CN102000575A - Cobalt-based Fischertropsch synthesis catalyst for slurry-bed reactor, and preparation method and application thereof - Google Patents
Cobalt-based Fischertropsch synthesis catalyst for slurry-bed reactor, and preparation method and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 127
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 36
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title abstract description 15
- 239000010941 cobalt Substances 0.000 title abstract description 14
- 229910017052 cobalt Inorganic materials 0.000 title abstract description 14
- 239000002002 slurry Substances 0.000 claims abstract description 37
- 238000001556 precipitation Methods 0.000 claims abstract description 25
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 150000001868 cobalt Chemical class 0.000 claims abstract description 15
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 11
- 150000003624 transition metals Chemical class 0.000 claims abstract description 11
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 8
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052751 metal Inorganic materials 0.000 claims abstract description 5
- 239000002184 metal Substances 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 238000005299 abrasion Methods 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 24
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical group [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 22
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 22
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- 230000009467 reduction Effects 0.000 claims description 11
- 239000010953 base metal Substances 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 9
- 239000004005 microsphere Substances 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 8
- 230000001376 precipitating effect Effects 0.000 claims description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 239000004411 aluminium Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000003153 chemical reaction reagent Substances 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 3
- 239000001099 ammonium carbonate Substances 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 229940011182 cobalt acetate Drugs 0.000 claims description 3
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical group [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 101150003085 Pdcl gene Proteins 0.000 claims description 2
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- 238000000247 postprecipitation Methods 0.000 claims description 2
- 239000002244 precipitate Substances 0.000 claims description 2
- 229910052702 rhenium Inorganic materials 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- 239000007921 spray Substances 0.000 claims description 2
- 230000003068 static effect Effects 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 229910052684 Cerium Inorganic materials 0.000 claims 1
- 229910052719 titanium Inorganic materials 0.000 claims 1
- 238000005406 washing Methods 0.000 abstract description 9
- 239000012065 filter cake Substances 0.000 abstract description 4
- 239000012266 salt solution Substances 0.000 abstract description 4
- 239000012752 auxiliary agent Substances 0.000 abstract description 3
- 238000000975 co-precipitation Methods 0.000 abstract description 2
- 238000001914 filtration Methods 0.000 abstract description 2
- 239000000377 silicon dioxide Substances 0.000 abstract description 2
- 239000003513 alkali Substances 0.000 abstract 1
- 239000000969 carrier Substances 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- 238000004537 pulping Methods 0.000 abstract 1
- 238000005507 spraying Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 238000001694 spray drying Methods 0.000 description 14
- 238000005303 weighing Methods 0.000 description 14
- 239000007789 gas Substances 0.000 description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- -1 cobalt nitrate Chemical class 0.000 description 7
- 150000002431 hydrogen Chemical class 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 230000000704 physical effect Effects 0.000 description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 5
- 230000032683 aging Effects 0.000 description 5
- 229910021529 ammonia Inorganic materials 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- NGIISMJJMXRCCT-UHFFFAOYSA-N [Ru].[N+](=O)(O)[O-] Chemical compound [Ru].[N+](=O)(O)[O-] NGIISMJJMXRCCT-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 2
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- 238000010009 beating Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000012018 catalyst precursor Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- UJVRJBAUJYZFIX-UHFFFAOYSA-N nitric acid;oxozirconium Chemical compound [Zr]=O.O[N+]([O-])=O.O[N+]([O-])=O UJVRJBAUJYZFIX-UHFFFAOYSA-N 0.000 description 1
- 239000010412 oxide-supported catalyst Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000006188 syrup Substances 0.000 description 1
- 235000020357 syrup Nutrition 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
Abstract
The invention discloses a cobalt-based Fischertropsch synthesis catalyst for a slurry-bed reactor, and a preparation method and the application thereof. The cobalt-based Fischertropsch synthesis catalyst for the slurry-bed reactor comprises the following components based on weight ratio: 5.0-40.0% of Co metal, 0-2.0% of noble metal, 0-10% of non-noble metal in the transition metal, and 48-95% of carriers. The preparation method of the cobalt-based Fischertropsch synthesis catalyst comprises the following steps of: mixing cobalt salt solution with a soluble salt solution of auxiliary agent in the required proportion, adding alkali precipitant, washing and filtering the obtained precipitation slurry to obtain coprecipitation filter cake, directly adding silica/aluminum sol to the wet filter cake, pulping and uniformly mixing to obtain the slurry of catalyst, and finally spraying, drying and roasting to obtain microsphere-type slurry-bed Fischertropsch synthesis catalyst. The preparation method is simple, and the prepared catalyst has good sphericity, uniformly grain size distribution and high index of abrasion resistance; and the invention is suitable for Fischertropsch synthesis slurry-bed reactors.
Description
Technical field
The invention belongs to a kind of catalyst and preparation thereof and application, specifically be suitable for Co based Fischer-Tropsch synthesis catalyst and the preparation and the application of paste state bed reactor.
Technical background
The synthetic process that coal, natural gas or living beings is changed into hydro carbons through synthesis gas under catalyst action that is meant of Fischer-Tropsch.Can obtain numerous clean fuels and chemicals such as gasoline, produce oil, wax, naphtha, low-carbon alkene by this process, so its process is paid close attention to widely and is studied.Usually, the Fischer-Tropsch synthesis device adopts fixed bed reactors, fluidized-bed reaction and paste state bed reactor.Higher production efficiency, operation control realize easily because the reaction of slurry attitude bed has, the preparation production cost is low, are convenient to numerous advantages such as transportation installations, are the development trends of reactor technology and study the forward position in the world at present.Advantages such as the catalyst that Fischer-Tropsch synthesis adopts is divided into iron-based and cobalt-based two classes, and cobalt-base catalyst has high activity in course of reaction, low water gas shift reaction and become Fischer-Tropsch synthetic in the most rising catalyst.Therefore, the Co based Fischer-Tropsch synthesis catalyst that obtains to be suitable for paste state bed reactor will have great technological competitiveness and great commercial promise.
The research of cobalt-base catalyst has the history of nearly hundreds of years.Generally speaking, cobalt-base catalyst often with the cobalt salt direct impregnation on the indifferent oxide carrier, add second component again and be auxiliary agent to improve or fortifying catalytic agent performance.Catalyst precursor is by adding a small amount of different binding agents etc. so that final extruded moulding.As the leader of Co based Fischer-Tropsch synthesis catalyst research, Shell company has carried out broad research at cobalt-base catalyst.It is carrier that its research contents mainly adopts silica, and is that the drawback that solves its exposure has been carried out multiple modification.Yet the cobalt-base catalyst of Shell company is mainly used in fixed bed reactors, its catalyst preparation process and the required catalyst of incompatible slurry attitude bed.It is carrier that Exoon company adopts titanium oxide, at fixed bed and paste state bed reactor application numerous patents.But there is obvious drawback in its catalyst, and the cobalt load capacity of titanium dioxide carrier is low on the one hand, and its load capacity is lower than 15%; On the other hand, during titania oxide supported catalyst low-temperature bake, its anti-wear performance can not satisfy the requirement of slurry attitude bed.Though high-temperature roasting can improve catalyst strength, can cause strong metal-support interaction, influence catalyst performance.
Summary of the invention
Provide a kind of high activity during purpose of the present invention, be used for spherical Fischer-Tropsch synthesis cobalt-based catalyst and the preparation method and the application of paste state bed reactor.
The weight ratio of catalyst of the present invention consists of: the Co metal: 5.0～40.0%, and bullion content: 0～2.0%; Base metal in the transition metal: 0～10%, carrier is 48%-95%.
Aforesaid noble metal is Ru, Re, Pd etc.
Base metal is La, Zr, Ti, Ce etc. in the aforesaid transition metal.
Aforesaid carrier is SiO
2, Al
2O
3
Preparation method of the present invention mixes with the soluble-salt solution of auxiliary agent cobalt salt solution in required ratio, add the bases precipitating reagent then, to obtain the co-precipitation filter cake after the precipitation slurry washing filtration that obtain, Ludox or aluminium colloidal sol are directly added in the wet filter cake, and making beating mixes and makes catalyst pulp.At last, spray-dried, roasting, it is cobalt group catalyst synthesized to obtain the microspheroidal syrup state bed Fischer Tropsch.
Concrete preparation method of the present invention comprises the steps:
(1), consist of: the Co metal by the catalyst weight ratio: 5.0～40.0%, bullion content: 0～2.0%; Base metal in the transition metal: 0～10%, carrier is 48%～95%, and cobalt salt is joined in the deionized water, cobalt salt concentration is 0.5～5mol/L;
(2), by catalyst weight than forming, the base metal soluble-salt of noble metal, transition metal is joined in step (1) solution;
(3), will make the solution that concentration is 1～5mol/L in the bases precipitating reagent adding deionized water;
(4), above-mentioned two kinds of solution are joined in the settling vessel that band stirs jointly in 40～90 ℃, precipitate under pH value 7～10 conditions, precipitation finishes that the back is static wore out 1～6 hour, obtains precipitating slurry, washs to free from admixture;
(5), by catalyst weight than forming, be that the carrier colloidal sol of 10～40wt% mixes with post precipitation filter material and concentration, obtain solid content after mixing and be 10～60% catalyst pulp, be spray dried to microballoon cobalt-base catalyst powder then;
(6), obtain powder 300～600 ℃ of constant temperature calcining 3-10h in Muffle furnace, acquisition preformed catalyst.
Cobalt salt can be organic cobalt salt such as cobalt acetate as mentioned above, inorganic cobalt salt such as cobalt nitrate, preferred cobalt nitrate;
The soluble-salt of noble metal is RuCl as mentioned above
4, PdCl
4, H
2PtCl
4Deng soluble-salt, the base metal soluble-salt in the transition metal is La (NO
3)
3, Zr (NO
3)
4, TiCl
4, Ce (NO
3)
3Deng;
The bases precipitating reagent can be ammoniacal liquor, NaOH, sodium carbonate, ammonium carbonate etc. as mentioned above, preferred ammoniacal liquor;
Carrier colloidal sol is Ludox or aluminium colloidal sol as mentioned above, and the concentration of Ludox or aluminium colloidal sol is preferably 10～30%;
Spray-dired as mentioned above pressure is 1～10MPa, preferred 1.5～5MPa; 200～350 ℃ of inlet temperatures, preferred 255～320 ℃, 60～170 ℃ of outlet temperatures, preferred 80～130 ℃
The catalyst that the present invention makes, wherein the particle of microsphere diameter 50～180 mu m ranges reaches more than 95%, and abrasion index is 1～2% hour
-1, specific area is 100～300m
2/ g.
The prepared catalyst of the present invention is used pure hydrogen reduction in fixed bed, the stirring-type paste state bed reactor is adopted in reaction.The catalyst reduction condition is: 250～500 ℃, and 0.2～1.2MPa, volume space velocity 500～2500h
-1, constant temperature 6～24h; Reaction condition is, 190～250 ℃, and 0.5～5.0MPa, volume space velocity 500～3000h
-1, speed of agitator is 400～1400rpm, H
2: the CO mol ratio is 1～3: 1.
The invention has the advantages that:
(1) method for preparing catalyst is simple, and the catalyst spherical degree that obtains is good, and particle diameter is evenly distributed, and the index height that resistance to wears is suitable for Fischer-Tropsch synthetic pulp state bed reactor, and the operating condition gentleness (reaction condition is, 190～250 ℃, and 0.5～5.0MPa).
(2) this catalyst can obtain high capacity amount active specy, the catalyst activity height, and selectivity is good.Methane selectively is lower than 7% in the Fischer-Tropsch synthetic, and the C5+ selectivity is higher than 85%.
(3) catalyst is beneficial to catalyst and separates long service life with product in slurry attitude bed.
The specific embodiment
Following embodiment will the present invention is described further, and protection scope of the present invention is not subjected to the restriction of these embodiment.
Embodiment 1
Preparation of Catalyst: weight content 15wt% in final catalyst takes by weighing cobalt nitrate by simple substance cobalt, adds the cobalt nitrate solution that deionized water is mixed with concentration 1L/mol.Prepare the ammonia spirit of 5L/mol simultaneously, above-mentioned two kinds of solution are added in the precipitation reactor under 40 ℃ of stirring conditions of heating simultaneously, control precipitation pH value is 7.5.Wore out 1 hour after precipitation is finished, after the material washing, the Ludox of getting 10 (wt) % content according to the final vector contg of catalyst evenly mixes the spray-drying slurry that obtains 10% solid content with above-mentioned slurries.The spray-drying condition is as follows: 350 ℃ of slurry inlet temperatures, 170 ℃ of outlet temperatures; Pressure 10MPa.Thus obtained microsphere 300 ℃ of roastings 10 hours in Muffle furnace obtain catalyst.Final catalyst weight is: Co: SiO
2=15: 85.The catalyst physical property sees Table 1.
Get above-mentioned catalyst 20g and reduce in fixed bed with pure hydrogen, reducing condition is, 250 ℃, and 0.2MPa, 500h
-1(V/V), constant temperature 6h.Adopt nitrogen protection after reduction finishes, catalyst is transferred in the 1L slurry attitude bed stirred tank that the 500ml atoleine is housed, change synthesis gas into and react, reaction condition is 190 ℃, 0.5MPa, 1200h
-1(V/V), 700rpm, H
2/ CO (mol)=1/1.Reaction result sees Table 2.
Embodiment 2
Preparation of catalysts: weight content 20wt% in final catalyst takes by weighing cobalt nitrate by simple substance cobalt, adds the cobalt nitrate solution of deionized water compound concentration 0.5L/mol, and content is that 3wt% takes by weighing lanthanum nitrate and is added in the cobalt nitrate solution by weight simultaneously.Prepare the ammonia spirit of 1L/mol simultaneously, above-mentioned two kinds of solution are added in the precipitation reactor under 90 ℃ of stirring conditions simultaneously, control precipitation pH value is about 10.Wore out 6 hours after precipitation is finished, the Ludox that 30 (wt) % content is got according to the final vector contg of catalyst in material washing back evenly mixes the spray-drying slurry that obtains solid content 60% with above-mentioned slurries.The spray-drying condition is as follows: 200 ℃ of slurry inlet temperatures, 60 ℃ of outlet temperatures; Pressure 1MPa.Thus obtained microsphere 600 ℃ of roastings 3 hours in Muffle furnace obtain catalyst.Final catalyst weight is: Co: La: SiO
2=20: 3: 77.The catalyst physical property sees Table 1.
Get above-mentioned catalyst 20g and reduce in fixed bed with pure hydrogen, reducing condition is, 500 ℃, and 1.2MPa, 2500h
-1(V/V), constant temperature 12h.Under the nitrogen protection, catalyst is transferred in the 1L slurry attitude bed stirred tank that the 500ml atoleine is housed after reduction finishes, switched to synthesis gas and react, reaction condition is 250 ℃, 5.0MPa, 3000h
-1(V/V), 1400rpm, H
2/ CO (mol)=3/1.Reaction result sees Table 2.
Embodiment 3
Preparation of catalysts: weight content 40wt% in final catalyst takes by weighing cobalt nitrate by simple substance cobalt, adds the cobalt nitrate solution of deionized water compound concentration 0.5L/mol, and content 10wt% takes by weighing cerous nitrate and is added in the cobalt nitrate solution by weight.Prepare the ammonia spirit of 5L/mol simultaneously, above-mentioned two kinds of solution are added in the precipitation reactor under 80 ℃ of stirring conditions simultaneously, control precipitation pH value is about 9.Precipitation was finished aging 4 hours, and the Ludox that 20 (wt) % content is got according to the final vector contg of catalyst in material washing back evenly mixes the spray-drying slurry that obtains solid content 40% with above-mentioned slurries.The spray-drying condition is as follows: 300 ℃ of slurry inlet temperatures, 100 ℃ of outlet temperatures; Pressure 3MPa.Thus obtained microsphere 350 ℃ of roastings 4 hours in Muffle furnace obtain catalyst.Final catalyst weight is: Co: La: SiO
2=40: 10: 50.The catalyst physical property sees Table 1.
Get above-mentioned catalyst 20g and reduce in fixed bed with pure hydrogen, reducing condition is, 350 ℃, and 0.2MPa, 1500h
-1(V/V), 500rpm, 12h.Under the nitrogen protection, catalyst is transferred in the 1L slurry attitude bed stirred tank that the 500ml atoleine is housed after reduction finishes, switched to synthesis gas and react, reaction condition is 210 ℃, 2.0MPa, 1500h
-1(V/V), 1000rpm, H
2/ CO (mol)=2/1.Reaction result sees Table 2.
Embodiment 4
Preparation of catalysts: weight content 5wt% in final catalyst takes by weighing cobalt acetate by simple substance cobalt, adds the cobalt nitrate solution of deionized water compound concentration 5L/mol, and content 0.5wt% takes by weighing the nitric acid ruthenium and is added in the cobalt nitrate solution by weight.Prepare the ammonia spirit of 2L/mol simultaneously, above-mentioned two kinds of solution are added in the precipitation reactor under 70 ℃ of stirring conditions simultaneously, control precipitation pH value is about 8.Precipitation was finished aging 2 hours, and the Ludox that 30 (wt) % content is got according to the final vector contg of catalyst in material washing back evenly mixes the spray-drying slurry that obtains solid content 40% with above-mentioned slurries.The spray-drying condition is as follows: 250 ℃ of slurry inlet temperatures, 80 ℃ of outlet temperatures; Pressure 2.5MPa.Thus obtained microsphere 500 ℃ of roastings 6 hours in Muffle furnace obtain catalyst.Final catalyst weight is: Co: Ru: SiO
2=5: 0.5: 94.5.The catalyst physical property sees Table 1.
Get above-mentioned catalyst 20g and reduce in fixed bed with pure hydrogen, reducing condition is, 400 ℃, and 1.20MPa, 1000h
-1(V/V), constant temperature 12h.Under the nitrogen protection, catalyst is transferred in the 1L slurry attitude bed stirred tank that the 500ml atoleine is housed after reduction finishes, switched to synthesis gas and react, reaction condition is 230 ℃, 2.0MPa, 2000h
-1(V/V), 800rpm, H
2/ CO (mol)=2/1.Reaction result sees Table 2.
Embodiment 5
Preparation of catalysts: weight content 35wt% in final catalyst takes by weighing cobalt nitrate by simple substance cobalt, adds the cobalt nitrate solution of deionized water compound concentration 2L/mol, and content 5wt% takes by weighing zirconium nitrate and is added in the cobalt nitrate solution by weight.Prepare the sodium hydrate aqueous solution of 1L/mol simultaneously, above-mentioned two kinds of solution are added in the precipitation reactor under 50 ℃ of stirring conditions simultaneously, control precipitation pH value is about 8.Precipitation was finished aging 6 hours, and the Ludox that 15 (wt) % content is got according to the final vector contg of catalyst in material washing back evenly mixes the spray-drying slurry that obtains solid content 10% with above-mentioned slurry.The spray-drying condition is as follows: 270 ℃ of slurry inlet temperatures, 130 ℃ of outlet temperatures; Pressure 4.5MPa.Thus obtained microsphere 450 ℃ of roastings 8 hours in Muffle furnace obtain catalyst.Final catalyst weight is: Co: Zr: SiO
2=35: 5: 60.The catalyst physical property sees Table 1.
Get above-mentioned catalyst 20g and reduce in fixed bed with pure hydrogen, reducing condition is, 380 ℃, and 0.5MPa, 1000h
-1(V/V), constant temperature 20h.Under the nitrogen protection, catalyst is transferred in the 1L slurry attitude bed stirred tank that the 500ml atoleine is housed after reduction finishes, switched to synthesis gas and react, reaction condition is 220 ℃, 2.5MPa, 2000h
-1(V/V), 800rpm, H
2/ CO (mol)=2/1.Reaction result sees Table 2.
Embodiment 6
Preparation of catalysts: weight content 20wt% in final catalyst takes by weighing cobalt nitrate by simple substance cobalt, add the cobalt nitrate solution of deionized water compound concentration 2L/mol, content 5wt% takes by weighing zirconyl nitrate and 0.2wt% and takes by weighing palladium bichloride and be added in the cobalt nitrate solution by weight.Prepare the ammonium bicarbonate aqueous solution of 1L/mol simultaneously, above-mentioned two kinds of solution are added in the precipitation reactor under 50 ℃ of temperature stirring conditions simultaneously, control precipitation pH value is about 7.Precipitation was finished aging 3 hours, and the Ludox that 20 (wt) % content is got according to the final vector contg of catalyst in material washing back evenly mixes the spray-drying slurry that obtains solid content 25% with above-mentioned slurries.The spray-drying condition is as follows: 320 ℃ of slurry inlet temperatures, 120 ℃ of outlet temperatures; Pressure 2MPa.Thus obtained microsphere 400 ℃ of roastings 10 hours in Muffle furnace obtain catalyst.Final catalyst weight is: Co: Pd: Zr: SiO
2=20: 0.2: 5: 74.8.The catalyst physical property sees Table 1.
Get above-mentioned catalyst 20g and reduce in fixed bed with pure hydrogen, reducing condition is, 300 ℃, and 1.5MPa, 1000h
-1(V/V), constant temperature 16h.Under the nitrogen protection, catalyst is transferred in the 1L slurry attitude bed stirred tank that the 500ml atoleine is housed after reduction finishes, switched to synthesis gas and react, reaction condition is 210 ℃, 3.0MPa, 2000h
-1(V/V), 800rpm, H
2/ CO (mol)=1/1.Reaction result sees Table 2.
Embodiment 7
Preparation of catalysts: weight content 40wt% in final catalyst takes by weighing cobalt nitrate by simple substance cobalt, adds the cobalt nitrate solution of deionized water compound concentration 3L/mol, and content 0.2wt% takes by weighing the nitric acid ruthenium and is added in the cobalt nitrate solution by weight.Prepare the aqueous sodium carbonate of 1L/mol simultaneously, above-mentioned two kinds of solution are added in the precipitation reactor under 70 ℃ of temperature stirring conditions simultaneously, control precipitation pH value is about 7.Precipitation was finished aging 3 hours, and the aluminium colloidal sol that 30 (wt) % content is got according to the final vector contg of catalyst in material washing back evenly mixes the spray-drying slurry that obtains solid content 50% with above-mentioned slurries.The spray-drying condition is as follows: 350 ℃ of slurry inlet temperatures, 130 ℃ of outlet temperatures; Pressure 5MPa.Thus obtained microsphere 350 ℃ of roastings 3 hours in Muffle furnace obtain catalyst.Final catalyst weight is: Co: Ru: Al
2O
3=40: 0.2: 54.8.The catalyst physical property sees Table 1.
Get above-mentioned catalyst 20g and reduce in fixed bed with pure hydrogen, reducing condition is, 450 ℃, and 1.5MPa, 2000h
-1(V/V), constant temperature 10h.Under the nitrogen protection, catalyst is transferred in the 1L slurry attitude bed stirred tank that the 500ml atoleine is housed after reduction finishes, switched to synthesis gas and react, reaction condition is 210 ℃, 3.0MPa, 2000h
-1(V/V), 800rpm, H
2/ CO (mol)=2/1.Reaction result sees Table 2.
Table 1 catalyst particle size distributes
Table 2 catalyst reaction result
Claims (15)
1. Co based Fischer-Tropsch synthesis catalyst that is used for paste state bed reactor is characterized in that the weight ratio of catalyst consists of: the Co metal: 5.0～40.0%, and bullion content: 0～2.0%; Base metal in the transition metal: 0～10%, carrier is 48%～95%.
2. a kind of Co based Fischer-Tropsch synthesis catalyst that is used for paste state bed reactor as claimed in claim 1 is characterized in that described noble metal is Ru, Re or Pd.
3. a kind of Co based Fischer-Tropsch synthesis catalyst that is used for paste state bed reactor as claimed in claim 1 is characterized in that base metal is La, Zr, Ti or Ce in the described transition metal.
4. a kind of Co based Fischer-Tropsch synthesis catalyst that is used for paste state bed reactor as claimed in claim 1 is characterized in that described carrier is SiO
2Or Al
2O
3
5. a kind of Co based Fischer-Tropsch synthesis catalyst that is used for paste state bed reactor as claimed in claim 1 is characterized in that the particle of microsphere diameter 50～180 mu m ranges in the described catalyst reaches more than 95%, and abrasion index is 1～2% hour
-1, specific area is 100～300m
2/ g.
6. as each described a kind of preparation method who is used for the Co based Fischer-Tropsch synthesis catalyst of paste state bed reactor of claim 1-5, it is characterized in that comprising the steps:
(1), consist of: the Co metal by the catalyst weight ratio: 5.0～40.0%, bullion content: 0～2.0%; Base metal in the transition metal: 0～10%, carrier is 48%～95%, and cobalt salt is joined in the deionized water, cobalt salt concentration is 0.5～5mol/L;
(2), by catalyst weight than forming, the base metal soluble-salt of noble metal, transition metal is joined in step (1) solution;
(3), will make the solution that concentration is 1～5mol/L in the bases precipitating reagent adding deionized water;
(4), above-mentioned two kinds of solution are joined in the settling vessel that band stirs jointly in 40～90 ℃, precipitate under pH value 7～10 conditions, precipitation finishes that the back is static wore out 1～6 hour, obtains precipitating slurry, washs to free from admixture;
(5), by catalyst weight than forming, be that the carrier colloidal sol of 10～40wt% mixes with post precipitation filter material and concentration, obtain solid content after mixing and be 10～60% catalyst pulp, be spray dried to microballoon cobalt-base catalyst powder then;
(6), obtain powder 300～600 ℃ of constant temperature calcining 3-10h in Muffle furnace, acquisition preformed catalyst.
7. a kind of preparation method who is used for the Co based Fischer-Tropsch synthesis catalyst of paste state bed reactor as claimed in claim 6 is characterized in that described cobalt salt is organic cobalt salt or inorganic cobalt salt
8. a kind of preparation method who is used for the Co based Fischer-Tropsch synthesis catalyst of paste state bed reactor as claimed in claim 7 is characterized in that described organic cobalt salt is a cobalt acetate, and inorganic cobalt salt is a cobalt nitrate.
9. a kind of preparation method who is used for the Co based Fischer-Tropsch synthesis catalyst of paste state bed reactor as claimed in claim 6, the soluble-salt that it is characterized in that described noble metal is RuCl
4, PdCl
4Or H
2PtCl
4
10. a kind of preparation method who is used for the Co based Fischer-Tropsch synthesis catalyst of paste state bed reactor as claimed in claim 6 is characterized in that the base metal soluble-salt in the described transition metal is La (NO
3)
3, Zr (NO
3)
4, TiCl
4Or Ce (NO
3)
3
11. a kind of preparation method who is used for the Co based Fischer-Tropsch synthesis catalyst of paste state bed reactor as claimed in claim 6 is characterized in that described bases precipitating reagent is ammoniacal liquor, NaOH, sodium carbonate or ammonium carbonate.
12. a kind of preparation method who is used for the Co based Fischer-Tropsch synthesis catalyst of paste state bed reactor as claimed in claim 6 is characterized in that described carrier colloidal sol is Ludox or aluminium colloidal sol, the concentration of Ludox or aluminium colloidal sol is 10～30%.
13. a kind of preparation method who is used for the Co based Fischer-Tropsch synthesis catalyst of paste state bed reactor as claimed in claim 6 is characterized in that described spray-dired pressure is 1～10MPa, 200～350 ℃ of inlet temperatures, 60～170 ℃ of outlet temperatures.
14. a kind of preparation method who is used for the Co based Fischer-Tropsch synthesis catalyst of paste state bed reactor as claimed in claim 13 is characterized in that described spray-dired pressure is 1.5～5MPa; 255～320 ℃ of inlet temperatures, 80～130 ℃ of outlet temperatures.
15. as each described a kind of application that is used for the Co based Fischer-Tropsch synthesis catalyst of paste state bed reactor of claim 1-5, it is characterized in that catalyst uses pure hydrogen reduction in fixed bed, the stirring-type paste state bed reactor is adopted in reaction.The catalyst reduction condition is: 250～500 ℃, and 0.2～1.2MPa, volume space velocity 500～2500h
-1, constant temperature 6～24h; Reaction condition is, 190～250 ℃, and 0.5～5.0MPa, volume space velocity 500～3000h
-1, speed of agitator is 400～1400rpm, H
2: the CO mol ratio is 1～3: 1.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1785515A (en) * | 2005-12-14 | 2006-06-14 | 中国科学院山西煤炭化学研究所 | Catalyst used for synthesizing middle distillate from synthetic gas, its preparation method and application |
| EP2127729A1 (en) * | 2008-05-30 | 2009-12-02 | Mazda Motor Corporation | Exhaust gas purification catalyst |
-
2010
- 2010-09-20 CN CN 201010291503 patent/CN102000575A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1785515A (en) * | 2005-12-14 | 2006-06-14 | 中国科学院山西煤炭化学研究所 | Catalyst used for synthesizing middle distillate from synthetic gas, its preparation method and application |
| EP2127729A1 (en) * | 2008-05-30 | 2009-12-02 | Mazda Motor Corporation | Exhaust gas purification catalyst |
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