CN103586033A - Cobalt-based Fischer-Tropsch synthesis catalyst and preparation method and application thereof - Google Patents
Cobalt-based Fischer-Tropsch synthesis catalyst and preparation method and application thereof Download PDFInfo
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- CN103586033A CN103586033A CN201310529710.9A CN201310529710A CN103586033A CN 103586033 A CN103586033 A CN 103586033A CN 201310529710 A CN201310529710 A CN 201310529710A CN 103586033 A CN103586033 A CN 103586033A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 67
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 30
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 30
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 24
- 239000010941 cobalt Substances 0.000 title claims abstract description 24
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims description 24
- 239000002131 composite material Substances 0.000 claims abstract description 41
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 37
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 37
- 239000013078 crystal Substances 0.000 claims abstract description 23
- 229910052751 metal Inorganic materials 0.000 claims abstract description 13
- 239000002184 metal Substances 0.000 claims abstract description 13
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 11
- 150000003624 transition metals Chemical group 0.000 claims abstract description 11
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 7
- 150000001342 alkaline earth metals Chemical class 0.000 claims abstract description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000001301 oxygen Substances 0.000 claims abstract description 4
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 4
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 51
- 238000000034 method Methods 0.000 claims description 36
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 25
- 230000008569 process Effects 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 18
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 13
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 claims description 12
- 229910052799 carbon Inorganic materials 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 11
- 229910052700 potassium Inorganic materials 0.000 claims description 11
- 239000011591 potassium Substances 0.000 claims description 11
- 239000012752 auxiliary agent Substances 0.000 claims description 9
- 229910052742 iron Inorganic materials 0.000 claims description 9
- 229910021645 metal ion Inorganic materials 0.000 claims description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 8
- 239000008139 complexing agent Substances 0.000 claims description 7
- 238000001802 infusion Methods 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 230000009467 reduction Effects 0.000 claims description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 6
- 238000005245 sintering Methods 0.000 claims description 6
- 229910052726 zirconium Inorganic materials 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 4
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- 229910052788 barium Inorganic materials 0.000 claims description 4
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- 239000011651 chromium Substances 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 238000007598 dipping method Methods 0.000 claims description 4
- 238000001704 evaporation Methods 0.000 claims description 4
- 230000008020 evaporation Effects 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- 239000011733 molybdenum Substances 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- 229910052707 ruthenium Inorganic materials 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 239000010936 titanium Substances 0.000 claims description 4
- 229910052720 vanadium Inorganic materials 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- 229910052790 beryllium Inorganic materials 0.000 claims description 2
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 239000011575 calcium Substances 0.000 claims description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- 238000005470 impregnation Methods 0.000 claims description 2
- 238000011068 loading method Methods 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- DBRMBYFUMAFZOB-UHFFFAOYSA-N molybdenum nitric acid Chemical compound [Mo].[N+](=O)(O)[O-] DBRMBYFUMAFZOB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052705 radium Inorganic materials 0.000 claims description 2
- HCWPIIXVSYCSAN-UHFFFAOYSA-N radium atom Chemical compound [Ra] HCWPIIXVSYCSAN-UHFFFAOYSA-N 0.000 claims description 2
- 238000011084 recovery Methods 0.000 claims description 2
- 229910052712 strontium Inorganic materials 0.000 claims description 2
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract description 20
- 229930195733 hydrocarbon Natural products 0.000 abstract description 14
- 150000002430 hydrocarbons Chemical class 0.000 abstract description 14
- 239000007788 liquid Substances 0.000 abstract description 14
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- 239000000654 additive Substances 0.000 abstract description 2
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- 239000007789 gas Substances 0.000 description 14
- 239000000243 solution Substances 0.000 description 11
- 238000011156 evaluation Methods 0.000 description 8
- 239000000446 fuel Substances 0.000 description 8
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 8
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- 239000000047 product Substances 0.000 description 5
- 229910004298 SiO 2 Inorganic materials 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 4
- 239000002283 diesel fuel Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000009257 reactivity Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 229910004250 CaCoO Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
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- 229910000510 noble metal Inorganic materials 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
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- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 238000006424 Flood reaction Methods 0.000 description 1
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- YYLGKUPAFFKGRQ-UHFFFAOYSA-N dimethyldiethoxysilane Chemical compound CCO[Si](C)(C)OCC YYLGKUPAFFKGRQ-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses a cobalt-based Fischer Tropsch synthesis catalyst; the catalyst contains 70%-95%, preferably 85% above by weight of a composite metal oxide, and a metal additive; the composite metal oxide shows a cubic crystal form and has a structure formula of ABO3-y, wherein A is an alkaline earth metal, B is transition metals at least comprising cobalt, the mole content of the cobalt in the transition metals is higher than 75%, preferably higher than 80% , y is the mole number of oxygen vacancies existing in the composite oxide. The catalyst can improve a diesel fraction proportion in a liquid hydrocarbon product and reduce methane selectivity.
Description
Technical field
The present invention relates to a kind of Co based Fischer-Tropsch synthesis catalyst and its preparation method and application, relate in particular to and a kind ofly take synthesis gas as raw material, prepare the carbon atom concentrated Co based Fischer-Tropsch synthesis catalyst and its preparation method and application that distributes.
Background technology
Liquid fuel is the blood that modern society relies and turns round, and it is mainly produced by crude refining, processing.In recent years, owing to the worry of crude supply prospect having been caused to liquid fuel price continuous rise, a large amount of uses of liquid fuel simultaneously have also brought serious problem of environmental pollution, and setting up continuable clean fuel liquid production method is the effective means that solves above-mentioned two problems.Fischer-tropsch synthesis process refers to coal, natural gas, living beings etc. is first converted into synthesis gas (CO and H containing carbon resource
2mixture), then synthesis gas is polymerized on catalyst to the process of gaseous state, liquid state and solid hydrocarbons, synthesis gas polymerization process is below called as Fischer-Tropsch synthesis (Fischer-Tropsch Synthesis).The liquid hydrocarbon of the synthetic preparation of Fischer-Tropsch, after hydrogenation upgrading, has the identical character of liquid fuel of producing with petroleum refining.Due to the known reserves of coal, the natural gas reserves of verifying much larger than oil, living beings are a kind of reproducible resources, therefore fischer-tropsch synthesis process can be within the longer time for society provides the sufficient liquid fuel that gasoline and diesel oil etc. are representative of take, be the technology of desirable production petroleum replacing fuel.
Fischer-tropsch reaction carries out on catalyst, and the catalyst (high activity, high selectivity, high stability) with excellent properties is the technical guarantee that realizes efficient fischer-tropsch synthesis process.Catalyst activity is high, can improve the specific productivity of reaction unit, and selective height can improve the utilization rate of reaction raw materials, high running at full capacity, the minimizing non-normal stop that is conducive to maintain reaction unit of stability.To the middle discovery of studying for a long period of time of fischer-tropsch reaction: nickel, ruthenium, iron and cobalt have fischer-tropsch reaction activity.Nickel-base catalyst, under fischer-tropsch reaction condition, can produce too many methane, and the while self is easy to generate volatile carbonyl nickel and runs off from reactor, is difficult to realize commercial Application.Ruthenium is the most active known fischer-tropsch reaction catalyst, but its high price and limited reserves have hindered its use on industrial Fischer-Tropsch device, and it is generally to add in iron-based and cobalt-base catalyst, improve their reactivity worth with auxiliary agent form.Only have iron-based and cobalt-base catalyst to be successfully used in Fischer-Tropsch compound probability.Ferrum-based catalyst and cobalt-base catalyst have bigger difference in reactivity worth.
Ferrum-based catalyst can have very high reactivity, but research [Fuel 76 (1997) 273.] finds that the CO reacting is converted into CO with higher ratio along with CO conversion ratio raises
2rather than hydrocarbon, generate hydrocarbon selectively along with CO conversion ratio raises and decline.In order to obtain higher hydrocarbon productive rate, it is suitable to lower CO conversion per pass work that ferrum-based catalyst is considered to, by reaction end gas, loop secondary response mode and reach high CO total conversion (synthesis gas utilization rate) and high hydrocarbon-selective, but this working method has increased the workloads such as tail gas separation, gas circulation compression and corresponding energy consumption, and the gross efficiency that has limited fischer-tropsch synthesis process improves.
Forming what contrast with ferrum-based catalyst reactivity worth is cobalt-base catalyst, and it is less that its performance is subject to generate in fischer-tropsch reaction the impact of water, and because its water-gas shift activity is very weak, the CO in synthesis gas is converted into hydrocarbon.So, use the fischer-tropsch synthesis process of cobalt-base catalyst to work in high conversion per pass mode, can save the operation to reaction end gas compression cycle, shortened technological process, be conducive to improve the gross efficiency of fischer-tropsch synthesis process.
US6765026B2 discloses a kind of Fischer-Tropsch synthesis method that special catalyst carries out catalysis of applying.The catalyst precursor that the method adopts is the soluble compounds of a kind of iron group (especially cobalt) metal or soluble compounds or the salt of salt and platinum.Presoma is contacted with the solution of hydroxyhy-drocarbyl amines or ammonium hydroxide, obtain a kind of special catalyst, make C
5 +hydrocarbon selective reaches 58% ~ 80%.
CN101224430A has reported a kind of hydrophobic organic modification of Co group Fischer-Tropsch synthesized catalyst, and noble metal and cobalt load on silica supports, then carries out organically-modified.Wherein when noble metal adopts Pt, catalyst system 15%Co0.8%Pt/SiO
2, organically-modified reagent adopts dimethyldiethoxysilane modification, and on pressurization static bed, reaction condition is 230 ℃, 1.0MPa, 1000h
-1(V/V), H
2/ CO=3/1, the conversion ratio of CO is 72.7%.
CN200810039490.0 discloses a kind of for the synthetic precipitated ferrum-cobalt catalyst of Fischer-Tropsch, the composition of this catalyst comprises: elemental iron, element cobalt 2～50g/100gFe, Element Potassium 1～10g/100gFe and in the siliceous oxygen species 5～100g/100gFe of silica weight.Preparation method is for adding precipitating reagent the mixed solution of iron-containing liquor and cobalt-carrying solution, after precipitating aging 24h, washing and filtering, obtain the co-precipitation filter cake of iron content cobalt, deionized water is added in filter cake, making beating makes it even, under constantly at the uniform velocity stirring, add SiO 2 powder and potassium carbonate powder, or add SiO 2 powder and potassium silicate colloid, mix, obtained catalyst pulp is dry, roasting, obtain described precipitated ferrum-cobalt catalyst, and its weight ratio consists of Fe: Co: K: SiO
2=100: 2～50: 1～10: 5～100.The sintering temperature of described catalyst pulp is that 400～500 ℃, roasting time are 2～6 hours.The method has higher gas conversion ratio equally.
In sum, Co based Fischer-Tropsch synthesis catalyst is compared ferrum-based catalyst and so, at the conversion ratio of synthesis gas and reduce in carbon dioxide selective and there is obvious advantage, but in high conversion, also existing liquid hydrocarbon product distribution relatively disperses, the long paraffinic components of carbochain is on the high side, the problems such as the selective height of methane; Be unfavorable for follow-up processing and utilization, the solution of these problems can further improve application and the popularization of Co based Fischer-Tropsch synthesis catalyst.
Summary of the invention
For the deficiencies in the prior art, the present invention discloses a kind of Co based Fischer-Tropsch synthesis catalyst and its preparation method and application.This catalyst can improve diesel oil distillate in liquid hydrocarbon product ratio, reduce the selective of methane.
, composite metal oxide and metal promoter that described catalyst is 70%-95% by weight content form, and preferably contain more than 85% composite metal oxide; Described composite metal oxide is cubic-crystal and structural formula is ABO
3-y, wherein, A is alkaline-earth metal, and B is at least to comprise the transition metal of cobalt, and in transition metal, the molar content of cobalt is more than 75%, and preferably more than 80%, y is the molal quantity in the oxygen room that exists in composite oxides.
In Co based Fischer-Tropsch synthesis catalyst of the present invention, described alkaline-earth metal comprises one or more in beryllium, magnesium, calcium, strontium, barium, radium.The described transition metal that is at least cobalt comprises one or more in iron, nickel, manganese, copper, zinc, chromium, vanadium, titanium, molybdenum, zirconium except cobalt.Described auxiliary agent is various auxiliary agents used in prior art, comprises one or more in zirconium, potassium, ruthenium, platinum, nickel, manganese, copper, zinc, chromium, vanadium, titanium, molybdenum, zirconium.
In Co based Fischer-Tropsch synthesis catalyst of the present invention, described catalyst is by the composite metal oxide BaMo of cubic-crystal
1-xco
xo
3-y(wherein, 0.85<x< 0.95) and metal promoter potassium form.These composite oxides and potassium produce synergy and further improve diesel oil distillate in liquid hydrocarbon product.
A preparation method for Co based Fischer-Tropsch synthesis catalyst, comprises being cubic-crystal and structural formula is ABO
3-ythe preparation of composite metal oxide and the load of metal promoter.
In the inventive method, being cubic-crystal and structural formula is ABO
3-ycomposite metal oxide adopt complexometry, but be not limited to the method, allly in prior art can form cubic-crystal and structural formula is ABO
3-ycomposite metal oxide preparation method all can, but preferred complexometry.Described complexometry comprises following process: first by alkaline-earth metal with the presoma of transition metal that is at least cobalt with complexing agent mixing wiring solution-forming and stir; Then carry out moisture evaporation, solution is transformed into the gel of thickness by transparent colloidal sol; Final drying, roasting, make after roasting and have cubic-crystal and structural formula is ABO
3-ycomposition metal oxidation, namely there is the composite metal oxide of perovskite structure.The composite metal oxide BaMo that is cubic-crystal with preparation
1-xco
xo
3-y(0.85<x< 0.95) is example, specifically comprise following content: take barium nitrate, cobalt nitrate, nitric acid molybdenum is presoma, take citric acid or ethylene glycol as complexing agent, wiring solution-forming mixing and stirring, then carry out moisture evaporation, solution is transformed into the gel of thickness by transparent colloidal sol, final drying, roasting make BaMo after roasting
1-xco
xo
3-y(0.85<x< 0.95) composite metal oxide.
Above-mentioned complexometry preparation is cubic-crystal and structural formula is ABO
3-ycomposite metal oxide in, complexing agent and metal ion mol ratio are 1:1～8:1, are preferably 1:1～4:1.Preparation and agitating solution, at 20～90 ℃, are preferably at 50～70 ℃ and carry out.Stir speed (S.S.) is 200～500rpm, is preferably 300～400rpm.Mixing time is 3～8 hours, is preferably 4～6 hours.Baking temperature is 60～200 ℃, is preferably 80～150 ℃.Be 1～36 hour drying time, is preferably 8～24 hours.Sintering temperature is 600～1000 ℃, and roasting time is roasting 2 ~ 15 hours, is preferably at 700～900 ℃ roasting 3～8 hours.
In the inventive method, described metal promoter loading process adopts infusion process, incipient impregnation cross volume dipping, single-steeping or repeatedly dipping all can.For example there is the composite metal oxide BaMo of perovskite structure
1-xco
xo
3-y(0.85<x< 0.95) upper equi-volume impregnating carried metal auxiliary agent potassium that adopts.
A method of reducing for Co based Fischer-Tropsch synthesis catalyst, reduction temperature is 400～1000 ℃, preferred 500-700 ℃, the recovery time is 1-5h, reducing atmosphere is the low-carbon alkanes of hydrogen or C1-C3, preferably the latter.Adopt the CO hydrogenation catalyst of low-carbon alkanes reduction can reduce the selective of methane, improve the performance of catalyst.
The present invention adopt B position containing cobalt be cubic-crystal and structural formula is ABO
3-ycomposite metal oxide as fischer-tropsch synthetic catalyst, when keeping high conversion, improved the content of diesel oil distillate in liquid hydrocarbon product, reduce the selective of methane, solved in prior art the ubiquitous liquid hydrocarbon product carbon number of Co based Fischer-Tropsch synthesis catalyst high and distribute wide, the higher problem of methane selectively.The present invention has in the preparation process of composite metal oxide of perovskite structure, and the variation of preparation condition can have a strong impact on generation and the purity of perovskite structure.In all conditions are controlled, choosing of sintering temperature is vital, although it is more close with the present invention that some catalyst of the prior art forms, because the crystalline structure of constituent content and inherence is obviously different, so do not there is the premium properties of catalyst of the present invention.
Accompanying drawing explanation
Fig. 1 be the embodiment of the present invention 1 prepared be cubic-crystal and structural formula is BaCoO
3-ythe X-ray diffractogram of composite metal oxide.
The specific embodiment
Below in conjunction with embodiment, further illustrate process and the effect of the inventive method, but be not limited to following examples.
Embodiment 1
The mixed aqueous solution that preparation contains ferric nitrate and barium nitrate, is that 1.2:1 takes appropriate citric acid by metal ion total amount mol ratio in citric acid and mixed aqueous solution, in mixed aqueous solution, adds slowly citric acid, and stir on dropping limit, limit.Stir after 5 hours, brown solution has dewatered and has become thick gel, gel is taken out in the drying box of putting into 110 ℃ to dried overnight.Then take out dried predecessor, be placed in Muffle furnace constant temperature calcining 4 hours at 800 ℃, obtain having the composite metal oxide BaCoO of cubic-crystal
3-y, adopt infusion process at composite metal oxide BaCoO
3-ythe auxiliary agent potassium that upper load weight content is 10%, is dried 8 hours at 80 ℃, and in 350 ℃, roasting makes catalyst in 4 hours and is designated as C-1, and evaluation result is in Table 1.
Embodiment 2
The mixed aqueous solution that preparation contains calcium nitrate, manganese nitrate and barium nitrate, is that 2:1 takes appropriate citric acid by metal ion total amount mol ratio in citric acid and mixed aqueous solution, in mixed aqueous solution, adds slowly citric acid, and stir on dropping limit, limit.Stir after 5 hours, brown solution has dewatered and has become thick gel, gel is taken out in the drying box of putting into 110 ℃ to dried overnight.Then take out dried predecessor, be placed in Muffle furnace constant temperature calcining 6 hours at 700 ℃, obtain having the composite metal oxide CaCo of cubic-crystal
0.9mo
0.1o
3-y, adopt infusion process at composite metal oxide CaCo
0.9mo
0.1o
3-ythe potassium that upper load weight content is 10%, is dried 8 hours at 80 ℃, and in 350 ℃, roasting makes catalyst in 4 hours and is designated as C-2, and evaluation result is in Table 1.
Embodiment 3
The mixed aqueous solution that preparation contains barium nitrate, ferric nitrate and manganese nitrate, is that 2:1 takes appropriate citric acid by metal ion total amount mol ratio in citric acid and mixed aqueous solution, in mixed aqueous solution, adds slowly citric acid, and stir on dropping limit, limit.Stir after 5 hours, brown solution has dewatered and has become thick gel, gel is taken out in the drying box of putting into 110 ℃ to dried overnight.Then take out dried predecessor, be placed in Muffle furnace constant temperature calcining 6 hours at 700 ℃, obtain having the composite metal oxide BaCo of cubic-crystal
0.9mo
0.1o
3-y, adopt infusion process at composite metal oxide BaCo
0.9mo
0.1o
3-ythe potassium that upper load weight content is 10%, is dried 8 hours at 80 ℃, and in 350 ℃, roasting makes catalyst in 4 hours and is designated as C-3, and evaluation result is in Table 1.
Embodiment 4
The mixed aqueous solution that preparation contains barium nitrate, ferric nitrate and manganese nitrate, is that 4:1 takes appropriate citric acid by metal ion total amount mol ratio in citric acid and mixed aqueous solution, in mixed aqueous solution, adds slowly citric acid, and stir on dropping limit, limit.Stir after 5 hours, brown solution has dewatered and has become thick gel, gel is taken out in the drying box of putting into 110 ℃ to dried overnight.Then take out dried predecessor, be placed in Muffle furnace constant temperature calcining 8 hours at 600 ℃, obtain having the composite metal oxide BaMo of cubic-crystal
0.15co
0.85o
3-y, adopt infusion process at composite metal oxide BaMo
0.15co
0.85o
3-ythe auxiliary agent potassium that upper load weight content is 5%, is dried 8 hours at 80 ℃, and in 350 ℃, roasting makes catalyst C-4 in 4 hours, and evaluation result is in Table 1.
Embodiment 5
The mixed aqueous solution that preparation contains ferric nitrate, calcium nitrate, is that 3:1 takes appropriate citric acid by metal ion total amount mol ratio in citric acid and mixed aqueous solution, in mixed aqueous solution, adds slowly citric acid, and stir on dropping limit, limit.Stir after 5 hours, brown solution has dewatered and has become thick gel, gel is taken out in the drying box of putting into 110 ℃ to dried overnight.Then take out dried predecessor, be placed in Muffle furnace constant temperature calcining 5 hours at 1000 ℃, obtain having the composite metal oxide CaCoO of cubic-crystal
3-y, adopt infusion process at composite metal oxide CaCoO
3-ythe Cu additives that upper load weight content is 8%, is dried 8 hours at 80 ℃, and in 350 ℃, roasting makes catalyst in 4 hours and is designated as C-5, and evaluation result is in Table 1.
Comparative example 1
Adopt conventional coprecipitation to make the cobalt of non-perovskite structure, barium composite metal oxide, sintering temperature is 450 ℃, then floods auxiliary agent potassium, makes catalyst and is designated as B1, and in oxide, the weight content of barium, cobalt, potassium is with embodiment 1, and evaluation result is in Table 1.
Catalyst prepared by above-described embodiment and comparative example carries out activity rating, and evaluation test is carried out in high pressure CSTR, usings paraffin as solvent.First catalyst is reduced 5 hours, reduction temperature is 650 ℃, and wherein embodiment 3 adopts methane gas reduction, and all the other adopt hydrogen reducing.After reduction, catalyst is put into reactor and carried out Fischer-Tropsch synthesis, reaction actual conditions is 200 ℃, 1000h
-1, 2.0MPa, H
2/ CO=2(mol ratio).The operation result of 200h is conversion per pass in Table the conversion ratio of 1, CO.
Table 1 embodiment and comparative example fischer-tropsch synthetic catalyst evaluation result
Claims (15)
1. a Co based Fischer-Tropsch synthesis catalyst, is characterized in that: composite metal oxide and metal promoter that described catalyst is 70%-95% by weight content form; Described composite metal oxide is cubic-crystal and structural formula is ABO
3-y, wherein, A is alkaline-earth metal, and B is at least to comprise the transition metal of cobalt, and in transition metal, the molar content of cobalt is more than 75%, and y is the molal quantity in the oxygen room that exists in composite oxides.
2. catalyst according to claim 1, is characterized in that: the weight content of composite metal oxide is more than 85%; In transition metal, the molar content of cobalt is more than 80%.
3. catalyst according to claim 1, is characterized in that: described alkaline-earth metal comprises one or more in beryllium, magnesium, calcium, strontium, barium, radium.
4. catalyst according to claim 1, is characterized in that: the described transition metal that is at least cobalt comprises one or more in iron, nickel, manganese, copper, zinc, chromium, vanadium, titanium, molybdenum, zirconium except cobalt.
5. catalyst according to claim 1, is characterized in that: described auxiliary agent comprises one or more in zirconium, potassium, ruthenium, platinum, nickel, manganese, copper, zinc, chromium, vanadium, titanium, molybdenum, zirconium.
6. catalyst according to claim 1, is characterized in that: described catalyst is by the composite metal oxide BaMo of cubic-crystal
1-xco
xo
3-y(wherein, 0.85<x< 0.95) and metal promoter potassium form.
7. the preparation method of the arbitrary described catalyst of claim 1-6, is characterized in that: comprise being cubic-crystal and structural formula is ABO
3-ythe preparation of composite metal oxide and the load of metal promoter.
8. method according to claim 7, is characterized in that: being cubic-crystal structural formula is ABO
3-ycomposite metal oxide adopt complexometry, described complexometry comprises following process: first by alkaline-earth metal with the presoma of transition metal that is at least iron with complexing agent mixing wiring solution-forming and stir; Then carry out moisture evaporation, solution is transformed into the gel of thickness by transparent colloidal sol; Final drying, roasting, make after roasting and have cubic-crystal and structural formula is ABO
3-ycomposite metal oxide.
9. method according to claim 8, it is characterized in that: take barium nitrate, cobalt nitrate, nitric acid molybdenum is presoma, take citric acid or ethylene glycol as complexing agent, wiring solution-forming mixing and stirring, then carry out moisture evaporation, solution is transformed into the gel of thickness by transparent colloidal sol, final drying, roasting make the BaMo that is cubic-crystal after roasting
1-xco
xo
3-y(0.85<x< 0.95) composite metal oxide.
10. method according to claim 8, is characterized in that: complexing agent and metal ion mol ratio are 1:1～8:1; Preparation and agitating solution are at 20～90 ℃; Stir speed (S.S.) is 200～500rpm; Mixing time is 3～8 hours; Baking temperature is 60～200 ℃; Be 1～36 hour drying time; Sintering temperature is 600～1000 ℃, and roasting time is roasting 2 ~ 15 hours.
11. methods according to claim 10, is characterized in that: complexing agent and metal ion mol ratio are 1:1～4:1; Preparation and agitating solution carry out at 50～70 ℃; Stir speed (S.S.) is 300～400rpm; Mixing time is 4～6 hours; Baking temperature is 80～150 ℃; Be 8～24 hours drying time; Sintering temperature is 700～900 ℃, roasting time 3～8 hours.
12. methods according to claim 7, is characterized in that: described metal promoter loading process adopts infusion process, incipient impregnation cross volume dipping, single-steeping or repeatedly dipping all can.
13. methods according to claim 12, is characterized in that: be the BaMo of cubic-crystal
1-xco
xo
3-yon (0.85<x< 0.95) composite metal oxide, adopt equi-volume impregnating carried metal auxiliary agent K.
The method of reducing of the arbitrary described catalyst of 14. claim 1-6, is characterized in that: reduction temperature is 400～1000 ℃, and the recovery time is 1-5h, and reducing atmosphere is the low-carbon alkanes of hydrogen or C1-C3.
15. method of reducing according to claim 14, is characterized in that: reduction temperature is 500-700 ℃, the low-carbon alkanes that reducing atmosphere is C1-C3.
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| Title |
|---|
| 房玉真: "纳米钙钛矿催化剂用于CO加氢反应的研究", 《中国博士学位论文全文数据库 工程科技I辑》, no. 6, 15 June 2012 (2012-06-15) * |
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