CN103272603B - Fischer-Tropsch catalyst containing zinc-cobalt base and preparation method thereof - Google Patents
Fischer-Tropsch catalyst containing zinc-cobalt base and preparation method thereof Download PDFInfo
- Publication number
- CN103272603B CN103272603B CN201310191525.3A CN201310191525A CN103272603B CN 103272603 B CN103272603 B CN 103272603B CN 201310191525 A CN201310191525 A CN 201310191525A CN 103272603 B CN103272603 B CN 103272603B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- sio
- mentioned
- precursor
- carrier
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 216
- 238000002360 preparation method Methods 0.000 title claims abstract description 35
- HSSJULAPNNGXFW-UHFFFAOYSA-N [Co].[Zn] Chemical compound [Co].[Zn] HSSJULAPNNGXFW-UHFFFAOYSA-N 0.000 title abstract 2
- 239000011701 zinc Substances 0.000 claims description 71
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 50
- 238000000034 method Methods 0.000 claims description 46
- 239000002243 precursor Substances 0.000 claims description 38
- 229910052725 zinc Inorganic materials 0.000 claims description 38
- 238000001035 drying Methods 0.000 claims description 36
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 33
- 230000008569 process Effects 0.000 claims description 30
- 230000000694 effects Effects 0.000 claims description 25
- 238000005470 impregnation Methods 0.000 claims description 13
- 238000001556 precipitation Methods 0.000 claims description 13
- 238000001802 infusion Methods 0.000 claims description 12
- 238000000975 co-precipitation Methods 0.000 claims description 8
- 230000008021 deposition Effects 0.000 claims description 8
- 238000000151 deposition Methods 0.000 claims description 8
- 238000007598 dipping method Methods 0.000 claims description 8
- 238000001354 calcination Methods 0.000 claims description 5
- 238000000354 decomposition reaction Methods 0.000 claims description 5
- 238000004898 kneading Methods 0.000 claims description 5
- 238000001994 activation Methods 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 230000004913 activation Effects 0.000 claims description 2
- 150000003863 ammonium salts Chemical class 0.000 claims description 2
- 150000004675 formic acid derivatives Chemical class 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N nitrate group Chemical group [N+](=O)([O-])[O-] NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 150000003891 oxalate salts Chemical class 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 36
- 239000011593 sulfur Substances 0.000 abstract description 28
- 229910052717 sulfur Inorganic materials 0.000 abstract description 28
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 11
- 230000003197 catalytic effect Effects 0.000 abstract description 8
- 235000012239 silicon dioxide Nutrition 0.000 abstract description 8
- 229910052681 coesite Inorganic materials 0.000 abstract description 5
- 229910052906 cristobalite Inorganic materials 0.000 abstract description 5
- 239000000377 silicon dioxide Substances 0.000 abstract description 5
- 229910052682 stishovite Inorganic materials 0.000 abstract description 5
- 229910052905 tridymite Inorganic materials 0.000 abstract description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract 2
- 229910052593 corundum Inorganic materials 0.000 abstract 2
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 2
- 230000015572 biosynthetic process Effects 0.000 description 27
- 238000002803 maceration Methods 0.000 description 27
- 238000003786 synthesis reaction Methods 0.000 description 26
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 24
- 229910017052 cobalt Inorganic materials 0.000 description 22
- 239000010941 cobalt Substances 0.000 description 22
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 22
- 239000000203 mixture Substances 0.000 description 21
- 239000007789 gas Substances 0.000 description 20
- 239000008367 deionised water Substances 0.000 description 18
- 229910021641 deionized water Inorganic materials 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 13
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 13
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 13
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 12
- 238000002156 mixing Methods 0.000 description 10
- 239000000843 powder Substances 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- 239000005864 Sulphur Substances 0.000 description 9
- 229910052782 aluminium Inorganic materials 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 239000004411 aluminium Substances 0.000 description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 8
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical class O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 8
- 239000011148 porous material Substances 0.000 description 8
- JGPSMWXKRPZZRG-UHFFFAOYSA-N zinc;dinitrate;hexahydrate Chemical class O.O.O.O.O.O.[Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O JGPSMWXKRPZZRG-UHFFFAOYSA-N 0.000 description 8
- 239000004215 Carbon black (E152) Substances 0.000 description 7
- 239000002253 acid Substances 0.000 description 7
- 229930195733 hydrocarbon Natural products 0.000 description 7
- 150000002430 hydrocarbons Chemical class 0.000 description 7
- 239000012535 impurity Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 229910010413 TiO 2 Inorganic materials 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 230000009467 reduction Effects 0.000 description 6
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000011259 mixed solution Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 4
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 4
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 206010013786 Dry skin Diseases 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 231100000614 poison Toxicity 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000004062 sedimentation Methods 0.000 description 3
- 238000007493 shaping process Methods 0.000 description 3
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 231100000331 toxic Toxicity 0.000 description 3
- 230000002588 toxic effect Effects 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 229960000583 acetic acid Drugs 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 229910001593 boehmite Inorganic materials 0.000 description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000006477 desulfuration reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 235000003599 food sweetener Nutrition 0.000 description 2
- 239000012362 glacial acetic acid Substances 0.000 description 2
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 230000007096 poisonous effect Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 230000001603 reducing effect Effects 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- -1 sulphur compound Chemical class 0.000 description 2
- 239000003765 sweetening agent Substances 0.000 description 2
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 238000006424 Flood reaction Methods 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 230000004308 accommodation Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000008901 benefit Effects 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
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000012018 catalyst precursor Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- GIRSNHSKDRUFIG-UHFFFAOYSA-N hexane;methanedithione Chemical compound S=C=S.CCCCCC GIRSNHSKDRUFIG-UHFFFAOYSA-N 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 229910052622 kaolinite Inorganic materials 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Landscapes
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a Fischer-Tropsch catalyst containing zinc-cobalt base and a preparation method thereof. The catalyst comprises the following components in parts by weight: 10-30 parts of Co, 1-10 parts of Zn and 100 parts of Al2O3 and/or a SiO2 carrier; and more preferably, the catalyst comprises 15-25 parts of Co, 3-7 parts of Zn and 100 parts of Al2O3 and/or a SiO2 carrier. The catalyst has very good catalytic performance and feed gas sulfur content fluctuation resistance.
Description
Technical field
The present invention relates to a kind of containing zinc co-based fischer-tropsch Catalysts and its preparation method, especially relate to that a kind of Sulfur tolerance is enhanced containing zinc co-based fischer-tropsch Catalysts and its preparation method.
Background technology
Fischer-Tropsch synthesis refers to synthesis gas (H
2+ CO) under catalyst action, under uniform temperature and pressure, change into the reaction of hydrocarbon and other chemicals.In recent years, due to be becoming tight petroleum resources day and crude oil price continue soaring, F-T synthesis is subject to the extensive concern of countries in the world researcher.Usually, the available following reaction equation of reaction of F-T synthesis generation hydrocarbon represents:
mCO+(2m-1)H
2→C
mH
2m+2+mH
2O (1)
mCO+2mH
2→C
mH
2m+mH
2O (2)
2mCO+(m+1)H
2→C
mH
2m+2+mCO
2(3)
Fischer-Tropsch synthesis normally carries out in Fischer-Tropsch synthesis device, such reactor comprises the paste state bed reactor occurred fixed bed reactors, circulating fluid bed reactor, fixed fluidized-bed reactor and the nineties in last century, such as slurry bubble column reactor (SBCR).Because the reactors such as fixed bed are more expensive than paste state bed reactor, and be difficult to because Fischer-Tropsch synthesis is exothermic reaction control reaction temperature.So, paste state bed reactor more advantage more standby than other reacting appliances such as fixed beds.
The catalyst of dissimilar and different composition has different catalytic performances and the different reactor scope of application, such as, ferrum-based catalyst, especially precipitated iron catalyst or supported cobalt series catalysts are generally used in fixed bed reactors and paste state bed reactor, and fused iron catalyst is generally used in fluidized-bed reactor.
In Fischer-Tropsch synthesis and technique thereof, catalyst is one of its most important core technology, and therefore, for many years, people are devoted to the various fischer-tropsch synthetic catalysts of the excellent performance that R and D and reactor and reaction process match always.
Iron (Fe), cobalt (Co), nickel (Ni), ruthenium (Ru) are the main metal element of the active component that can be used as fischer-tropsch synthetic catalyst, and theoretical research for a long time and practical experience show: Fe and Co is the two kinds of metallic elements be worth as the most industrial applications of catalyst activity component.At present, fischer-tropsch synthetic catalyst general is in the world iron (Fe) series catalysts and the large system of cobalt (Co) series catalysts two mainly, wherein, iron (Fe) series catalysts Fischer-Tropsch synthetic distribution is wider, and cobalt (Co) series catalysts F-T synthesis is to C
5?C
25interval hydrocarbon product is selective higher.
Because cobalt (Co) metal price is expensive, so, how to improve the exploitation focus that the activity of cobalt (Co) series catalysts and stability are cobalt (Co) series catalysts always.The principal element affecting cobalt (Co) series catalysts activity has size and decentralization, the reduction degree etc. of catalyst crystal grain.And the principal element affecting cobalt (Co) series catalysts stability has mechanical strength, the water resistant thermal oxide ability and anti-poisoning capability etc. of catalyst.
In raising cobalt (Co) series catalysts is active, research shows, adds short reduction auxiliary agent in catalyst, and because of sintering, size increases in reduction activation process effectively can to avoid cobalt (Co) crystal grain, thus, the catalyst of high catalytic activity and high stability can be obtained.
In cobalt (Co) catalyst based stability, the catalyst based negative interaction by impurity toxic content of cobalt (Co) affects clearly, and especially, it can not the impurity such as sulfur-bearing and sulphur compound.Syntroleum company and Eastman Chemical company have studied the inactivation catalyst based to long-life cobalt (Co) of impurity poisonous substance in synthesis gas.First, selection impurity index is the synthesis gas of the commercialization gas purification technique process of 0, on this benchmark, carry out 10 times again and 100 times of impurity toxic content scale-ups compare, research finds: the increase of impurity toxic content causes the decline highly significant of cobalt (Co) catalyst based activity.(see Fischer Tropsch Catalyst Test on Coal ?Derived Synthesis Gas ?www.syntroleum.com ?White Paper Text Eastman), for the requirement of impurity poisonous substance sulphur minimum content in synthesis gas, the conclusion of different reactor and reaction different phase has a long way to go.Such as; Sasol requires that synthesis gas sulfur content can not, higher than 0.2ppm, and if will keep long-term steady running, also need sulfur content to be reduced to 0.02ppm (see Dry M.E. in fixed bed reactors; CatalysisToday; 2002,71,227; The F – T process:1950 – 2000); if paste state bed reactor, owing to there is not the condition of catalyst protection bed, in synthesis gas, sulfur content index should have lower restriction.
Containing H in crude synthesis gas
2s, CS
2, COS sulfides, so, synthesis gas needs through desulfuration purification before entering Fischer-Tropsch synthesis device, but 100% desulfurization can not be ensured, and because cobalt (Co) is catalyst based very responsive to sulfur content, the sulfur content fluctuation range allowed is very narrow, but the operation of upstream gas gasifying device and gas cleaning plant can not ensure that sulfur content fluctuates for a long time in very narrow scope.Therefore, the Sulfur tolerance how improving cobalt (Co) catalyst based is very important to the stable operation of F-T synthesis device.
The people such as Neil J.Coville (see Nobuntu N.Madikizela ?Mnqanqeni, Neil J.Coville.The preparation and study of sol – gel synthesized Co/Zn/TiO
2fischer – Tropschcatalysts.Applied Catalysis A:General 317 (2007) 195 – 203) result of study show: Zn, as a kind of catalyst promoter, can improve the catalytic activity of cobalt metal.The people such as Dragomir B.Bukura are (see Zhendong Pan, Dragomir B.Bukur.Fischer – Tropsch synthesis onCo/ZnO catalyst-Effect of pretreatment procedure.Applied Catalysis A:General404 (2011) 74 – 80) have studied with ZnO the reducing property of the Co/ZnO catalyst being carrier, result shows: ZnO or Zn is conducive to the reduction of Co, and this perhaps can be interpreted as the catalytic activity what Zn can improve cobalt metal.
In addition, Zn is a kind of widely used gas sweetening agent, has good binding ability with sulphur.The people such as NeilJ.Coville have studied Co/Zn/TiO
2the sulfur resistive ability of catalyst (see Nobuntu N.Madikizela ?Mnqanqeni, Neil J.Coville.The effect of sulfur addition during thepreparation of Co/Zn/TiO
2fischer – Tropsch catalysts.Applied Catalysis A:General340 (2008) 7 – 15), result shows: Co ?add Zn in TiO2 catalyst catalyst can be made to have the CO conversion ratio similar with not adding Zn catalyst.。
In addition, CN1245255C discloses a kind of Fischer-Tropsch synthetic iron-based catalyst and preparation method thereof, and the key component of this catalyst is Fe-Zn-Cu-K-SiO
2, this catalyst adopts coprecipitation Kaolinite Preparation of Catalyst precursor precipitate, and it is shaping to adopt spray drying process to carry out.Although containing Zn component in the catalyst disclosed in the document, because it is ferrum-based catalyst, there is not catalyst to the hypersusceptible problem of sulphur, so its introducing is not the Sulfur tolerance in order to improve catalyst.
CN102008960B discloses a kind of oxide carrier-loaded cobalt catalyst and preparation method thereof.In the publication, catalyst is with the Al through boric acid or borate modification
2o
3or SiO
2for carrier, carrier boracic 0.01-10 % by weight after process, carrier adopts infusion process load 10-35 % by weight cobalt, then introduces one or both metals of comprising in Mg, Ca, Ba, Ru, Zr, La, Ce and Pt as catalyst promoter by rear infusion process or co-impregnation.
CN102319569A discloses a kind of low-temperature reduction type Co based Fischer-Tropsch synthesis catalyst and preparation method thereof.In the publication, catalyst take ZnO as carrier, catalyst comprises: 3-15 % by weight Co and 85-97 % by weight ZnO, and this method for preparing catalyst comprises: first obtain ZnO porous carrier by coprecipitation, then loaded on ZnO porous carrier by active component Co by infusion process.This catalyst can reduce at low temperatures.
Above-mentioned document is introduced with for referencial use in full at this.
Cobalt (Co) base fischer-tropsch synthetic catalyst disclosed in above-mentioned prior art or be carrier with ZnO, specific surface area of catalyst is lower, is unfavorable for the dispersion of Co crystal grain, or not mentioned when unstripped gas sulfur content fluctuates, the change of catalyst performance.
The present invention is devoted to solve above-mentioned technical barrier, and strives developing or develop active and that Sulfur tolerance is all good cobalt (Co) base fischer-tropsch catalysts.
Summary of the invention
According to a first aspect of the invention, provide a kind of containing zinc co-based fischer-tropsch catalyst, with parts by weight, comprising: 10-30 part Co; 1-10 part Zn; With 100 parts of Al
2o
3and/or SiO
2carrier; More preferably, with parts by weight, comprising: 15-25 part Co; 3-7 part Zn; With 100 parts of Al
2o
3and/or SiO
2carrier, wherein, Co and Zn is present in the form of the oxide in catalyst before catalyst uses, and catalyst is reduced activation before use.
Described Al
2o
3and/or SiO
2porous carrier is prepared with the precipitation method, kneading method or sol-gal process, or be purchased.
According to a second aspect of the invention, a kind of above-mentioned preparation method containing zinc co-based fischer-tropsch catalyst is provided, comprises the following steps successively:
(1) by infusion process, coprecipitation or deposition-precipitation by the precursor load of catalyst promoter Zn at above-mentioned Al
2o
3and/or SiO
2on porous carrier;
(2) at the precursors decompose temperature of above-mentioned catalyst promoter Zn or on, the Al of the roasting precursor of drying and impregnation or deposit those catalyst promoter Zn
2o
3and/or SiO
2porous carrier;
(3) by infusion process, coprecipitation or deposition-precipitation by the precursor load of above-mentioned catalyst activity component Co at the Al that deposited above-mentioned catalyst promoter Zn
2o
3and/or SiO
2on porous carrier;
(4) under the decomposition temperature of the precursor of above-mentioned catalyst activity component Co or on, roasting drying and impregnation or deposited the Al of precursor of above-mentioned catalyst activity component Co
2o
3and/or SiO
2porous carrier, obtains above-mentioned Al
2o
3and/or SiO
2load containing zinc co-based fischer-tropsch catalyst,
Wherein, described dipping, deposition, drying and/or calcination steps are optionally repeatedly.
According to a third aspect of the invention we, reoffer a kind of above-mentioned preparation method containing zinc co-based fischer-tropsch catalyst, comprise the following steps successively:
(1) by infusion process, coprecipitation or deposition-precipitation by the precursor load of the precursor of catalyst activity component Co and catalyst promoter Zn at above-mentioned Al
2o
3and/or SiO
2on porous carrier;
(2) under the decomposition temperature of the precursor of above-mentioned catalyst activity component Co and/or the precursor of catalyst promoter Zn or on roasting drying and impregnation or deposited the Al of the precursor of above-mentioned catalyst activity component Co and the precursor of catalyst promoter Zn
2o
3and/or SiO
2porous carrier, obtains above-mentioned Al
2o
3and/or SiO
2load containing zinc co-based fischer-tropsch catalyst,
Wherein, described dipping, deposition, drying and/or calcination steps are optionally repeatedly.
According to of the present invention second and the third aspect, in the above-mentioned methods, the precursor of said Co and Zn is the nitrate of Co and Zn, chloride, carbonate, bicarbonate, sulfate, oxalates, formates, acetate and/or ammonium salt.
Detailed description of the invention
By being further explained in detail the present invention below with reference to the description of embodiment and accompanying drawing, but below describe only for enabling general technical staff of the technical field of the invention clearly understand principle of the present invention and marrow, and do not mean that any type of restriction is carried out to the present invention.
The present invention proposes a kind of containing zinc Co based Fischer-Tropsch synthesis catalyst and preparation method thereof, the activity of this catalyst and sulfur tolerance are all good.
As mentioned above; Zn and ZnO is a kind of widely used gas sweetening agent; itself and sulphur have good binding ability; if introduce a small amount of Zn and/or ZnO as catalyst aid in the Co based Fischer-Tropsch synthesis catalyst extremely responsive to sulfur content; not only can improve the reducing power of catalyst activity component Co; thus improve its catalytic activity; the more important thing is: Zn and/or ZnO is combined with sulphur; thus; protect the murder by poisoning of catalyst activity component Co from sulphur and sulfide, the most effectively improve the sulfur tolerance of catalyst.
The present invention is containing Al in zinc co-based fischer-tropsch catalyst
2o
3and/or SiO
2porous carrier can be prepared with the precipitation method or sol-gal process, or adopts the Al be purchased
2o
3and/or SiO
2porous carrier.Exemplarily property and nonrestrictive above-mentioned Al
2o
3and/or SiO
2the example of porous carrier preparation method is as described below:
A: the precipitation method prepare Al
2o
3porous carrier:
(1) first, certain density Al (NO is prepared
3)
3the aqueous solution;
(2) then, to Al (NO
3)
3ammoniacal liquor (precipitating reagent) is slowly dripped complete to precipitation in the aqueous solution, or by Al (NO
3)
3the aqueous solution adds in stillpot with ammoniacal liquor stream, and keeps pH value between 5-10;
(3) then, sedimentary solution left standstill ageing half an hour will be produced, then spend deionized water and filtration, afterwards, proceed in baking oven dry;
(4) last, in Muffle furnace or roaster at 500-900 DEG C roasting sediment 1-10 hour, obtain Al
2o
3porous carrier.
B: sol-gal process prepares Al
2o
3and/or SiO
2porous carrier:
(1) first, in container, add deionized water, aluminium isopropoxide and/or ethyl orthosilicate and absolute ethyl alcohol successively in proportion, stir simultaneously, and react 4-6 hour in 80-90 DEG C of water-bath, thus form the colloidal sol containing aluminium and/or silicon;
(2) subsequently, colloidal sol is put into drying box dry 5-6 hour at 80 DEG C, thus, form the xerogel containing aluminium and/or silicon;
(3) again by xerogel roasting 3-15 hour at 300-900 DEG C, Al is obtained
2o
3and/or SiO
2porous carrier.
C: kneading method prepares Al
2o
3and/or SiO
2porous carrier
(1) first, in proportion aluminium hydroxide dry powder and/or silicic acid dry powder are fully mixed;
(2) then, in said mixture, the mixture of acid or acid and the water accounting for said mixture 1-30 % by weight is slowly dripped, to make said mixture completely peptized;
(3) above-mentioned completely peptized mixture is carried out abundant kneading, kneading or pugging mullering, until mixture presents good plasticity;
(4) carry out extruded with extruder to said mixture, the mixture shape after shaping can be changed into granular, strip, bulk, sheet etc.;
(5) dry above-mentioned shaping mixture in 70-160 DEG C of drying baker or drying box;
(6) in roaster or Muffle furnace at 300-900 DEG C the above-mentioned drying composite 1-10 hour of roasting, obtain Al
2o
3and/or SiO
2porous carrier.
But above-mentioned aluminium hydroxide dry powder boehmite, pseudobochmite, boehmite or aluminum hydroxide solid elastomer powder; Above-mentioned silicic acid dry powder may also be dried Ludox, the mixture of above-mentioned acid or acid and water is actually peptizing agent, described acid can be inorganic acid or organic acid, such as, nitric acid, hydrochloric acid, glacial acetic acid and/or citric acid, different sour addition may be different, as nitric acid can be 1% ~ 30% of aluminium hydroxide weight, hydrochloric acid, glacial acetic acid and/or citric acid also can within the scope of these, as long as peptizing agent addition makes aluminium hydroxide dry powder and/or silicic acid dry powder and boric acid and/or boratory mixture completely peptized.The mixture of above-mentioned acid or acid and water can add simultaneously, also can separate or add in batches.
Above-mentioned Al
2o
3and/or SiO
2the precursor mixed solution containing zinc co-based fischer-tropsch catalyst useful catalyst auxiliary agent Zn and catalyst activity component Co of porous carrier load floods above-mentioned Al
2o
3and/or SiO
2prepared by the method for porous carrier, or use above-mentioned Al
2o
3and/or SiO
2prepared by the method that porous carrier powder adds through deposition-precipitation in the precursor mixed solution of catalyst promoter Zn and catalyst activity component Co, when adopting infusion process, the precursor of catalyst promoter Zn and catalyst activity component Co is immersed in above-mentioned Al by the mode of available total immersion stain or successively dipping
2o
3and/or SiO
2on porous carrier.Exemplarily property and the nonrestrictive above-mentioned example containing zinc co-based fischer-tropsch method for preparing catalyst is as described below:
D: infusion process (I) preparation is containing zinc co-based fischer-tropsch catalyst:
(1) Al first, will prepared by one of above-mentioned A-C method
2o
3and/or SiO
2porous carrier ZnO/Co
3o
4precursor composite solution, such as, the mixed solution dipping of zinc nitrate and cobalt nitrate, in maceration extract the water yield be the 1-3 of pore volume doubly;
(2) subsequently, by the Al after dipping
2o
3and/or SiO
2porous carrier puts into 80-140 DEG C of drying baker or the dry 4-12 hour of drying box;
(3) at above-mentioned ZnO/Co
3o
4precursors decompose temperature under or on, the such as Al of roasting after drying and impregnation at 350-450 DEG C
2o
3and/or SiO
2porous carrier 2-6 hour;
(4) above-mentioned dipping, drying and calcining step is repeated, until reach ZnO/Co
3o
4/ Al
2o
3and/or SiO
2required part by weight, thus, obtain above-mentioned containing zinc co-based fischer-tropsch catalyst.
E: infusion process (II) preparation is containing zinc co-based fischer-tropsch catalyst:
(1) Al first, will prepared by one of above-mentioned A-C method
2o
3and/or SiO
2porous carrier powder joins ZnO/Co in proportion
3o
4precursor composite solution, such as zinc nitrate and cobalt nitrate mixed solution in, and vigorous stirring, thus form uniform suspension;
(2) by after the suspension evaporating water of formation, drier 4-12 hour in 80-140 DEG C of drying baker or drying box is inserted;
(3) at above-mentioned ZnO/Co
3o
4precursor, such as zinc nitrate and/or cobalt nitrate decomposition temperature under or on, the such as dry and deposition ZnO/Co of roasting at 350-450 DEG C
3o
4the Al of precursor
2o
3and/or SiO
2porous carrier 2-6 hour, obtains above-mentioned containing zinc co-based fischer-tropsch catalyst.
F: deposition-precipitation preparation is containing zinc co-based fischer-tropsch catalyst:
(1) Al will prepared by one of above-mentioned A-C method
2o
3and/or SiO
2porous carrier powder joins ZnO/Co in proportion
3o
4precursor composite solution, such as zinc nitrate and cobalt nitrate mixed solution in, then, regulate solution pH value until form precipitated liquid by adding ammoniacal liquor;
(2) then, by solution left standstill ageing half an hour, then spend deionized water and filtration, dry, obtaining deposition sedimentation has ZnO/Co
3o
4the Al of precursor
2o
3and/or SiO
2porous carrier;
(3) deposition sedimentation there is ZnO/Co
3o
4the Al of precursor
2o
3and/or SiO
2porous carrier puts into 80-140 DEG C of drying baker or the dry 4-12 hour of drying box;
(4) under the decomposition temperature of the precursor of above-mentioned ZnO/CoO, such as zinc nitrate and/or cobalt nitrate or on, such as at 350-450 DEG C, the dry and deposition sedimentation of roasting has ZnO/Co
3o
4the Al of precursor
2o
3and/or SiO
2porous carrier, obtains above-mentioned containing zinc co-based fischer-tropsch catalyst.
Embodiment
Describe the present invention in more detail by following examples, but these specific embodiments are only demonstration and illustration purpose, they are not intended to limit the scope of the invention.
Following number or ratio are all parts by weight or part by weight, except as otherwise noted.
Embodiment 1: preparative chemistry consists of 1Zn/10Co/100SiO
2catalyst
(1) sol-gal process prepares SiO
2porous carrier
First, in container, add deionized water, ethyl orthosilicate and absolute ethyl alcohol successively, stir simultaneously, and react 6 hours in 85 DEG C of water-baths, thus form siliceous colloidal sol; Subsequently, colloidal sol is put into drying box at 80 DEG C dry 6 hours, thus, form siliceous xerogel; Again by xerogel roasting 9 hours at 650 DEG C, obtain SiO2 porous carrier, this porous carrier specific area is 200m
2/ g, pore volume is 0.8mL/g.
(2) preparation catalyst
49.5 grams of cobalt nitrate hexahydrates and 4.55 grams of zinc nitrate hexahydrates are dissolved in 68 ml deionized water, are made into the maceration extract of cobalt nitrate and zinc nitrate, take the SiO of 100 grams of preparations in above-mentioned steps (1)
2porous carrier, after maceration extract is mixed with porous carrier, drying 6 hours at 140 DEG C, obtain the intermediate of catalyst, described catalyst intermediate is put into 400 DEG C of Muffle furnace roastings 4 hours, obtained the present invention is containing zinc co-based fischer-tropsch catalyst, and this catalyst is marked as catalyst A.
Comparative example 1: preparative chemistry composition 10Co/100SiO
2catalyst
(1) sol-gal process prepares SiO
2porous carrier repeats the process of step (1) in embodiment 1.
(2) preparation catalyst
Except not adding except zinc nitrate hexahydrate, repeat the process of step (2) in embodiment 1, obtained co-based fischer-tropsch catalyst, this catalyst is marked as catalyst A-A.
Embodiment 2: preparative chemistry consists of 5Zn/20Co/100SiO
2catalyst
(1) sol-gal process prepares SiO
2porous carrier
First, in container, add deionized water, ethyl orthosilicate and absolute ethyl alcohol successively, stir simultaneously, and react 5 hours in 80 DEG C of water-baths, thus form siliceous colloidal sol; Subsequently, colloidal sol is put into drying box at 80 DEG C dry 6 hours, thus, form siliceous xerogel; Again by xerogel roasting 10 hours at 550 DEG C, obtain SiO2 porous carrier, this porous carrier specific area is 250m
2/ g, pore volume is 1.3mL/g.。
(2) preparation catalyst
99 grams of cobalt nitrate hexahydrates and 22.75 grams of zinc nitrate hexahydrates are dissolved in 241 ml deionized water, are made into the maceration extract of cobalt nitrate and zinc nitrate, take the SiO of 100 grams of preparations in above-mentioned steps (1)
2porous carrier, maceration extract is divided into two parts, make maceration extract at twice with porous carrier Homogeneous phase mixing, after each and porous carrier Homogeneous phase mixing of maceration extract, mixture all at 110 DEG C dry 8 hours, obtains catalyst intermediate, and the described catalyst intermediate obtained through twice impregnation drying is put into 425 DEG C of Muffle furnace roastings 3 hours, obtained the present invention is containing zinc co-based fischer-tropsch catalyst, and this catalyst is marked as catalyst B.
Embodiment 3: preparative chemistry consists of 9Zn/30Co/100SiO
2catalyst
(1) sol-gal process prepares SiO
2porous carrier
First, in container, add deionized water, ethyl orthosilicate and absolute ethyl alcohol successively, stir simultaneously, and react 4 hours in 85 DEG C of water-baths, thus form siliceous colloidal sol; Subsequently, colloidal sol is put into drying box at 80 DEG C dry 6 hours, thus, form siliceous xerogel; Again by xerogel roasting 10 hours at 500 DEG C, obtain SiO2 porous carrier, this porous carrier specific area is 300m
2/ g, pore volume is 1.8mL/g.
(2) preparation catalyst
148.5 grams of cobalt nitrate hexahydrates and 41 grams of zinc nitrate hexahydrates are dissolved in 524 ml deionized water, are made into the maceration extract of cobalt nitrate and zinc nitrate, take the SiO of 100 grams of preparations in above-mentioned steps (1)
2porous carrier, maceration extract is divided into three parts, maceration extract is divided three times and porous carrier Homogeneous phase mixing, after each and porous carrier Homogeneous phase mixing of maceration extract, mixture all at 80 DEG C dry 10 hours, obtains catalyst intermediate, and the described catalyst intermediate obtained through three impregnation dryings is put into 450 DEG C of Muffle furnace roastings 2 hours, obtained the present invention is containing zinc co-based fischer-tropsch catalyst, and this catalyst is marked as catalyst C.
Embodiment 4: preparative chemistry consists of 1Zn/10Co/100Al
2o
3catalyst
(1) sol-gal process prepares Al
2o
3porous carrier
First, in container, add deionized water, aluminium isopropoxide and absolute ethyl alcohol successively, stir simultaneously, and react 6 hours in 85 DEG C of water-baths, form the colloidal sol containing aluminium; Subsequently, colloidal sol is put into drying box at 80 DEG C dry 5 hours, form the xerogel containing aluminium; Again by xerogel roasting 8 hours at 650 DEG C, obtain Al
2o
3porous carrier, this porous carrier specific area is 150m
2/ g, pore volume is 0.5mL/g.
(2) preparation catalyst
49.5 grams of cobalt nitrate hexahydrates and 4.55 grams of zinc nitrate hexahydrates are dissolved in 35 ml deionized water, are made into the maceration extract of cobalt nitrate and zinc nitrate, take the Al of 100 grams of preparations in above-mentioned steps (1)
2o
3porous carrier, after maceration extract is mixed with porous carrier, drying 6 hours at 140 DEG C, obtain the intermediate of catalyst, described catalyst intermediate is put into 350 DEG C of Muffle furnace roastings 6 hours, obtained the present invention is containing zinc co-based fischer-tropsch catalyst, and this catalyst is marked as catalyst D.
Comparative example 4: preparative chemistry consists of the catalyst of 10Co/100ZnO
(1) preparation catalyst
49.5 grams of cobalt nitrate hexahydrates and 4.55 grams of zinc nitrate hexahydrates are dissolved in 35 ml deionized water, are made into the maceration extract of cobalt nitrate and zinc nitrate.Take ZnO (the Alfa Aesar that 100g is purchased, 99.99%), ZnO is joined in maceration extract, stir, make uniform suspension, then at 120 DEG C dry 15 hours, at 500 DEG C, roasting is obtained after 5 hours took ZnO as the co-based fischer-tropsch catalyst of carrier, and this catalyst is marked as catalyst D-D.
Embodiment 5: preparative chemistry consists of 5Zn/20Co/100Al
2o
3catalyst
(1) sol-gal process prepares Al
2o
3porous carrier
First, in container, add deionized water, aluminium isopropoxide and absolute ethyl alcohol successively, stir simultaneously, and react 4 hours in 80 DEG C of water-baths, form the colloidal sol containing aluminium; Subsequently, colloidal sol is put into drying box at 80 DEG C dry 5 hours, form the xerogel containing aluminium; Again by xerogel roasting 6 hours at 550 DEG C, obtain Al
2o
3porous carrier, this porous carrier specific area is 170m
2/ g, pore volume is 0.8mL/g.
(2) preparation catalyst
99 grams of cobalt nitrate hexahydrates and 22.75 grams of zinc nitrate hexahydrates are dissolved in 131 ml deionized water, are made into the maceration extract of cobalt nitrate and zinc nitrate, take the Al of 100 grams of preparations in above-mentioned steps (1)
2o
3porous carrier, maceration extract is divided into two parts, make maceration extract at twice with porous carrier Homogeneous phase mixing, after each and porous carrier Homogeneous phase mixing of maceration extract, mixture all at 110 DEG C dry 8 hours, obtains the intermediate of catalyst, and the described catalyst intermediate obtained through twice impregnation drying is put into 375 DEG C of Muffle furnace roastings 5 hours, obtained the present invention is containing zinc co-based fischer-tropsch catalyst, and this catalyst is marked as catalyst E.
Embodiment 6: preparative chemistry consists of 9Zn/30Co/100Al
2o
3catalyst
(1) sol-gal process prepares Al
2o
3porous carrier
First, in container, add deionized water, aluminium isopropoxide and absolute ethyl alcohol successively, stir simultaneously, and react 4 hours in 80 DEG C of water-baths, form the colloidal sol containing aluminium; Subsequently, colloidal sol is put into drying box at 80 DEG C dry 6 hours, form the xerogel containing aluminium; Again by xerogel roasting 6 hours at 450 DEG C, obtain Al
2o
3porous carrier, this porous carrier specific area is 200m
2/ g, pore volume is 1.0mL/g.
(2) preparation catalyst
148.5 grams of cobalt nitrate hexahydrates and 41 grams of zinc nitrate hexahydrates are dissolved in 260 ml deionized water, are made into the maceration extract of cobalt nitrate and zinc nitrate, take the Al of 100 grams of preparations in above-mentioned steps (1)
2o
3porous carrier, maceration extract is divided into three parts, maceration extract is divided three times and porous carrier Homogeneous phase mixing, after each and porous carrier Homogeneous phase mixing of maceration extract, mixture all at 80 DEG C dry 10 hours, obtains catalyst intermediate, and the described catalyst intermediate obtained through three impregnation dryings is put into 400 DEG C of Muffle furnace roastings 3 hours, obtained the present invention is containing zinc co-based fischer-tropsch catalyst, and this catalyst is marked as catalyst F.
Comparative example 6: preparative chemistry consists of 1Zn/10Co/100TiO
2catalyst
(1) sol-gal process prepares TiO
2porous carrier
First, in container, add deionized water, butyl titanate and absolute ethyl alcohol successively, stir simultaneously, and react 4 hours in 80 DEG C of water-baths, form the colloidal sol of titaniferous; Subsequently, colloidal sol is put into drying box at 80 DEG C dry 6 hours, form the xerogel of titaniferous; Again by xerogel roasting 6 hours at 450 DEG C, obtain TiO
2porous carrier, this porous carrier specific area is 40m
2/ g, pore volume is 0.5mL/g.
(2) preparation catalyst
49.5 grams of cobalt nitrate hexahydrates and 4.55 grams of zinc nitrate hexahydrates are dissolved in 105 ml deionized water, are made into the maceration extract of cobalt nitrate and zinc nitrate, take the TiO of 100 grams of preparations in above-mentioned steps (1)
2porous carrier, maceration extract is divided into three parts, maceration extract is divided three times and porous carrier Homogeneous phase mixing, after each and porous carrier Homogeneous phase mixing of maceration extract, mixture all at 80 DEG C dry 10 hours, obtain catalyst intermediate, the described catalyst intermediate obtained through three impregnation dryings is put into 400 DEG C of Muffle furnace roastings 3 hours, obtained with TiO
2for carrier containing zinc co-based fischer-tropsch catalyst, this catalyst is marked as catalyst F-F.
Test case 1
The sulfur tolerance of the catalyst in testing example 1-6, comparative example 1, comparative example 4 and comparative example 6.
Evaluation method: get 1.5g Catalyst packing and enter in fixed bed reactors, with the pure H of 10L/ (g-catalyst .h) flow
2in 400 DEG C, reduction after 10 hours under condition of normal pressure, at H
2: CO=2:1, gas flow is 5L/ (g-catalyst .h), pressure 2.0MPa, reacts under temperature 210 DEG C of conditions.When catalyst reaches stable state, and after the reaction time arrives 50 hours, the instantaneous carbon disulfide hexane solution adding different volumes in reaction gas, the instantaneous concentration of sulphur in reactor is made to reach 0.05ppm-5ppm respectively, and investigate the change of reaction time 50-80 hour inner catalyst performance, to investigate catalyst to the tolerance in synthesis gas during sulfur content fluctuation.
Evaluating catalyst under different sulfur content condition the results are shown in Table 1.The catalyst selected is: the catalyst in embodiment 1-6, comparative example 1, comparative example 4 and comparative example 6, its particle diameter is between 40 ~ 100 microns, and average grain diameter is about 80 microns.The Macroscopic physical architectural feature of catalyst is in table 2.
Adopt CO conversion ratio and the C of conventional method measurement or calculating fischer-tropsch reaction
5 +hydrocarbon-selective.Namely CO conversion ratio is determined by CO content in mensurated gas composition product; By measuring C
5 +the calculation of yield C of hydrocarbon
5 +hydrocarbon-selective.Experimental results represents in table 3 below.
Table 1
| Embodiment | Catalyst is numbered | Chemical composition (weight ratio) |
| 1 | A | 1Zn/10Co/100SiO 2 |
| Contrast 1 | A-A | 10Co/100SiO 2 |
| 2 | B | 5Zn/20Co/100SiO 2 |
| 3 | C | 9Zn/30Co/100SiO 2 |
| 4 | D | 1Zn/10Co/100Al 2O 3 |
| Contrast 4 | D-D | 10Co/100ZnO |
| 5 | E | 5Zn/20Co/100Al 2O 3 |
| 6 | F | 9Zn/30Co/100Al 2O 3 |
| Contrast 6 | F-F | 1Zn/10Co/100TiO 2 |
Table 2
Table 3
As can be known from Table 2: the present invention shows excellent sulfur tolerance containing zinc co-based fischer-tropsch catalyst A-F, when the sulfur content in synthesis gas is up to 5ppm, its CO conversion ratio and C
5 +hydrocarbon-selective is not affected, and this illustrates: the sulphur in synthesis gas does not poison catalyst of the present invention when 0.5-5ppm fluctuates.
The sulfur tolerance of the catalyst in comparing embodiment 1 and comparative example 1, comparative example 4, acquired results represents in the following Table 4.
Table 4
As can be seen from Table 4: catalyst A of the present invention (embodiment 1) is compared with existing catalyst A-A (comparative example 1), and Sulfur tolerance obtains great improvement; Catalyst A of the present invention is compared with existing catalyst C-C (comparative example 3), CO conversion ratio is extremely excellent, although existing catalyst C-C (comparative example 3) also has good Sulfur tolerance, but because the specific area of ZnO carrier is lower, make catalyst activity surface lower.So, the sulfur tolerance of comprehensive consideration catalyst and catalytic performance, Al of the present invention
2o
3and/or SiO
2the combination property containing zinc co-based fischer-tropsch catalyst of porous carrier load is best beyond doubt.
Therefore, in the balance of catalyst sulfur tolerance and catalytic performance, the present invention achieves beyond thought technique effect containing zinc co-based fischer-tropsch catalyst.
The term that this description is used and form of presentation are only used as descriptive and nonrestrictive term and form of presentation, are not intended to by any equivalents thereof exclude of the feature that represents and describe or its part outside when using these terms and form of presentation.
Although show and described several embodiment of the present invention, the present invention has not been restricted to described embodiment.On the contrary; those skilled in the art should recognize can carry out any accommodation and improvement to these embodiments when not departing from principle of the present invention and spirit, and protection scope of the present invention determined by appended claim and equivalent thereof.
Claims (6)
1., containing a zinc co-based fischer-tropsch catalyst, with parts by weight, comprising:
10-30 part Co;
1-10 part Zn; With
100 parts of Al
2o
3and/or SiO
2carrier,
Wherein, Co and Zn is present in the form of the oxide in catalyst before catalyst uses, and catalyst is reduced activation before use.
2. catalyst according to claim 1, with parts by weight, comprising:
15-25 part Co;
3-7 part Zn; With
100 parts of Al
2o
3and/or SiO
2carrier.
3. catalyst according to claim 1 and 2, wherein, Al
2o
3and/or SiO
2carrier be prepare with the precipitation method, kneading method or sol-gal process or be purchased.
4., according to one of any described preparation method containing zinc co-based fischer-tropsch catalyst of claim 1-3, comprise the following steps successively:
(1) by infusion process, coprecipitation or deposition-precipitation by the precursor load of catalyst promoter Zn at above-mentioned Al
2o
3and/or SiO
2on carrier;
(2) at the precursors decompose temperature of above-mentioned catalyst promoter Zn or on the Al of the roasting precursor of drying and impregnation or deposit those catalyst promoter Zn
2o
3and/or SiO
2carrier;
(3) by infusion process, coprecipitation or deposition-precipitation by the precursor load of above-mentioned catalyst activity component Co at the Al that deposited above-mentioned catalyst promoter Zn
2o
3and/or SiO
2on carrier;
(4) at the precursors decompose temperature of above-mentioned catalyst activity component Co or on roasting drying and impregnation or deposited the Al of above-mentioned catalyst activity component Co
2o
3and/or SiO
2carrier, obtains above-mentioned Al
2o
3and/or SiO
2load containing zinc co-based fischer-tropsch catalyst,
Wherein, described dipping, deposition, drying and/or calcination steps are optionally repeatedly.
5., according to one of any described preparation method containing zinc co-based fischer-tropsch catalyst of claim 1-3, comprise the following steps successively:
(1) by infusion process, coprecipitation or deposition-precipitation by the precursor load of the precursor of catalyst activity component Co and catalyst promoter Zn at above-mentioned Al
2o
3and/or SiO
2on carrier;
(2) under the decomposition temperature of the precursor of above-mentioned catalyst activity component Co and/or the precursor of catalyst promoter Zn or on roasting drying and impregnation or deposited the Al of the precursor of above-mentioned catalyst activity component Co and the precursor of catalyst promoter Zn
2o
3and/or SiO
2carrier, obtains above-mentioned Al
2o
3and/or SiO
2load containing zinc co-based fischer-tropsch catalyst,
Wherein, described dipping, deposition, drying and/or calcination steps are optionally repeatedly.
6. the method according to claim 4 or 5, wherein, said precursor is nitrate, chloride, carbonate, bicarbonate, sulfate, oxalates, formates, acetate and/or ammonium salt.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310191525.3A CN103272603B (en) | 2013-05-21 | 2013-05-21 | Fischer-Tropsch catalyst containing zinc-cobalt base and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310191525.3A CN103272603B (en) | 2013-05-21 | 2013-05-21 | Fischer-Tropsch catalyst containing zinc-cobalt base and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103272603A CN103272603A (en) | 2013-09-04 |
| CN103272603B true CN103272603B (en) | 2015-05-27 |
Family
ID=49055283
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310191525.3A Active CN103272603B (en) | 2013-05-21 | 2013-05-21 | Fischer-Tropsch catalyst containing zinc-cobalt base and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103272603B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103831115B (en) * | 2013-12-04 | 2016-04-20 | 中国科学院山西煤炭化学研究所 | Cobalt group catalyst synthesized and the method for making of syrup state bed Fischer Tropsch and application |
| CN105312092B (en) * | 2014-06-20 | 2019-01-08 | 中国石油化工股份有限公司 | A kind of catalyst and preparation method thereof and Fischer-Tropsch synthesis method |
| CN104815672B (en) * | 2014-12-19 | 2017-03-08 | 神华集团有限责任公司 | A kind of preparation method for using carbonic acid glyceride as the co-based fischer-tropsch catalyst of dispersant |
| CN105618052B (en) * | 2016-02-25 | 2018-09-21 | 中科潞安能源技术有限公司 | A kind of porous aluminium oxide loaded cobalt fischer-tropsch synthetic catalyst and preparation method and application |
| CN107159213B (en) * | 2017-05-12 | 2020-12-15 | 浙江工业大学 | For high H2Catalyst for synthesizing methane by using gas with/CO ratio and preparation method thereof |
| CN113797914A (en) * | 2021-09-28 | 2021-12-17 | 中国科学院山西煤炭化学研究所 | Catalyst for synthesizing ethylene carbonate, preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102441393A (en) * | 2010-10-12 | 2012-05-09 | 中国石油化工股份有限公司 | Fischer-Tropsch synthesis catalyst by taking modified alumina as carrier and application thereof |
| CN102671665A (en) * | 2012-05-22 | 2012-09-19 | 中国科学院山西煤炭化学研究所 | Co-based Fischer-Tropsch synthesis catalyst with high Co content, as well as preparation method and application thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB0704003D0 (en) * | 2007-03-01 | 2007-04-11 | Oxford Catalysts | Promoted carbide-based fischer-tropsch catalyst, method for its preparation and uses thereof |
-
2013
- 2013-05-21 CN CN201310191525.3A patent/CN103272603B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102441393A (en) * | 2010-10-12 | 2012-05-09 | 中国石油化工股份有限公司 | Fischer-Tropsch synthesis catalyst by taking modified alumina as carrier and application thereof |
| CN102671665A (en) * | 2012-05-22 | 2012-09-19 | 中国科学院山西煤炭化学研究所 | Co-based Fischer-Tropsch synthesis catalyst with high Co content, as well as preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103272603A (en) | 2013-09-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103272603B (en) | Fischer-Tropsch catalyst containing zinc-cobalt base and preparation method thereof | |
| CN103203237B (en) | Aluminum oxide loaded methanation catalyst | |
| CN102341170B (en) | Composition including a lanthanum perovskite on an alumina or aluminium oxyhydroxide substrate, preparation method and use in catalysis | |
| CN102333594A (en) | Catalysts | |
| CN104588023B (en) | Fischer-Tropsch synthesis catalyst, and preparation method and application thereof | |
| CN103962123A (en) | ZrO2-loaded sulfur-tolerant methanation catalyst and preparation method thereof | |
| CN104741133A (en) | Method for preparing cobalt-based Fischer-Tropsch catalyst by taking polyethylene glycol as dispersing agent | |
| Pieta et al. | CO2 hydrogenation to methane over Ni-catalysts: the effect of support and Vanadia promoting | |
| CN105817222A (en) | Preparation method and application of catalyst composition for hydrocarbon Fischer-Tropsch synthesis | |
| CN103191720A (en) | Magnesium aluminate spinel-supported sulphur-tolerant methanation catalyst | |
| Daneshmand-Jahromi et al. | Preparation of aerogel-supported copper oxide for the methane chemical looping combustion (CLC) process | |
| CN103785391B (en) | A kind of high activity fischer-tropsch synthetic catalyst and its preparation method and application | |
| CN103801287B (en) | A kind of preparation method of load type sulfur-tolerant methanation catalyst | |
| CN102233282A (en) | Fischer-Tropsch synthesis catalyst taking silicon oxide-aluminum oxide as carrier and application thereof | |
| Choya et al. | On the effect of the synthesis route of the support in Co3O4/CeO2 catalysts for the complete oxidation of methane | |
| CN105289632A (en) | Hydrocarbon oil desulfurization catalyst and preparation method thereof, and hydrocarbon oil desulfurization method | |
| CN103933966A (en) | Preparation method of supported sulphur-tolerant methanation catalyst | |
| CN106622276A (en) | Methane low-temperature combustion catalyst for boiling-bed reactor as well as preparation method and application of methane low-temperature combustion catalyst | |
| CN106955735A (en) | A kind of method of desulfurization of hydrocarbon oil catalyst and preparation method thereof and desulfurization of hydrocarbon oil | |
| CN102049259A (en) | Preparation method of cobalt-based catalyst for Fischer-Tropsch synthesis | |
| CN105879854B (en) | A kind of catalyst for methanation in presence of sulfur and its preparation method and application | |
| CN104511282A (en) | Desulfurization catalyst and preparation method thereof, and hydrocarbon oil desulfurization method | |
| CN104511308A (en) | Desulfurization catalyst, preparation method thereof and hydrocarbon oil desulfurizing method | |
| CN104511286A (en) | Desulfurization catalyst, preparation method thereof and hydrocarbon oil desulfurizing method | |
| CN104588022A (en) | High-activity Fischer-Tropsch synthesis catalyst, and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CP03 | Change of name, title or address | ||
| CP03 | Change of name, title or address |
Address after: No. 22, diazepam West Binhe Road, Dongcheng District, Beijing, Beijing Co-patentee after: National Institute of Clean and Low Carbon Energy Patentee after: National energy investment Refco Group Ltd Address before: 100011 Shenhua building 22, West Binhe Road, Dongcheng District, Beijing Co-patentee before: National Institute of Clean and Low Carbon Energy Patentee before: Shenhua Group LLC |
|
| CP01 | Change in the name or title of a patent holder | ||
| CP01 | Change in the name or title of a patent holder |
Address after: 100011 Beijing Dongcheng District, West Binhe Road, No. 22 Patentee after: CHINA ENERGY INVESTMENT Corp.,Ltd. Patentee after: Beijing low carbon clean energy research institute Address before: 100011 Beijing Dongcheng District, West Binhe Road, No. 22 Patentee before: CHINA ENERGY INVESTMENT Corp.,Ltd. Patentee before: Beijing low carbon clean energy research institute |