CN102441392B - Method for preparing low-cost high-activity cobalt-based Fischer-Tropsch synthetic catalyst - Google Patents
Method for preparing low-cost high-activity cobalt-based Fischer-Tropsch synthetic catalyst Download PDFInfo
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Abstract
The invention discloses a method for preparing a low-cost high-activity cobalt-based Fischer-Tropsch synthetic catalyst, which comprises the following steps of: firstly carrying out surface modification on a silica gel carrier by using a saccharic acidic solution; and then, loading a metal promoter X1, a metal promoter X2 and an active component Co (cobalt), wherein the metal promoter X1 is one or more of Re, Zr, Hf, Ce and Th, and the metal promoter X2 is one or more of Ni, Mo and W. The catalyst prepared through the method disclosed by the invention has high activity, good stability and low cost; and the preparation method is simple and is applicable to industrial application.
Description
Technical field
The present invention relates to a kind of preparation method of low-cost high-activity cobalt-based Fischer-Tropsch synthetic catalyst, relate in particular to a kind ofly take modified silica-gel as carrier, add the preparation method of the Co based Fischer-Tropsch synthesis catalyst of low cost that metal promoter modifies, high-activity stable.
Background technology
Synthetic synthesis gas (the CO+H that refers to of Fischer-Tropsch
2) catalyze and synthesize the reaction of liquid hydrocarbon fuel on catalyst.Exhaustion day by day along with petroleum resources has been subject to 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 the fischer-tropsch catalysts of nearly 80 years, people have found that Fe, Co and Ru etc. are the metals with fischer-tropsch activity, wherein iron catalyst has high activity to water gas shift reaction, the easy carbon distribution of catalyst and poisoning when reaction temperature is high, and the chain growth ability is relatively poor, is unfavorable for synthetic long-chain product, and Ru be very limited natural resources and expensive price limit it as the application of industrial catalyst.Use cobalt-base catalyst can not only generate to greatest extent heavy hydrocarbon, and cobalt-base catalyst carbon distribution tendency is low, active high, therefore significant take cobalt-base catalyst as the research on basis.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 is the focus of research.
Only adopt the reactive metal cobalt, catalyst activity and selectively unsatisfactory.Cobalt-base catalyst is easy sintering in preparation process, causes the activated centre not play a role to greatest extent, and therefore, normal some noble metals that add can obviously improve catalytic performance in the cobalt-base catalyst preparation 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%, methane be selectively 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.) after reaction 100h, the volume conversion ratio of CO is 87%, and in product, the yield of hydrocarbon is 0.349kg/h/kg cat.; After reaction 400h, the volume conversion ratio of CO is 84%, and in product, the yield of hydrocarbon is 0.336kg/h/kgcat..For catalyst system 20%Co0.05%Pt/100Al
2O
3(Wt.) after reaction 100h, the volume conversion ratio of CO is 73%, and in product, the yield of hydrocarbon is 0.291kg/h/kg cat..After reaction 400h, the volume conversion ratio of CO is 63%, and in product, the yield of hydrocarbon is 0.250kg/h/kg cat..
Although adopt precious metals pt can promote the reduction of cobalt, the high degree of dispersion that has kept simultaneously catalyst, increased the number in activated centre, when certain content, can significantly increase the activity stability of catalyst, improve the TOF of catalyst, but the precious metals pt cost is high, is not suitable in industrial a large amount of uses.Prior art shows, adopts existing conventional preparation method, when using other base metal as auxiliary agent, and the stability of catalyst and selectively do not reach the effect of using precious metals pt.
Summary of the invention
For the deficiencies in the prior art, the 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 acid solution of sugar to carry out surface modification to silica-gel carrier, then adopt infusion process carried metal auxiliary agent X1, metal promoter X2 and active component Co, described metal promoter X1 is one or more in Re, Zr, Hf, Ce and Th etc., and metal promoter X2 is one or more in Ni, Mo and W.
In the preparation method of Co based Fischer-Tropsch synthesis catalyst of the present invention, silica-gel carrier can adopt existing silica gel product, and as macropore or pore dry microspheres etc., silica gel can adopt commodity on demand, also can be by existing method preparation.
In the preparation method of Co based Fischer-Tropsch synthesis catalyst of the present invention, the sugar that the acid solution of sugar used uses comprises various suitable water-soluble sugar, as various monose or disaccharide, specifically comprise the aqueous solution such as fructose, glucose, sucrose, maltose, the preferably sucrose acid solution.Concrete method of modifying to silica-gel carrier is that the acid solution of a certain amount of silica gel with sugar mixed, dry, roasting after fully stirring.Silica gel is 1: 1.5～1: 15 with adopting the mass ratio that the acid solution contain sugar mixes, and is preferably 1: 4～1: 12.In the acid solution of sugar, the mass concentration of sugar is 1%-35%, preferred 5%-20%.Sugary acid solution pH is 0.1-6.5, and preferred pH value is 1-3, can use the pH value of inorganic acid arbitrarily or organic acid regulator solution, is preferably hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, formic acid, acetic acid etc.Silica gel is 50-95 ℃ with the acid solution mixing temperature that contains sugar, is preferably 60～80 ℃, and the mixed processing time is 0.5-10h, preferred 2-5h.Mixing rear baking temperature is 50-150 ℃, and be 0.5-36h drying time, preferably dry 8-24h under 60-120 ℃.Roasting is at 600-1200 ℃ of lower roasting 2-15 hour, preferably at 800-1000 ℃ of lower roasting 4-10 hour.Wherein silica gel mixes with the acid solution that contains sugar and follow-up drying and roasting can be carried out once, also can repeatedly carry out repeatedly, as 2～5 times.Roasting process adopts vacuum condition or carries out under inert gas atmosphere.
In 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 then step impregnation method of impregnating metal auxiliary agent X2 and active component Co.Metal promoter X2 and active component Co can adopt co-impregnation, also can adopt first impregnating metal auxiliary agent X2, then flood the step impregnation method of active component Co.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: first adopt the solution impregnation modified silica gel carrier of containing metal auxiliary agent X1 element salt, then adopt the solution impregnation of containing metal auxiliary agent X2 element salt and active component Co salt, can comprise drying steps and calcination steps after per step dipping.Drying steps under 50-150 ℃ dry 8-24 hour, calcination steps was at 280-600 ℃ of lower roasting 2-10 hour.In the catalyst of preparation, the weight percentage of metal promoter X1 is 0.5%-6%, 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 take modified silica-gel as carrier, take cobalt as active component, one or more in Re, Zr, Hf, Ce and the Th are as metal promoter X1, as metal promoter X2, adopt said method preparation of the present invention with one or more in Ni, Mo and W.
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, the acid solution of suitable sugar 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 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, methane selectively adopt precious metals pt the time, descended 2-3 percentage point.
2, greatly reduce the catalyst cost, improved Catalyst and promoted the use of.
3, the catalyst preparation is simple, and technology is ripe, is conducive to the industrial production of catalyst.
The specific embodiment
Further illustrate process and the effect of the inventive method below in conjunction with embodiment.
Example 1
(pore volume is 1.06ml/g, and specific area is 386.81m to take commercially available silica gel
2/ g, following examples are all used this silica gel) 30g, dripping distilled water to just moistening, the volume that consumes water is 48ml.Be that 5% the aqueous solution equals 3 with the sulphur acid for adjusting pH value with the sucrose mass concentration, and the mass ratio that makes silica gel and mixed solution is 1: 4, be with silica gel and the abundant mix and blend of sucrose acid solution 2 hours under 60 ℃ in temperature, in 60 ℃ dry 24 hours, then roasting 10 hours in vacuum or nitrogen atmosphere in 800 ℃.
By final catalyst zirconium content 1wt%, take nitrate trihydrate zirconium 1.41g, adding distil water is treated to dissolve fully to 48g, adds in the carrier silica gel after 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 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 after 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.
Evaluating catalyst test is in the high pressure CSTR, and as solvent, with reduction under 350 ℃ of pure hydrogen 12 hours, pressure was 1.0MPa with paraffin.Switching synthesis gas after cooling reacts.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).C-1 catalyst Fischer-Tropsch synthesis result is as shown in table 1.
Example 2
Take commercially available silica gel, drip distilled water to just moistening, the volume that consumes water is 48ml.Be that 15% the aqueous solution equals 2 with the salt acid for adjusting pH value with the sucrose mass concentration, and the mass ratio that makes silica gel and mixed solution is 1: 9, be with silica gel and the abundant mix and blend of sucrose acid solution 3.5 hours under 70 ℃ in temperature, in 100 ℃ dry 16 hours, vacuum baking 8 hours in 900 ℃ then.
By final catalyst zirconium content 3wt%, take nitrate trihydrate zirconium 4.23g, adding distil water is treated to dissolve fully to 48g, adds in the carrier silica gel after 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 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 after above-mentioned dipping zirconium, aging 3 hours, 150 ℃ of dryings 8 hours, roasting is 2 hours in 600 ℃, sample repeat previous step.The gained catalyst is designated as CFT-2.Catalyst activity evaluation experimental condition is with embodiment 1.CFT-2 catalyst Fischer-Tropsch synthesis result is as shown in table 1.
Example 3
Take commercially available silica gel, drip distilled water to just moistening, the volume that consumes water is 48ml.Be that 20% the aqueous solution equals 1 with the sulphur acid for adjusting pH value with the sucrose mass concentration, and the mass ratio that makes silica gel and mixed solution is 1: 12, be with silica gel and the abundant mix and blend of sucrose acid solution 5 hours under 80 ℃ in temperature, in 120 ℃ dry 8 hours, vacuum baking 4 hours in 1000 ℃ then.
By final catalyst zirconium content 2wt%, take nitrate trihydrate zirconium 2.82g, adding distil water is treated to dissolve fully to 48g, adds in the carrier silica gel after 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 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 after 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.CFT-3 catalyst Fischer-Tropsch synthesis result is as shown in table 1.
Example 4
Take commercially available silica gel 30g, drip distilled water to just moistening, the volume that consumes water is 48ml.Be that 5% the aqueous solution equals 3 with the second acid for adjusting pH value with the sucrose mass concentration, and the mass ratio that makes silica gel and mixed solution is 1: 4, be with silica gel and the abundant mix and blend of sucrose acid solution 2 hours under 60 ℃ in temperature, in 60 ℃ dry 24 hours, then roasting 10 hours in vacuum or nitrogen atmosphere in 800 ℃.
By final catalyst zirconium content 2wt%, take nitrate trihydrate zirconium 2.82g, adding distil water is treated to dissolve fully to 48g, adds in the carrier silica gel after 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 ammonium molybdate 0.55g, adding distil water is treated to dissolve fully to 48g, adds in the sample after 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 after above-mentioned dipping zirconium and molybdenum, and aging 3 hours, 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.CFT-4 catalyst Fischer-Tropsch synthesis result is as shown in table 1.
Example 5
Take commercially available silica gel, drip distilled water to just moistening, the volume that consumes water is 48ml.Be that 15% the aqueous solution equals 2 with the sulphur acid for adjusting pH value with glucose quality concentration, and the mass ratio that makes silica gel and mixed solution is 1: 9, be with the abundant mix and blend of the acid solution of silica gel and glucose 3.5 hours under 70 ℃ in temperature, in 100 ℃ dry 16 hours, vacuum baking 8 hours in 900 ℃ then.
By final catalyst zirconium content 2wt%, take nitrate trihydrate zirconium 2.82g, adding distil water is treated to dissolve fully to 48g, adds in the carrier silica gel after 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 ammonium metatungstate 0.43g, adding distil water is treated to dissolve fully to 48g, adds in the sample after 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 after above-mentioned dipping zirconium and tungsten, and aging 3 hours, 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.CFT-5 catalyst Fischer-Tropsch synthesis result is as shown in table 1.
Example 6
By final catalyst zirconium content 2wt%, take nitrate trihydrate zirconium 2.82g, adding distil water is treated to dissolve fully to 48g, adds in the carrier silica gel after above-mentioned modification to flood, aging 3 hours, 80 ℃ of dryings 12 hours, roasting is 4 hours in 350 ℃.Take commercially available silica gel, drip distilled water to just moistening, the volume that consumes water is 48ml.Be that 15% the aqueous solution equals 2 with the sulphur acid for adjusting pH value with the fructose mass concentration, and the mass ratio that makes silica gel and mixed solution is 1: 9, be with silica gel and the abundant mix and blend of fructose acid solution 3.5 hours under 70 ℃ in temperature, in 100 ℃ dry 16 hours, vacuum baking 8 hours in 900 ℃ then.
By final catalyst zirconium content 2wt%, take nitrate trihydrate zirconium 2.82g, adding distil water is treated to dissolve fully to 48g, adds in the carrier silica gel after 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 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 after 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.CFT-6 catalyst Fischer-Tropsch synthesis result is as shown in table 1.
Comparative example:
Take commercially available silica gel 30g, drip distilled water to first profit, the volume that consumes water is 48ml, is 15% ethanolamine solutions with 48ml concentration, adds silica gel under 80 ℃, stirs.Aging 30 hours, 90 ℃ of dryings 16 hours.By final catalyst zirconium content 2wt%, take nitrate trihydrate zirconium 2.82g, adding distil water is treated to dissolve fully to 48g, adds in the carrier silica gel after 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 cobalt nitrate hexahydrate 29.64g and chloroplatinic acid, adding distil water is treated to dissolve fully to 48g, adds in the sample after 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.CB-1 catalyst Fischer-Tropsch synthesis result is as shown in table 1.
The reactivity worth of table 1 catalyst
Claims (7)
1. the preparation method of a low-cost high-activity cobalt-based Fischer-Tropsch synthetic catalyst, it is characterized in that comprising following process: at first adopt the acid solution of sugar to carry out surface modification to silica-gel carrier, then adopt infusion process carried metal auxiliary agent X1, metal promoter X2 and active component Co, described metal promoter X1 is Re, Zr, Hf, one or more in Ce and Th, metal promoter X2 is Ni, one or more in Mo and W, the sugar that the acid solution of described sugar uses comprises monose or disaccharide, concrete method of modifying to silica-gel carrier is that the acid solution of silica gel with sugar mixed, dry after fully stirring, roasting, roasting process adopts vacuum condition or carries out under inert gas atmosphere, silica gel is 1: 1.5～1: 15 with the mass ratio that the acid solution of sugar mixes, in the acid solution of sugar, the mass concentration of sugar is 1%-35%, the acid solution pH of sugar is 0.1-6.5, silica gel is 50-95 ℃ with the acid solution mixing temperature of sugar, the mixed processing time is 0.5-10h, mixing rear baking temperature is 50-150 ℃, be 0.5-36h drying time, roasting was at 600-1200 ℃ of lower roasting 2-15 hour, silica gel mixes with the acid solution of sugar and follow-up drying and roasting are carried out 2～5 times repeatedly, the weight percentage of described metal promoter X1 is 0.5%-6%, the weight percentage of metal promoter X2 is 0.1%-3%, the weight percentage of cobalt is 5%-35%.
2. in accordance with the method for claim 1, it is characterized in that: silica gel is 1: 4～1: 12 with the mass ratio that the acid solution of sugar mixes, and in the acid solution of sugar, the mass concentration of sugar is 5%-20%, and the acid solution pH of sugar is 1-3.
3. in accordance with the method for claim 1, it is characterized in that: silica gel is 60～80 ℃ with the acid solution mixing temperature of sugar, and the mixed processing time is 2-5h, and mixing rear baking temperature is 60-120 ℃, be 8-24h drying time, and roasting was at 800-1000 ℃ of lower roasting 4-10 hour.
4. it is characterized in that in accordance with the method for claim 1: the weight percentage of described metal promoter X1 is 1%-3%; The weight percentage of metal promoter X2 is 0.5%-1.5%.
5. in accordance with the method for 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 then step impregnation method of impregnating metal auxiliary agent X2 and active component Co.
6. according to the described method of claim 1 or 5, it is characterized in that: metal promoter X2 and active component Co adopt co-impregnation or adopt first impregnating metal auxiliary agent X2, then flood the step impregnation method of active component Co.
7. Co based Fischer-Tropsch synthesis catalyst, take modified silica-gel as carrier, take cobalt as active component, one or more in Re, Zr, Hf, Ce and the Th are as metal promoter X1,, it is characterized in that as metal promoter X2 with one or more in Ni, Mo and W: Co based Fischer-Tropsch synthesis catalyst adopts the described method preparation of arbitrary claim in claim 1 to 6.
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