.02bar.After dipping, Rotary Evaporators are utilized
55 DEG C are warming up to, continuation heats 10 hours to sample drying at pressure 0.02bar, and the drying sample after first time is impregnated is put
Enter Muffle furnace, the dipping preparation for the first time of completion in 5 hours is roasted at 300 DEG C；The sample for completing dipping preparation for the first time is put into
In Rotary Evaporators evaporative flask, 50 DEG C are heated to, is evacuated to system pressure 0.02bar, continues to would be heated to the second of 50 DEG C
Secondary maceration extract imports, and impregnates 3 hours at 50 DEG C, after dipping, is warming up to 55 DEG C using Rotary Evaporators, continuation is being pressed
Heating 10 hours under power 0.02bar makes sample drying.Drying sample is put into Muffle furnace, and is roasted 5 hours at 300 DEG C, is made
It is standby to obtain load type cobalt-base fischer-tropsch synthetic catalyst, it is denoted as C6.In catalyst C6, contain CeO relative to 100 parts by weight2
Al2O3Carrier, the content of Co are 40 parts by weight, and the content of Pt is 0.03 parts by weight, and the content of Re is 0.7 parts by weight.
Embodiment 7
The embodiment is for illustrating load type cobalt-base fischer-tropsch synthetic catalyst provided by the invention and preparation method thereof.
Cobalt nitrate hexahydrate 66.7g is weighed, 59.3g deionized water stirring and dissolving is added, first time dipping solution is prepared；
Cobalt nitrate hexahydrate 88.9g, four ammino platinum nitrate 0.0496g and ammonium perrhenate 0.2881g are separately weighed, 31g deionized water is added and stirs
Dissolution is mixed, second of dipping solution is prepared；Cobalt nitrate hexahydrate 66.7g, four ammino platinum nitrate 0.0496g and high rhenium are weighed again
Sour ammonium 0.2881g is added 15.3g deionized water stirring and dissolving, third time dipping solution is prepared.Contain La with commercially available2O3's
Al2O3(La2O3Content: 5 weight %) it is carrier, it is Puralox Scca 20/ which, which is with the trade mark that SASOL company produces,
200 Al2O3Carrier is matrix, using lanthanum nitrate as lanthanum source on the matrix, impregnates the La of upper 5 weight %2O3And at 500 DEG C
It is made after roasting 2 hours；The group of the carrier becomes 5 weight %La2O3With 95 weight %Al2O3, the specific surface area of the carrier is
190m2/ g, pore volume 0.8mL/g.It weighs the 100g carrier to be put into Rotary Evaporators evaporative flask, and carrier is heated to 45
DEG C, being evacuated to system pressure is 0.2bar, after first time maceration extract is heated to 45 DEG C, using negative pressure by maceration extract through rotating
Evaporimeter catheter is added in carrier, impregnates 4 hours at pressure 0.2bar.After dipping, heated up using Rotary Evaporators
To 60 DEG C, continuation is heated 8 hours at pressure 0.2bar makes sample drying, and the drying sample after first time is impregnated is put into Muffle
Furnace roasts the dipping preparation for the first time of completion in 2 hours in the case where 250 DEG C of nitrogen atmospheres are protected；It will complete the sample of dipping preparation for the first time
Product are put into Rotary Evaporators evaporative flask, are heated to 45 DEG C, are evacuated to system pressure 0.2bar, continue to would be heated to 45 DEG C
Second of maceration extract imports, and impregnates 4 hours at 45 DEG C, after dipping, is warming up to 60 DEG C using Rotary Evaporators, continues
Heating 8 hours under pressure 0.2bar makes sample drying.Drying sample is put into Muffle furnace, is roasted in the case where 250 DEG C of nitrogen atmospheres are protected
It burns and completes within 2 hours second of dipping preparation；The sample for completing second of dipping preparation is put into Rotary Evaporators evaporative flask, is added
Heat is evacuated to system pressure 0.2bar to 45 DEG C, continues would be heated to 45 DEG C of third time maceration extract and imports, soaks at 45 DEG C
Stain 4 hours, after dipping, 60 DEG C are warming up to using Rotary Evaporators, continuation is heated 8 hours at pressure 0.2bar makes sample
It is dry.Drying sample is put into Muffle furnace, is roasted 2 hours in the case where 400 DEG C of nitrogen atmospheres are protected, load type cobalt-base expense is prepared
Tropsch synthesis catalyst is denoted as C7.In catalyst C7, contain La relative to 100 parts by weight2O3Al2O3Carrier, Co's contains
Amount is 45 parts by weight, and the content of Pt is 0.05 parts by weight, and the content of Re is 0.4 parts by weight.
Embodiment 8
The embodiment is for illustrating load type cobalt-base fischer-tropsch synthetic catalyst provided by the invention and preparation method thereof.
Cobalt nitrate hexahydrate 98.8g, four ammino platinum nitrate 0.0794g and ammonium perrhenate 0.0576g are weighed, 36.8g is added and goes
First time dipping solution is prepared in ionized water stirring and dissolving；Separately weigh cobalt nitrate hexahydrate 98.8g, four ammino platinum nitrates
0.0794g and ammonium perrhenate 0.0576g is added 19.5g deionized water stirring and dissolving, second of dipping solution is prepared；Again
Cobalt nitrate hexahydrate 49.4g, four ammino platinum nitrate 0.0397g and ammonium perrhenate 0.0288g are weighed, 16.7g deionized water is added and stirs
Dissolution is mixed, third time dipping solution is prepared.Contain SiO with commercially available2、TiO2And La2O3Modified Al2O3(SiO2、TiO2With
La2O3Content is respectively as follows: 2.5 weight %, 2.5 weight % and 5 weight %) it is carrier, which is to contain La with embodiment 72O3
Al2O3(La2O3Content: 5 weight %) carrier be matrix, using ethyl orthosilicate as silicon source, using butyl titanate as titanium source, altogether
Impregnate the SiO of upper 2.5 weight %2With 2.5 weight %TiO2And it is made after being roasted 2 hours at 500 DEG C；The group of the carrier becomes 5
Weight %La2O3, 2.5 weight %TiO2, 2.5 weight %SiO2With 90 weight %Al2O3；The specific surface area of the carrier is 180m2/
G, pore volume 0.7mL/g.It weighs 100g carrier to be put into Rotary Evaporators evaporative flask, and carrier is heated to 40 DEG C, take out true
Sky to system pressure is 0.5bar, and first time maceration extract is heated to 50 DEG C, utilizes negative pressure by maceration extract through rotary evaporation later
Instrument catheter is added in carrier, impregnates 1 hour at pressure 0.5bar.After dipping, 95 are warming up to using Rotary Evaporators
DEG C, continuation is heated 1 hour at pressure 0.5bar makes sample drying, and the drying sample after first time is impregnated is put into Muffle furnace,
The dipping preparation for the first time of completion in 2 hours is roasted at 250 DEG C；The sample for completing dipping preparation for the first time is put into Rotary Evaporators
In evaporative flask, 40 DEG C are heated to, being evacuated to system pressure is 0.5bar, continues would be heated to 40 DEG C of second of maceration extract and leads
Enter, impregnated 1 hour at 40 DEG C, after dipping, be warming up to 95 DEG C using Rotary Evaporators, continues to add at pressure 0.5bar
Heat makes sample drying for 4 hours, completes second of dipping preparation；The sample for completing second of dipping preparation is put into Rotary Evaporators
In evaporative flask, 40 DEG C are heated to, is evacuated to system pressure 0.5bar, continues would be heated to 40 DEG C of third time maceration extract and leads
Enter, impregnated 1 hour at 40 DEG C, after dipping, be warming up to 95 DEG C using Rotary Evaporators, continues to add at pressure 0.5bar
Heat makes sample drying in 4 hours.Drying sample is put into Muffle furnace, is roasted 2 hours at 250 DEG C, load type cobalt-base is prepared
Fischer-tropsch synthetic catalyst is denoted as C8.In catalyst C8, contain SiO relative to 100 parts by weight2、TiO2And La2O3Load
Body, the content of Co are 50 parts by weight, and the content of Pt is 0.1 parts by weight, and the content of Re is 0.1 parts by weight.
Comparative example 1
This comparative example is catalyzed as the comparative example of embodiment 4 for load type cobalt-base F- T synthesis more provided by the invention
Agent and load type cobalt-base fischer-tropsch synthetic catalyst of the Pt and Re dosage not within preferred scope of the present invention.
Load type cobalt-base catalyst is prepared according to the method for embodiment 4, unlike, in catalyst preparation process, chlorine
The dosage of platinic acid is 0.398g, and the dosage of rhenium trichloride is 2.357g, and load type cobalt-base fischer-tropsch synthetic catalyst is prepared, and is remembered
For DC4.In catalyst DC4, contain SiO relative to 100 parts by weight2Al2O3Carrier, the content of Co are 30 parts by weight, Pt
Content be 0.15 parts by weight, the content of Re is 1.5 parts by weight.
Within the scope of the dosage of Pt and Re is fallen into disclosed in CN101269336A in above-mentioned load type cobalt-base catalyst, but
Not within the preferred amount ranges of load type cobalt-base catalyst Pt and Re of the present invention.
Comparative example 2
This comparative example is catalyzed as the comparative example of embodiment 3 for load type cobalt-base F- T synthesis more provided by the invention
Agent and Pt and Re the dosage not load type cobalt-base F- T synthesis disclosed in the CN101269336A within preferred scope of the present invention
Catalyst.
Cobalt nitrate hexahydrate 123.5g, chloroplatinic acid 2.65g and rhenium trichloride 2.36g are weighed, 60.52g deionized water is added and stirs
Dissolution is mixed, maceration extract is prepared.With it is commercially available have enrich hollow and macropore SiO2For carrier, the SiO2Carrier is to wear dimension
The carrier that the trade mark of this company production is Davisil 62, the specific surface area of the carrier are 303m2/ g, pore volume 1.1mL/g.
It weighs 100g carrier and is heated to 70 DEG C, maceration extract is heated to 70 DEG C and is uniformly sprayed on carrier, keeps 30 at 70 DEG C
After minute, impregnated carrier is put into the drying box of nitrogen atmosphere protection, after 0.5 hour dry at 90 DEG C, 0.8bar,
It is put into Muffle furnace in a nitrogen atmosphere, is roasted 10 hours at 200 DEG C later, load type cobalt-base F- T synthesis is prepared and urges
Agent is denoted as DC3.In catalyst precarsor DC3, relative to 100 parts by weight there is the SiO for enriching hollow and macropore to carry
Body, the content of Co are 25 parts by weight, and the content of Pt is 1.0 parts by weight, and the content of Re is 1.5 parts by weight.
Within the scope of the dosage of Pt and Re is fallen into disclosed in CN101269336A in above-mentioned load type cobalt-base catalyst, but
Not within the preferred amount ranges of load type cobalt-base catalyst Pt and Re of the present invention.
Comparative example 3
The comparative example is for comparing the importance that Pt is indispensable in load type cobalt-base fischer-tropsch synthetic catalyst metal promoter.
Load type cobalt-base catalyst is prepared according to the method for embodiment 4, unlike, in catalyst preparation process, chlorine
The dosage of platinic acid is 0g, and the dosage of rhenium trichloride is 0.43g, and the load type cobalt-base fischer-tropsch synthetic catalyst of reference is prepared,
It is denoted as DC1.In catalyst DC1, contain SiO relative to 100 parts by weight2Al2O3Carrier, the content of Co are 30 parts by weight,
The content of Pt is 0 parts by weight, and the content of Re is 0.27 parts by weight.
Comparative example 4
The comparative example is for comparing the importance that Re is indispensable in load type cobalt-base fischer-tropsch synthetic catalyst metal promoter.
Load type cobalt-base catalyst is prepared according to the method for embodiment 4, unlike, in catalyst preparation process, chlorine
The dosage of platinic acid is 0.186g, and the dosage of rhenium trichloride is 0g, and the load type cobalt-base fischer-tropsch synthetic catalyst of reference is prepared,
It is denoted as DC2.In catalyst DC2, relative to the carrier of 100 parts by weight, the content of Co is 30 parts by weight, and the content of Pt is
0.07 parts by weight, the content of Re are 0 parts by weight.
Test case
Test case is used to illustrate the test of load type cobalt-base fischer-tropsch synthetic catalyst performance.
The evaluation of load type cobalt-base fischer-tropsch synthetic catalyst reactivity worth carries out on fixed-bed micro-reactor.Specifically,
1.5g load type cobalt-base fischer-tropsch synthetic catalyst and 6g quartz sand are fitted into after mixing in above-mentioned fixed-bed micro-reactor, so
After be passed through H2And by temperature rise to 375 DEG C, pressure normal pressure, hydrogen air speed be 5000h-1 under conditions of reduction activation 16h, obtain
To with the active activated catalyst of F- T synthesis.It is passed through synthesis gas (n (H2)/n (CO)=2.0) later, and condition is controlled
Fischer-Tropsch synthesis is carried out under conditions of temperature is 210 DEG C, pressure 2.1MPa, synthesis gas air speed are 3000h-1.Reaction produces
Object is collected by hot trap and cold-trap respectively, and reaction end gas is by gas-chromatography on-line analysis.After reaction reaches stable state, according to product and tail
Gas Analysis result calculation obtains CO conversion ratio and selectivity of product, wherein one way CO conversion ratio is that the CO of conversion accounts for air inlet CO's
Ratio, CH4Selectivity is the weight percent that methane accounts for total hydrocarbon products, C5+Selectivity is generation C5+Hydrocarbon products account for total hydrocarbon products
Weight percent.Acquired results are shown in Table 1.
Table 1
As can be seen from the above results, load type cobalt-base fischer-tropsch synthetic catalyst provided by the invention is not only with higher
Catalytic activity, but also the comparison of comparative example 1-2 with higher can be seen that work as and urge the load type cobalt-base F- T synthesis
The content of Pt and Re controls in currently preferred range in agent, rather than within the scope of disclosure CN101269336A
When, under identical catalytic active component Co load capacity, to C5+Long-chain heavy hydrocarbon (it is desirable that The more the better) has higher selectivity,
And to by-product CH4(it is desirable that more fewer better) has lower selectivity.
It can also be seen that by the data of table 1 above: only when Pt and Re are existed simultaneously as metal promoter in supported cobalt
In base fischer-tropsch synthetic catalyst, and the content of Pt and Re is within preferred amount ranges of the present invention, rather than other ranges,
Such as when within the scope of disclosure CN101269336A, the load type cobalt-base fischer-tropsch synthetic catalyst after reduction activation, which just has, is urged
Change activity height, C5+Long-chain heavy hydrocarbon selectivity is also high and by-product CH4The low unexpected technical effect of selectivity.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above
Detail within the scope of the technical concept of the present invention can be with various simple variants of the technical solution of the present invention are made, this
A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case where shield, it can be combined in any appropriate way.In order to avoid unnecessary repetition, the present invention to it is various can
No further explanation will be given for the combination of energy.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should also be regarded as the disclosure of the present invention.
Claims (16)
1. a kind of load type cobalt-base fischer-tropsch synthetic catalyst, which includes the catalysis of carrier and load on the carrier
Active component Co and metal promoter, the metal promoter contain Pt and Re simultaneously；Relative to the carrier of 100 parts by weight, Co's contains
Amount is 15-50 parts by weight, and the content of Pt is 0.01-0.1 parts by weight, and the content of Re is 0.05-1 parts by weight, and the weight of Pt and Re
Amount is than being (0.01-0.125): 1, the carrier is unmodified porous oxide and/or modified porous oxide, institute
It states unmodified porous oxide and is selected from SiO2、Al2O3、TiO2And ZrO2At least one of, the modified porous oxidation
Modified component in object is selected from least one of Si, Al, Ti, Ce, La and Zr, with the total of the modified porous oxide
On the basis of weight, the content of modified component therein is 1-10 weight %.
2. load type cobalt-base fischer-tropsch synthetic catalyst according to claim 1, wherein the carrier further contains carrier
Modifying agent.
3. load type cobalt-base fischer-tropsch synthetic catalyst according to claim 2, wherein the support modification agent includes SiO2、
TiO2、CeO2And La2O3At least one of, and carrier and support modification agent be not identical.
4. load type cobalt-base fischer-tropsch synthetic catalyst according to claim 2, wherein the dosage of support modification agent is carrier
The 0.5-10% of weight.
5. load type cobalt-base fischer-tropsch synthetic catalyst according to claim 1, wherein the specific surface area of the carrier is
20-400m2/ g, pore volume 0.2-2mL/g.
6. a kind of preparation method of load type cobalt-base fischer-tropsch synthetic catalyst, this method includes by catalytic active component Co and metal
Auxiliary agent is supported on carrier, and the metal promoter contains Pt and Re simultaneously；In the load type cobalt-base fischer-tropsch synthetic catalyst,
Relative to the carrier of 100 parts by weight, the content of Co is 15-50 parts by weight, and the content of Pt is 0.01-0.1 parts by weight, the content of Re
For 0.05-1 parts by weight, and the weight ratio of Pt and Re is (0.01-0.125): 1；The carrier is unmodified porous oxide
And/or modified porous oxide, the unmodified porous oxide are selected from SiO2、Al2O3、TiO2And ZrO2In at least
One kind, the modified component in the modified porous oxide are selected from least one of Si, Al, Ti, Ce, La and Zr, with
On the basis of the total weight of the modified porous oxide, the content of modified component therein is 1-10 weight %.
7. according to the method described in claim 6, wherein, the carrier further contains support modification agent.
8. according to the method described in claim 7, wherein, the support modification agent includes SiO2、TiO2、CeO2And La2O3In
At least one, and carrier and support modification agent be not identical.
9. according to the method described in claim 7, wherein, the dosage of support modification agent is the 0.5-10% of vehicle weight.
10. the method according to any one of claim 6-9, wherein Co and metal promoter are supported on the carrier
On method include by cobalt precursors, platinum precursor and rhenium precursor load on the carrier, be then dried and roast.
11. according to the method described in claim 10, wherein, cobalt precursors are nitrate, carbonate, sulfate and the hydrochloride of cobalt
At least one of.
12. according to the method described in claim 10, wherein, the platinum precursor be platinum nitrate and its complex and
At least one of chloroplatinic acid, chloroplatinate and its complex.
13. according to the method described in claim 10, wherein, the rhenium precursor is in perrhenic acid, ammonium perrhenate and rhenium trichloride
At least one.
14. being done according to the method described in claim 10, wherein, the condition of the drying includes that drying temperature is 55-130 DEG C
Dry pressure is 0-1bar, drying time 30min-5h；The condition of the roasting includes that maturing temperature is 180-450 DEG C, roasting
Time is 1-10h.
15. the load type cobalt-base fischer-tropsch synthetic catalyst as described in any one of claim 1-5 or by claim 6-
The load type cobalt-base fischer-tropsch synthetic catalyst that method described in any one of 14 is prepared is through restoring obtained supported cobalt
Base F- T synthesis activated catalyst.
16. a kind of method of F- T synthesis, including synthesis gas is reacted in the presence of fischer-tropsch synthetic catalyst, it is described to take
Tropsch synthesis catalyst is load type cobalt-base F- T synthesis activated catalyst described in claim 15.
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| CN108187708B (en) * | 2018-02-01 | 2021-05-04 | 中科合成油内蒙古有限公司 | Phosphorus-containing high-stability heavy hydrocarbon Fischer-Tropsch synthesis catalyst and preparation method and application thereof |
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| CN111905740B (en) * | 2019-05-07 | 2022-10-11 | 国家能源投资集团有限责任公司 | Preparation method of titanium oxide-loaded cobalt-based Fischer-Tropsch synthesis catalyst and cobalt-based Fischer-Tropsch synthesis catalyst |
| CN111905741A (en) * | 2019-05-07 | 2020-11-10 | 国家能源投资集团有限责任公司 | Alumina-loaded cobalt-based Fischer-Tropsch synthesis catalyst and preparation method thereof |
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| CN102580771A (en) * | 2011-12-14 | 2012-07-18 | 中国科学院山西煤炭化学研究所 | Ternary multi-level pore cobalt-based catalyst and preparation and application thereof |
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| JPS5621647A (en) * | 1979-07-13 | 1981-02-28 | Shell Int Research | Manufacture of fischerrtropsch catalyst |
| CN103442806A (en) * | 2011-02-07 | 2013-12-11 | 牛津催化剂有限公司 | Fischer-tropsch catalysts and method of preparation thereof |
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