CN102441391A - Preparation method of cobalt-based catalyst for Fischer Tropsch synthesis - Google Patents
Preparation method of cobalt-based catalyst for Fischer Tropsch synthesis Download PDFInfo
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Abstract
The invention discloses a preparation method of a cobalt-based catalyst for Fischer Tropsch synthesis. The preparation method comprises the following steps of: firstly, carrying out surface modification on a silicon gel carrier by adopting an ammonium salt-containing buffer solution; and secondly, loading a metal additive X1, a metal additive X2 and an active component Co by adopting an immersion method, wherein the metal additive X1 is one or more of Re, Zr, Hf, Ce and Th and the metal additive X2 is one or more of Ni, Mo and W. The cobalt-based catalyst prepared by adopting the preparation method provided by the invention has high activity, good stability and low cost; and the preparation method is simple and is suitable for industrial application.
Description
Technical field
The present invention relates to a kind of preparation method of Co based Fischer-Tropsch synthesis catalyst, relating in particular to a kind of is carrier with the modified silica-gel, adds the low cost of metal promoter modification, the preparation method of highly active Co based Fischer-Tropsch synthesis catalyst.
Background technology
Synthetic synthesis gas (the CO+H that is meant of Fischer-Tropsch
2) reaction of catalysis synthetic hydrocarbon liquid fuel on catalyst.Exhaustion day by day along with petroleum resources has received the attention of countries in the world more with the Fischer-Tropsch synthesis prepare liquid fuel.Catalyst is one of key technology of Fischer-Tropsch synthesis; In the research of nearly 80 years fischer-tropsch catalysts, people have found that Fe, Co and Ru etc. are the metals with fischer-tropsch activity, and wherein iron catalyst has high activity to water gas shift reaction; Catalyst was prone to carbon distribution and poisoning when reaction temperature was high; And the chain growth ability is relatively poor, is unfavorable for synthetic long-chain product, and Ru be very limited natural resource and expensive price limit it as the application of industrial catalyst.Use cobalt-base catalyst can not only generate heavy hydrocarbon to greatest extent, and cobalt-base catalyst carbon distribution tendency is low, active high, therefore is that the research on basis is significant with the cobalt-base catalyst.Various auxiliary elements play an important role to activity, the stability of fischer-tropsch catalysts, and the carrier of catalyst is with unformed SiO
2, TiO
2And Al
2O
3Be main.How active component, metal promoter and support modification are carried out effective and reasonable collocation, preparing the fischer-tropsch synthetic catalyst with high-activity stable property is the focus of research.
Only only adopt the reactive metal cobalt, catalyst activity and selectivity are unsatisfactory.Cobalt-base catalyst easy sintering in the preparation process causes the activated centre not play a role to greatest extent, therefore, prepares at cobalt-base catalyst that normal some noble metals that add can obviously improve catalytic performance in the process.CN101224430A has reported a kind of hydrophobic organic modification of Co group Fischer-Tropsch synthesized catalyst, wherein when noble metal adopts Pt, and catalyst system 15%Co0.8%Pt/SiO
2, organically-modified reagent adopts the 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 are 72.7%, and the selectivity of methane is 8.4%.
The employing Pt of US5733839 report is as auxiliary agent, and aluminium oxide is as the Co based Fischer-Tropsch synthesis catalyst of carrier.In slurry attitude bed system, be 220 ℃ in reaction temperature, pressure is 20bar, air speed is 2.0Nm
3/ h/kgcat.H
2/ CO=2/1 (V/V) is for catalyst system 30%Co0.05%Pt/100Al
2O
3(Wt.) the volume conversion ratio of CO is 87% behind the reaction 100h, and the yield of hydrocarbon is 0.349kg/h/kg cat. in the product; Behind the reaction 400h, the volume conversion ratio of CO is 84%, and the yield of hydrocarbon is 0.336kg/h/kgcat. in the product.For catalyst system 20%Co0.05%Pt/100Al
2O
3(Wt.) the volume conversion ratio of CO is 73% behind the reaction 100h, and the yield of hydrocarbon is 0.291kg/h/kg cat. in the product.Behind the reaction 400h, the volume conversion ratio of CO is 63%, and the yield of hydrocarbon is 0.250kg/h/kg cat. in the product.
Though adopt precious metals pt can promote the reduction of cobalt; The high degree of dispersion that has kept catalyst has simultaneously increased the number in activated centre, when certain content; Can significantly increase activity of such catalysts stability; Improve the TOF of catalyst, but the precious metals pt cost is high, does not suit in industry, to use in a large number.Prior art shows, adopts the existing conventional preparation method, and when using other base metal as auxiliary agent, the stability of catalyst and selectivity do not reach the effect of using precious metals pt.
Summary of the invention
To the deficiency of prior art, the present invention provides the preparation method of a kind of low cost, highly active Co based Fischer-Tropsch synthesis catalyst.
The preparation method of Co based Fischer-Tropsch synthesis catalyst of the present invention comprises following process: at first adopt the cushioning liquid of ammonium salt-containing that silica-gel carrier is carried out surface modification; Adopt infusion process carried metal auxiliary agent X1, metal promoter X2 and active component Co then; Described metal promoter X1 is one or more among Re, Zr, Hf, Ce and the Th etc., and metal promoter X2 is one or more among Ni, Mo and the W.
Among the preparation method of Co based Fischer-Tropsch synthesis catalyst of the present invention, silica-gel carrier can adopt existing silica gel product, and like macropore or pore dry microspheres etc., silica gel can adopt commodity on demand, also can be by existing method preparation.
Among the preparation method of Co based Fischer-Tropsch synthesis catalyst of the present invention, it can be to be selected from ammonium acetate, ammonium formate, ammonium carbonate, the carbonic hydroammonium etc. one or more that the method for modifying of silica-gel carrier is adopted the cushioning liquid impregnation process of ammonium salt-containing, ammonium salt.The weight concentration of ammonium salt is 1%-35% in the cushioning liquid, is preferably 5%-20%.Dipping can adopt saturated dipping or supersaturation dipping, carries out drying behind the dipping, also can proceed calcination process.The impregnation process temperature is 50-95 ℃, is preferably 60～80 ℃, and the impregnation process time is 2-150h, preferred 10-100h.Baking temperature is 50-150 ℃, and be 0.5-36h drying time, preferably dry 8-24h under 60-120 ℃.Roasting is at 280-600 ℃ of following roasting 2-15 hour, preferably at 300-500 ℃ of following roasting 4-10 hour.
Among the preparation method of Co based Fischer-Tropsch synthesis catalyst of the present invention, the preferred metal promoter X1 that adopts is Zr, and metal promoter X2 is Ni.The preferred first impregnating metal auxiliary agent X1 of the carrying method of metal promoter and active component Co, the step impregnation method of impregnating metal auxiliary agent X2 and active component Co then.Metal promoter X2 and active component Co can adopt co-impregnation, also can adopt first impregnating metal auxiliary agent X2, flood the step impregnation method of active component Co then.The dipping process of metal promoter and active component Co can adopt method well known to those skilled in the art.As adopt following process: adopt the solution impregnation modified silica-gel carrier of containing metal auxiliary agent X1 element salt earlier, adopt the solution impregnation of containing metal auxiliary agent X2 element salt and active component Co salt then, can comprise drying steps and calcination steps behind per step dipping.Drying steps descended dry 8-24 hour at 50-150 ℃, and calcination steps was at 280-600 ℃ of following roasting 2-10 hour.The weight percentage of metal promoter X1 is 0.5%-6% in the catalyst of preparation, preferred 1%-3%, and the weight percentage of reactive metal X2 is 0.1%-3%, preferred 0.5%-1.5%, the weight percentage of cobalt is 5%-35%.
Co based Fischer-Tropsch synthesis catalyst of the present invention is carrier with the modified silica-gel; With the cobalt is active component; With among Re, Zr, Hf, Ce and the Th one or more is metal promoter X1, as metal promoter X2, adopts method for preparing of the present invention with among Ni, Mo and the W one or more.
Compared with prior art, the catalyst that obtains of the preparation method of the inventive method Co based Fischer-Tropsch synthesis catalyst has following advantage:
1, suitable cushioning liquid is under optimum conditions to the surface treatment of silica-gel carrier; Form the coordinated effect with suitable auxiliary agent; Change the interaction between carrier, promoter metal and the activated centre, realized replacing precious metal additive to improve the purpose of catalyst activity with the base metal auxiliary agent.In addition; Compare with adopting precious metal additive Pt, under the close condition of synthesis gas initial conversion, the catalyst of the inventive method preparation demonstrates better stability and lower methane selectively; When the selectivity of methane adopts precious metals pt, descended 2-3 percentage point.
2, greatly reduce the catalyst cost, improved catalyst industry and promoted the use of.
3, Preparation of Catalyst is simple, and technology is ripe, helps the commercial production of catalyst.
The specific embodiment
Further specify the process and the effect of the inventive method below in conjunction with embodiment.
Instance 1
Take by weighing commercially available silica gel 30g, drip distilled water to just moistening, the volume of consume water is 48ml, is 5% sal volatile with 48ml concentration, adds down in the silica gel at 60 ℃, stirs.Handled 100 hours, 60 ℃ of dryings 24 hours, roasting is 10 hours in 300 ℃.By final catalyst zirconium content 1wt%, take by weighing nitrate trihydrate zirconium 1.41g, adding distil water is treated to dissolve fully to 48g, adds in the carrier silica gel after the above-mentioned modification to flood, aging 3 hours, 50 ℃ of dryings 24 hours, roasting is 10 hours in 280 ℃.By final catalyst cobalt content 5wt%, Ni content 0.5wt% meter takes by weighing cobalt nitrate hexahydrate 7.41g and six water nickel nitrate 0.74g; Adding distil water is treated to dissolve fully to 48g, adds in the sample behind the above-mentioned dipping zirconium; Aging 3 hours, 50 ℃ of dryings 24 hours, roasting is 10 hours in 280 ℃.The gained catalyst is designated as CFT-1.
The evaluating catalyst test, was reduced 12 hours down for 350 ℃ with pure hydrogen as solvent with paraffin in the high pressure CSTR, and pressure is 1.0MPa.The cooling back is switched synthesis gas and is reacted.Reaction effluent is collected by hot trap, cold-trap respectively.Reaction condition is 180-250 ℃, 2.5Nm
3/ h/kg cat., 2.0MPa, H
2/ CO=2 (mol ratio).The result is as shown in table 1 for C-1 catalyst Fischer-Tropsch synthesis.
Instance 2
Take by weighing commercially available silica gel 30g, drip distilled water to just moistening, the volume of consume water is 48ml, is 20% sal volatile with 48ml concentration, adds down in the silica gel at 80 ℃, stirs.Handled 120 ℃ of dryings 8 hours 10 hours.By final catalyst zirconium content 3wt%, take by weighing nitrate trihydrate zirconium 4.23g, adding distil water is treated to dissolve fully to 48g, adds in the carrier silica gel after the above-mentioned modification to flood, aging 3 hours, 150 ℃ of dryings 8 hours, roasting is 2 hours in 600 ℃.By final catalyst cobalt content 35wt%, Ni content 1.5% floods reactive metal and auxiliary agent Ni in two steps.The first step takes by weighing cobalt nitrate hexahydrate 25.94 and six water nickel nitrate 1.11g, and adding distil water treats to dissolve fully 1 to 48g; Add in the sample behind the above-mentioned dipping zirconium, aging 3 hours, 150 ℃ of dryings 8 hours; Roasting is 2 hours in 600 ℃, sample repeat a step.The gained catalyst is designated as CFT-2.Catalyst activity evaluation experimental condition is with embodiment 1.The result is as shown in table 1 for CFT-2 catalyst Fischer-Tropsch synthesis.
Instance 3
Take by weighing commercially available silica gel 30g, drip distilled water to just moistening, the volume of consume water is 48ml, is 15% sal volatile with 48ml concentration, adds down in the silica gel at 70 ℃, stirs.Handled 90 ℃ of dryings 16 hours 30 hours.By final catalyst zirconium content 2wt%, take by weighing nitrate trihydrate zirconium 2.82g, adding distil water is treated to dissolve fully to 48g, adds in the carrier silica gel after the above-mentioned modification to flood, aging 3 hours, 80 ℃ of dryings 12 hours, roasting is 4 hours in 350 ℃.By final catalyst cobalt content 20wt%, Ni content 1% takes by weighing cobalt nitrate hexahydrate 29.64g and six water nickel nitrate 1.48g; Adding distil water is treated to dissolve fully to 48g, adds in the sample behind the above-mentioned dipping zirconium; Aging 3 hours, 80 ℃ of dryings 12 hours, roasting is 4 hours in 350 ℃.The gained catalyst is designated as CFT-3.Catalyst activity evaluation experimental condition is with embodiment 1.The result is as shown in table 1 for CFT-3 catalyst Fischer-Tropsch synthesis.
Instance 4
Take by weighing commercially available silica gel 30g, drip distilled water to just moistening, the volume of consume water is 48ml, is 15% ammonium acetate solution with 48ml concentration, adds down in the silica gel at 70 ℃, stirs.Handled 90 ℃ of dryings 16 hours 30 hours.By final catalyst zirconium content 2wt%, take by weighing nitrate trihydrate zirconium 2.82g, adding distil water is treated to dissolve fully to 48g, adds in the carrier silica gel after the above-mentioned modification to flood, aging 3 hours, 80 ℃ of dryings 12 hours, roasting is 4 hours in 350 ℃.By final catalyst molybdenum content 1wt%, take by weighing ammonium molybdate 0.55g, adding distil water is treated to dissolve fully to 48g, adds in the sample behind the above-mentioned load zirconium, aging 3 hours, 80 ℃ of dryings 12 hours, roasting is 4 hours in 350 ℃.By final catalyst cobalt content 20wt%, cobalt nitrate hexahydrate 29.64g, adding distil water treat to dissolve fully to 48g, add in the sample behind above-mentioned dipping zirconium and the molybdenum, wore out 3 hours, and 80 ℃ of dryings 12 hours, roasting is 4 hours in 350 ℃.The gained catalyst is designated as CFT-4.Catalyst activity evaluation experimental condition is with embodiment 1.The result is as shown in table 1 for CFT-4 catalyst Fischer-Tropsch synthesis.
Instance 5
Take by weighing commercially available silica gel 30g, drip distilled water to just moistening, the volume of consume water is 48ml, is 15% ammonium formate solution with 48ml concentration, adds down in the silica gel at 70 ℃, stirs.Handled 90 ℃ of dryings 16 hours 30 hours.By final catalyst zirconium content 2wt%, take by weighing nitrate trihydrate zirconium 2.82g, adding distil water is treated to dissolve fully to 48g, adds in the carrier silica gel after the above-mentioned modification to flood, aging 3 hours, 80 ℃ of dryings 12 hours, roasting is 4 hours in 350 ℃.By final catalyst W content 1wt%, take by weighing ammonium metatungstate 0.43g, adding distil water is treated to dissolve fully to 48g, adds in the sample behind the above-mentioned load zirconium, aging 3 hours, 80 ℃ of dryings 12 hours, roasting is 4 hours in 350 ℃.By final catalyst cobalt content 20wt%, cobalt nitrate hexahydrate 29.64g, adding distil water treat to dissolve fully to 48g, add in the sample behind above-mentioned dipping zirconium and the tungsten, wore out 3 hours, and 80 ℃ of dryings 12 hours, roasting is 4 hours in 350 ℃.The gained catalyst is designated as CFT-5.Catalyst activity evaluation experimental condition is with embodiment 1.The result is as shown in table 1 for CFT-5 catalyst Fischer-Tropsch synthesis.
Instance 6
Take by weighing commercially available silica gel 30g, drip distilled water to just moistening, the volume of consume water is 48ml, is 15% ammonium bicarbonate solution with 48ml concentration, adds down in the silica gel at 70 ℃, stirs.Handled 90 ℃ of dryings 16 hours 30 hours.By final catalyst zirconium content 2wt%, take by weighing nitrate trihydrate zirconium 2.82g, adding distil water is treated to dissolve fully to 48g, adds in the carrier silica gel after the above-mentioned modification to flood, aging 3 hours, 80 ℃ of dryings 12 hours, roasting is 4 hours in 350 ℃.By final catalyst cobalt content 20wt%, Ni content 1% takes by weighing cobalt nitrate hexahydrate 29.64g and six water nickel nitrate 1.48g; Adding distil water is treated to dissolve fully to 48g, adds in the sample behind the above-mentioned dipping zirconium; Aging 3 hours, 80 ℃ of dryings 12 hours, roasting is 4 hours in 350 ℃.The gained catalyst is designated as CFT-6.Catalyst activity evaluation experimental condition is with embodiment 1.The result is as shown in table 1 for CFT-6 catalyst Fischer-Tropsch synthesis.
Comparative example:
Take by weighing commercially available silica gel 30g, drip distilled water to just moistening, the volume of consume water is 48ml, is 15% sal volatile with 48ml concentration, adds down in the silica gel at 70 ℃, stirs.Handled 90 ℃ of dryings 16 hours 30 hours.By final catalyst zirconium content 2wt%, take by weighing nitrate trihydrate zirconium 2.82g, adding distil water is treated to dissolve fully to 48g, adds in the carrier silica gel after the above-mentioned modification to flood, aging 3 hours, 80 ℃ of dryings 12 hours, roasting is 4 hours in 350 ℃.By final catalyst cobalt content 20wt%, Pt content 0.1% takes by weighing cobalt nitrate hexahydrate 29.64g and chloroplatinic acid; Adding distil water is treated to dissolve fully to 48g, adds in the sample behind the above-mentioned dipping zirconium; Aging 3 hours, 80 ℃ of dryings 12 hours, roasting is 4 hours in 350 ℃.The gained catalyst is designated as CB-1.Catalyst activity evaluation experimental condition is with embodiment 1.The result is as shown in table 1 for CB-1 catalyst Fischer-Tropsch synthesis.
The reactivity worth of table 1 catalyst
Claims (10)
1. the preparation method of a Co based Fischer-Tropsch synthesis catalyst; It is characterized in that comprising following process: at first adopt the cushioning liquid of ammonium salt-containing that silica-gel carrier is carried out surface modification; Adopt infusion process carried metal auxiliary agent X1, metal promoter X2 and active component Co then; Described metal promoter X1 is one or more among Re, Zr, Hf, Ce and the Th, and metal promoter X2 is one or more among Ni, Mo and the W.
2. according to the described method of claim 1, it is characterized in that: the ammonium salt of the cushioning liquid of ammonium salt-containing is selected from one or more in ammonium acetate, ammonium formate, ammonium carbonate and the carbonic hydroammonium, and the weight concentration of ammonium salt is 1%-35% in the cushioning liquid.
3. according to the described method of claim 1; It is characterized in that: the cushioning liquid impregnation process adopts saturated dipping or supersaturation dipping; Carry out drying after the impregnation process, baking temperature is 50-150 ℃, and be 0.5-36h drying time; Carry out calcination process after dry, roasting was at 280-600 ℃ of following roasting 2-15 hour.
4. according to the described method of claim 3, it is characterized in that: cushioning liquid impregnation process temperature is 50-95 ℃, and the impregnation process time is 2-150h.
5. according to claim 3 or 4 described methods, it is characterized in that: cushioning liquid impregnation process temperature is 60～80 ℃, and the impregnation process time is 10-100h.
6. according to the described method of claim 1, it is characterized in that: the weight percentage of described metal promoter X1 is 0.5%-6%, and the weight percentage of reactive metal X2 is 0.1%-3%, and the weight percentage of cobalt is 5%-35%.
7. according to the described method of claim 1, it is characterized in that: the weight percentage of described metal promoter X1 is 1%-3%; Metal promoter X2 amount percentage composition is 0.5%-1.5%.
8. according to the described method of claim 1, it is characterized in that: metal promoter X1, metal promoter X2 and active component Co adopt first impregnating metal auxiliary agent X1, the step impregnation method of impregnating metal auxiliary agent X2 and active component Co then.
9. according to claim 1 or 8 described methods, it is characterized in that: metal promoter X2 and active component Co adopt co-impregnation or adopt first impregnating metal auxiliary agent X2, flood the step impregnation method of active component Co then.
10. Co based Fischer-Tropsch synthesis catalyst; With the modified silica-gel is carrier; With the cobalt is active component; With among Re, Zr, Hf, Ce and the Th one or more is metal promoter X1, and as metal promoter X2, it is characterized in that: Co based Fischer-Tropsch synthesis catalyst adopts the said method preparation of arbitrary claim in the claim 1 to 9 with among Ni, Mo and the W one or more.
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| CN103586039A (en) * | 2013-11-01 | 2014-02-19 | 中国石油化工股份有限公司 | Cobalt-based Fischer-Tropsch synthesis catalyst and preparation method thereof |
| CN103586032A (en) * | 2013-11-01 | 2014-02-19 | 中国石油化工股份有限公司 | High stability cobalt-based Fischer-Tropsch synthesis catalyst and preparation method thereof |
| CN103586043A (en) * | 2013-11-01 | 2014-02-19 | 中国石油化工股份有限公司 | Preparation method of Fischer-Tropsch synthesis catalyst |
| CN112619662A (en) * | 2019-10-09 | 2021-04-09 | 中国石油化工股份有限公司 | Catalyst for producing low-carbon olefin and preparation method and application thereof |
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