CN103586033B - A kind of Co based Fischer-Tropsch synthesis catalyst and its preparation method and application - Google Patents
A kind of Co based Fischer-Tropsch synthesis catalyst and its preparation method and application Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 63
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 34
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims description 23
- 239000002131 composite material Substances 0.000 claims abstract description 37
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 34
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 34
- 239000013078 crystal Substances 0.000 claims abstract description 21
- 229910052751 metal Inorganic materials 0.000 claims abstract description 12
- 239000002184 metal Substances 0.000 claims abstract description 12
- 230000009467 reduction Effects 0.000 claims abstract description 9
- 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 34
- 230000008569 process Effects 0.000 claims description 19
- 238000001035 drying Methods 0.000 claims description 16
- 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
- 229910052700 potassium Inorganic materials 0.000 claims description 12
- 239000011591 potassium Substances 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 10
- 229910021645 metal ion Inorganic materials 0.000 claims description 8
- 239000012752 auxiliary agent Substances 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 238000001802 infusion Methods 0.000 claims description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- 239000008139 complexing agent Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 238000005245 sintering Methods 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 3
- 230000008020 evaporation Effects 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 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
- 238000011068 loading method Methods 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
- 238000011084 recovery Methods 0.000 claims description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract description 20
- 229910017052 cobalt Inorganic materials 0.000 abstract description 17
- 239000010941 cobalt Substances 0.000 abstract description 17
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 abstract description 15
- 239000007788 liquid Substances 0.000 abstract description 14
- 229930195733 hydrocarbon Natural products 0.000 abstract description 13
- 150000002430 hydrocarbons Chemical class 0.000 abstract description 13
- 239000004215 Carbon black (E152) Substances 0.000 abstract description 12
- 229910052723 transition metal Inorganic materials 0.000 abstract description 6
- 150000003624 transition metals Chemical class 0.000 abstract description 6
- 239000002283 diesel fuel Substances 0.000 abstract description 5
- 229910052784 alkaline earth metal Inorganic materials 0.000 abstract description 4
- 150000001342 alkaline earth metals Chemical class 0.000 abstract description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 3
- 239000001301 oxygen Substances 0.000 abstract description 3
- 229910052760 oxygen Inorganic materials 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 description 24
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 21
- 239000007864 aqueous solution Substances 0.000 description 15
- 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
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 7
- 229910052742 iron Inorganic materials 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 206010013786 Dry skin Diseases 0.000 description 5
- 238000001354 calcination Methods 0.000 description 5
- 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
- 230000009257 reactivity Effects 0.000 description 4
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 3
- 229910052788 barium Inorganic materials 0.000 description 3
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000005470 impregnation Methods 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
- 229910052759 nickel Inorganic materials 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 229910052707 ruthenium Inorganic materials 0.000 description 3
- 229910052726 zirconium Inorganic materials 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
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- 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
- 238000012545 processing Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000008279 sol Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000004111 Potassium silicate Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 238000010009 beating Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000012018 catalyst precursor Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- YYLGKUPAFFKGRQ-UHFFFAOYSA-N dimethyldiethoxysilane Chemical compound CCO[Si](C)(C)OCC YYLGKUPAFFKGRQ-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 230000000116 mitigating effect Effects 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 description 1
- 229910052913 potassium silicate Inorganic materials 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 229910052705 radium Inorganic materials 0.000 description 1
- HCWPIIXVSYCSAN-UHFFFAOYSA-N radium atom Chemical compound [Ra] HCWPIIXVSYCSAN-UHFFFAOYSA-N 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Abstract
The present invention discloses a kind of Co based Fischer-Tropsch synthesis catalyst, and described catalyst is that the composite metal oxide of 70%-95% and metal promoter form by weight content, preferably containing 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 the transition metal at least comprising cobalt, and in transition metal, the molar content of cobalt is more than 75%, and preferably more than 80%, y is the molal quantity of the Lacking oxygen existed in composite oxides.This catalyst can improve the ratio of diesel oil distillate in liquid hydrocarbon product, the selective of reduction methane.
Description
Technical field
The present invention relates to a kind of Co based Fischer-Tropsch synthesis catalyst and its preparation method and application, relating in particular to a kind of is raw material with synthesis gas, prepares concentrated Co based Fischer-Tropsch synthesis catalyst of carbon atom distribution and its preparation method and application.
Background technology
Liquid fuel is that modern society relies the blood of running, and it mainly to be produced by crude refining, processing.In recent years, owing to causing liquid fuel price continuous rise to the worry of crude supply prospect, a large amount of uses of liquid fuel simultaneously also bring serious problem of environmental pollution, and setting up continuable clean fuel liquid production method is the effective means solving above-mentioned two problems.Fischer-tropsch synthesis process refers to and 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 a catalyst the process of gaseous state, liquid state and solid hydrocarbons, synthesis gas polymerization process is below called as Fischer-Tropsch synthesis (Fischer-Tropsch Synthesis).Liquid hydrocarbon prepared by F-T synthesis, after hydrogenation upgrading, has the character identical with the liquid fuel that petroleum refining is produced.Because the known reserves of coal, natural gas verify reserves much larger than oil, living beings are a kind of reproducible resources, therefore fischer-tropsch synthesis process can, for society provides the sufficient liquid fuel being representative with gasoline and diesel oil etc. within the longer time, be the technology of desirable production petroleum replacing fuel.
Fischer-tropsch reaction carries out on a catalyst, and the catalyst (high activity, high selectivity, high stability) with excellent properties is the technical guarantee realizing 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, and stability is high is conducive to the running at full capacity, the minimizing non-normal stop that maintain reaction unit.Finding in the 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, self is easy to generate volatile carbonyl nickel and run off from reactor simultaneously, is difficult to realize commercial Application.Ruthenium is the most active known fischer-tropsch reaction catalyst, but its high price and limited reserves hinder its use on industrial Fischer Tropsch Facility, and it is generally add in iron-based and cobalt-base catalyst with auxiliary agent form, improve their reactivity worth.Iron-based and cobalt-base catalyst is only had to be used successfully in F-T synthesis industry.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 reacted is converted into CO with higher ratio along with CO conversion ratio raises
2instead of hydrocarbon, namely generate selective the rising along with CO conversion ratio of hydrocarbon and decline.In order to obtain higher Auditory steady-state responses, ferrum-based catalyst is considered to suitable to lower CO conversion per pass work, CO total conversion (synthesis gas utilization rate) that secondary response mode reaches high and high hydrocarbon-selective is carried out by reaction end gas circulation, but this working method adds workload and the corresponding energy consumption such as tail gas separation, gas circulation compression, and the gross efficiency limiting fischer-tropsch synthesis process improves.
Forming what contrast with ferrum-based catalyst reactivity worth is cobalt-base catalyst, and its performance is less by generating water mitigation in fischer-tropsch reaction, and because its water-gas shift activity is very weak, the CO in synthesis gas is mainly converted into hydrocarbon.So, use the fischer-tropsch synthesis process of cobalt-base catalyst can to work in high conversion per pass mode, the operation to reaction end gas compression cycle can be save, shorten technological process, be conducive to the gross efficiency improving fischer-tropsch synthesis process.
US6765026B2 discloses and a kind ofly applies the Fischer-Tropsch synthesis method that special catalyst carries out catalysis.The catalyst precursor that the method adopts is the soluble compounds of a kind of iron group (especially cobalt) metal or the soluble compounds of salt and platinum or salt.The solution of presoma with hydroxyhy-drocarbyl amines or ammonium hydroxide is contacted, obtains a kind of special catalyst, make C
5 +hydrocarbon selective reaches 58% ~ 80%.
CN101224430A reports 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 DEG C, 1.0MPa, 1000h
-1(V/V), H
2the conversion ratio of/CO=3/1, CO is 72.7%.
CN200810039490.0 discloses a kind of precipitated ferrum-cobalt catalyst for F-T synthesis, the composition of this catalyst comprises: elemental iron, element cobalt 2 ~ 50g/100gFe, Element Potassium 1 ~ 10g/100gFe and the siliceous oxygen species 5 ~ 100g/100gFe with silica weight.Preparation method is mixed solution precipitating reagent being added iron-containing liquor and cobalt-carrying solution, after aging 24h to be precipitated, 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, SiO 2 powder and potassium carbonate powder is added under constantly at the uniform velocity stirring, or add SiO 2 powder and potassium silicate colloid, mix, obtained catalyst pulp is dry, roasting, namely obtain described precipitated ferrum-cobalt catalyst, 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 400 ~ 500 DEG C, roasting time is 2 ~ 6 hours.The method has higher gas conversions equally.
In sum, Co based Fischer-Tropsch synthesis catalyst compares ferrum-based catalyst and so, synthesis gas conversion ratio and reduce carbon dioxide selective on there is obvious advantage, but while high conversion, also there is liquid hydrocarbon product distribution compare dispersion, 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 improve application and the popularization of Co based Fischer-Tropsch synthesis catalyst further.
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 the ratio of diesel oil distillate in liquid hydrocarbon product, the selective of reduction methane.
A kind of Co based Fischer-Tropsch synthesis catalyst, described catalyst is that the composite metal oxide of 70%-95% and metal promoter form by weight content, preferably containing 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 the transition metal at least comprising cobalt, and in transition metal, the molar content of cobalt is more than 75%, and preferably more than 80%, y is the molal quantity of the Lacking oxygen existed 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 being 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 to act synergistically and improve diesel oil distillate in liquid hydrocarbon product further.
A preparation method for Co based Fischer-Tropsch synthesis catalyst, comprises in cubic-crystal and structural formula is ABO
3-ythe preparation of composite metal oxide and the load of metal promoter.
In the inventive method, in 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-ythe preparation method of composite metal oxide, but preferred complexometry.Described complexometry comprises following process: first alkaline-earth metal and the presoma of transition metal being at least cobalt stirred with complexing agent mixing wiring solution-forming; Then carry out moisture evaporation, the colloidal sol of solution went from clear is transformed into the gel of thickness; Final drying, roasting, obtained after roasting have cubic-crystal and structural formula is ABO
3-ycomposition metal oxidation, namely there is the composite metal oxide of perovskite structure.With the composite metal oxide BaMo of preparation in cubic-crystal
1-xco
xo
3-y(0.85<x< 0.95) is example, specifically comprise following content: with barium nitrate, cobalt nitrate, nitric acid molybdenum for presoma, with citric acid or ethylene glycol for complexing agent, wiring solution-forming mixing and stirring, then moisture evaporation is carried out, the colloidal sol of solution went from clear is transformed into the gel of thickness, final drying, roasting, obtained BaMo after roasting
1-xco
xo
3-y(0.85<x< 0.95) composite metal oxide.
Above-mentioned complexometry preparation is in cubic-crystal and structural formula is ABO
3-ycomposite metal oxide in, complexing agent and metal ion mol ratio are 1:1 ~ 8:1, be preferably 1:1 ~ 4:1.Preparation and agitating solution, at 20 ~ 90 DEG C, carry out at being preferably 50 ~ 70 DEG C.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 DEG C, is preferably 80 ~ 150 DEG C.Drying time is 1 ~ 36 hour, is preferably 8 ~ 24 hours.Sintering temperature is 600 ~ 1000 DEG C, and roasting time is roasting 2 ~ 15 hours, is preferably roasting 3 ~ 8 hours at 700 ~ 900 DEG C.
In the inventive method, described metal promoter loading process adopts infusion process, incipient impregnation or cross volume impregnation, single-steeping or repeatedly flood.Such as there is the composite metal oxide BaMo of perovskite structure
1-xco
xo
3-y(0.85<x< 0.95) is upper adopts equi-volume impregnating carried metal auxiliary agent potassium.
A method of reducing for Co based Fischer-Tropsch synthesis catalyst, reduction temperature is 400 ~ 1000 DEG C, preferred 500-700 DEG C, and the recovery time is 1-5h, and reducing atmosphere is the low-carbon alkanes of hydrogen or C1-C3, preferred 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 in cubic-crystal and structural formula is ABO
3-ycomposite metal oxide as fischer-tropsch synthetic catalyst, the content of diesel oil distillate in liquid hydrocarbon product is improve while keeping high conversion, reduce the selective of methane, solve the high and problem that distribution is wide, methane selectively is higher of the ubiquitous liquid hydrocarbon product of Co based Fischer-Tropsch synthesis catalyst in prior art carbon number.The present invention has in the preparation process of the composite metal oxide of perovskite structure, and the change of preparation condition can have a strong impact on generation and the purity of perovskite structure.In all conditions control, choosing of sintering temperature is vital, although some catalyst composition of the prior art is more close with the present invention, because the crystalline structure of constituent content and inherence is obviously different, so do not have the premium properties of catalyst of the present invention.
Accompanying drawing explanation
Fig. 1 prepared by the embodiment of the present invention 1 in cubic-crystal and structural formula is BaCoO
3-ythe X-ray diffractogram of composite metal oxide.
Detailed description of the invention
Further illustrate process and the effect of the inventive method below in conjunction with embodiment, but be not limited to following examples.
Embodiment 1
Preparation contains the mixed aqueous solution of ferric nitrate and barium nitrate, is that 1.2:1 takes appropriate citric acid, in mixed aqueous solution, adds citric acid slowly by metal ion total amount mol ratio in citric acid and mixed aqueous solution, and dropping limit, limit is stirred.Stir after 5 hours, brown solution has dewatered and has become thick gel, is taken out by gel and puts in the drying box of 110 DEG C, dried overnight.Then take out dried predecessor, be placed in Muffle furnace constant temperature calcining 4 hours at 800 DEG C, obtain the composite metal oxide BaCoO with cubic-crystal
3-y, adopt infusion process at composite metal oxide BaCoO
3-yupper load weight content is the auxiliary agent potassium of 10%, and 80 DEG C of dryings 8 hours, in 350 DEG C, roasting 4 hours obtained catalyst were designated as C-1, and evaluation result is in table 1.
Embodiment 2
The mixed aqueous solution of preparation containing 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 citric acid slowly, and dropping limit, limit is stirred.Stir after 5 hours, brown solution has dewatered and has become thick gel, is taken out by gel and puts in the drying box of 110 DEG C, dried overnight.Then take out dried predecessor, be placed in Muffle furnace constant temperature calcining 6 hours at 700 DEG C, obtain the composite metal oxide CaCo with cubic-crystal
0.9mo
0.1o
3-y, adopt infusion process at composite metal oxide CaCo
0.9mo
0.1o
3-yupper load weight content is the potassium of 10%, and 80 DEG C of dryings 8 hours, in 350 DEG C, roasting 4 hours obtained catalyst were designated as C-2, and evaluation result is in table 1.
Embodiment 3
The mixed aqueous solution of preparation containing 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 citric acid slowly, and dropping limit, limit is stirred.Stir after 5 hours, brown solution has dewatered and has become thick gel, is taken out by gel and puts in the drying box of 110 DEG C, dried overnight.Then take out dried predecessor, be placed in Muffle furnace constant temperature calcining 6 hours at 700 DEG C, obtain the composite metal oxide BaCo with cubic-crystal
0.9mo
0.1o
3-y, adopt infusion process at composite metal oxide BaCo
0.9mo
0.1o
3-yupper load weight content is the potassium of 10%, and 80 DEG C of dryings 8 hours, in 350 DEG C, roasting 4 hours obtained catalyst were designated as C-3, and evaluation result is in table 1.
Embodiment 4
The mixed aqueous solution of preparation containing 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 citric acid slowly, and dropping limit, limit is stirred.Stir after 5 hours, brown solution has dewatered and has become thick gel, is taken out by gel and puts in the drying box of 110 DEG C, dried overnight.Then take out dried predecessor, be placed in Muffle furnace constant temperature calcining 8 hours at 600 DEG C, obtain the composite metal oxide BaMo with cubic-crystal
0.15co
0.85o
3-y, adopt infusion process at composite metal oxide BaMo
0.15co
0.85o
3-yupper load weight content is the auxiliary agent potassium of 5%, and 80 DEG C of dryings 8 hours, roasting 4 hours obtained catalyst C-4 in 350 DEG C, evaluation result was in table 1.
Embodiment 5
The mixed aqueous solution of preparation containing 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 citric acid slowly, and dropping limit, limit is stirred.Stir after 5 hours, brown solution has dewatered and has become thick gel, is taken out by gel and puts in the drying box of 110 DEG C, dried overnight.Then take out dried predecessor, be placed in Muffle furnace constant temperature calcining 5 hours at 1000 DEG C, obtain the composite metal oxide CaCoO with cubic-crystal
3-y, adopt infusion process at composite metal oxide CaCoO
3-yupper load weight content is the Cu additives of 8%, and 80 DEG C of dryings 8 hours, in 350 DEG C, roasting 4 hours obtained catalyst were designated as C-5, and evaluation result is in table 1.
Comparative example 1
Adopt conventional coprecipitation to obtain cobalt, the barium composite metal oxide of non-perovskite structure, sintering temperature is 450 DEG C, then impregnation aids potassium, and obtained catalyst 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.
Carry out activity rating to catalyst prepared by above-described embodiment and comparative example, evaluation test is carried out in high pressure CSTR, using paraffin as solvent.First carry out reduction 5 hours to catalyst, reduction temperature is 650 DEG C, and wherein embodiment 3 adopts methane gas to reduce, and all the other adopt hydrogen reducing.After reduction, catalyst is put into reactor and carry out Fischer-Tropsch synthesis, reaction actual conditions is 200 DEG C, 1000h
-1, 2.0MPa, H
2/ CO=2(mol ratio).The operation result of 200h is in table 1, and the conversion ratio of CO is conversion per pass.
Table 1 embodiment and comparative example fischer-tropsch synthetic catalyst evaluation result
Claims (9)
1. a Co based Fischer-Tropsch synthesis catalyst, is characterized in that: described catalyst is by the composite metal oxide BaMo in cubic-crystal
1-xco
xo
3-ywith metal promoter potassium composition, wherein 0.85<x< 0.95, the composite metal oxide BaMo of cubic-crystal in described catalyst
1-xco
xo
3-yweight content is 70%-95%.
2. the preparation method of catalyst described in claim 1, is characterized in that: comprise the composite metal oxide BaMo in cubic-crystal
1-xco
xo
3-ypreparation and the load of metal promoter potassium.
3. method according to claim 2, it is characterized in that: with barium nitrate, cobalt nitrate, nitric acid molybdenum for presoma, with citric acid or ethylene glycol for complexing agent, wiring solution-forming mixing and stirring, then moisture evaporation is carried out, the colloidal sol of solution went from clear is transformed into the gel of thickness, final drying, roasting, the obtained BaMo in cubic-crystal after roasting
1-xco
xo
3-ycomposite metal oxide.
4. method according to claim 3, is characterized in that: complexing agent and metal ion mol ratio are 1:1 ~ 8:1; Preparation and agitating solution are at 20 ~ 90 DEG C; Stir speed (S.S.) is 200 ~ 500rpm; Mixing time is 3 ~ 8 hours; Baking temperature is 60 ~ 200 DEG C; Drying time is 1 ~ 36 hour; Sintering temperature is 600 ~ 1000 DEG C, and roasting time is roasting 2 ~ 15 hours.
5. method according to claim 4, 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 DEG C; Stir speed (S.S.) is 300 ~ 400rpm; Mixing time is 4 ~ 6 hours; Baking temperature is 80 ~ 150 DEG C; Drying time is 8 ~ 24 hours; Sintering temperature is 700 ~ 900 DEG C, roasting time 3 ~ 8 hours.
6. method according to claim 2, is characterized in that: described metal promoter loading process adopts infusion process.
7. method according to claim 2, is characterized in that: at the BaMo in cubic-crystal
1-xco
xo
3-ycomposite metal oxide adopts equi-volume impregnating carried metal auxiliary agent K.
8. the method for reducing of catalyst described in claim 1, is characterized in that: reduction temperature is 400 ~ 1000 DEG C, and the recovery time is 1-5h, and reducing atmosphere is the low-carbon alkanes of hydrogen or C1-C3.
9. method of reducing according to claim 8, is characterized in that: reduction temperature is 500-700 DEG C, and reducing atmosphere is the low-carbon alkanes of C1-C3.
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