CN102861580B - A kind of preparation method of syngas conversion catalyst - Google Patents
A kind of preparation method of syngas conversion catalyst Download PDFInfo
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Abstract
A preparation method for syngas conversion catalyst take silica gel as carrier, adopts impregnation metal promoter and active component Co; Wherein, directly carry out sealing roasting after the impregnated activated component Co of described silica-gel carrier, sintering temperature is 280-600 DEG C, and roasting time is 2-12h.The inventive method processes carrier surface without the need to using acid, alkali and organic solvent etc., and the syngas conversion catalyst of preparation is not only active high, good stability, and preparation method is simple.
Description
Technical field
The present invention relates to a kind of preparation method of syngas conversion catalyst, relating in particular to a kind of take silica gel as the preparation method of the Co based Fischer-Tropsch synthesis catalyst of carrier.
Background technology
F-T synthesis refers to synthesis gas (CO+H
2) catalyze and synthesize the reaction of liquid hydrocarbon fuel on a catalyst.Along with the exhaustion day by day of petroleum resources, prepare with Fischer-Tropsch synthesis the attention that liquid fuel receives countries in the world more.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 effective active components of fischer-tropsch catalysts, the various auxiliary element such as Ru, Zr, K and Cu plays an important role to the activity of fischer-tropsch catalysts, stability, and the carrier of catalyst is generally with unformed SiO
2, TiO
2and Al
2o
3be main.How effective and reasonable collocation is carried out to active component, metal promoter and carrier, prepare the focus that the fischer-tropsch synthetic catalyst with high activity, high selectivity and high stability is research.Use cobalt-base catalyst can not only generate heavy hydrocarbon to greatest extent, and cobalt-base catalyst carbon deposit tendency is low, active high, the research therefore based on cobalt-base catalyst is significant.But in cobalt-base catalyst, metallic cobalt easily generates cobaltous silicate, cobalt titanate and cobalt aluminate compounds with above-mentioned carrier generation chemical action, reduces the activity and selectivity of catalyst, makes methane content in the reaction product increase considerably, C
5 +selectively significantly to reduce.When catalyst is in slurry bed system and fixed bed during long time running, hydrothermal meeting promotes the reaction of active component cobalt and carrier further, affects life-span and the activity of catalyst.Therefore, mostly adopt acid, alkali and organic solvent etc. to carry out modification to carrier at present, reduce the interaction between carrier and catalyst activity component, improve life-span and the activity of catalyst.
CN1509816A reports a kind of SiO
2the processing method of carrier, with one or more mixed solution treatment S iO of the carbonate of the solution of the hydroxide of alkali metal and ammonia, alkali metal and ammonia, bicarbonate, formates and acetate
2carrier, then obtained modification SiO after drying, roasting
2carrier.Use the ammonia spirit of 1%-25% to SiO in CN1454714A
2dry at carrier aged at room temperature 6-150 hour, 100-150 DEG C and carry out surface modification in 8-24 hour, improve the activity of Co based Fischer-Tropsch synthesis catalyst, at 220 DEG C, under 2MPa, CO conversion ratio is 90.1%, C
5 +selective is 85.7%.The hydroxide of alkali metal and ammonia can have obvious destruction to the surface of catalyst carrier, and some modifier also may introduce some impurity metal ions.
Zhang Junling etc. have studied ammonia modification and acetic acid Modification on Al in " SCI " the 24th volume the 2nd phase P301 ~ 304th research of reflex action " absorption of chemical modification alumina load cobalt-base catalyst with "
2o
3the reactivity worth of the fischer-tropsch synthetic catalyst of carrier loaded cobalt.Point out that ammonia is modified alumina load Co catalysts and can be promoted active and C
5 +the raising of hydrocarbon-selective, and acetic acid modifies activity and carbochain growth that aluminium oxide can restrain Co catalysts.But experiment shows, ammonia destroys obviously the pore structure of carrier, and the carrier of sour modification enhances the interaction between cobalt and carrier.
CN200480041633.1 discloses a kind of fischer-tropsch synthetic catalyst support modification method, processes at the single silicate solution of alumina carrier surface, to improve the intensity of catalyst, but does not improve the interaction between active metal and carrier.
Shi Lihong etc. utilize silanization effect to obtain alkyl-modified SiO at " catalysis journal " the 28th in volume o. 11th P999 ~ 1002 " the Fischer-Tropsch synthesis performance of organically-modified silica and load cobalt catalyst thereof "
2carrier, adopts equi-volume impregnating to prepare supported cobalt catalysts, points out SiO
2after organic group modification, improve the activity of catalyst, reduce methane selectively, but due to sterically hindered effect, can product slates be affected.
CN200510130076.7 discloses a kind of preparation method of Co based Fischer-Tropsch synthesis catalyst, first cobalt compound, aluminum contained compound and organic cosolvent and water are mixed into solution, this solution is heated under an oxygen-containing atmosphere burning, burn off organic cosolvent, obtain a kind of powder product, last in the presence of the air, by the method preparation of roasting 0.5-36 hour in 100-1000 DEG C of described powder product.The organic cosolvent wherein used is organic amine, one or more in organic acid, organic hydrazine.The method preparation process is complicated.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of with SiO
2for the preparation method of the syngas conversion catalyst of carrier.The inventive method processes carrier surface without the need to using acid, alkali and organic solvent etc., and the syngas conversion catalyst of preparation is not only active high, good stability, and preparation method is simple.
A preparation method for syngas conversion catalyst, comprises following process: take silica gel as carrier, adopts impregnation metal promoter and active component Co; Wherein directly carry out sealing roasting after the impregnated activated component Co of silica-gel carrier, sintering temperature is 280-600 DEG C, and roasting time is 2-12h.
Sealing roasting described in the inventive method is the roasting process of pressurization, and described firing pressure is the self-generated pressure in its sealing roasting process.
The preparation method of syngas conversion 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 prepare by existing method.
In the preparation method of syngas conversion catalyst of the present invention, metal promoter is one or more in Ni, Mo, W, Re, Zr, Hf, Ce and Th etc., the dipping process of metal promoter adopts conventional dipping method, such as adopt equi-volume impregnating or cross volume impregnation method, when metal promoter used is for adopting step impregnation method time two or more, also can adopt common dipping method, after dipping, drying steps and calcination steps can be comprised.Drying steps is dry 8-24 hour at 50-150 DEG C, and calcination steps is roasting 2-10 hour at 500-1000 DEG C.In the catalyst of preparation, the weight percentage of metal promoter is 0.5%-6%, preferred 1%-3%.
In the preparation method of syngas conversion catalyst of the present invention, in final catalyst, the weight percentage of cobalt is 5%-35%.
Syngas conversion catalyst of the present invention is carrier with silica gel, take cobalt as active component, using one or more in Re, Zr, Hf, Ce, Ni, Mo and W as metal promoter, adopts said method of the present invention to prepare.
Compared with prior art, the preparation method of syngas conversion catalyst of the present invention and catalyst tool have the following advantages:
1, directly sealing roasting is carried out after the impregnated activated component Co of silica-gel carrier in the inventive method, not only simplify preparation process and syngas conversion catalyst can be made to be placed in the acid atmosphere (decomposition of steam and active component nitrate) with certain pressure, while carrying out roasting, surface modification and expanding treatment are carried out to silica-gel carrier, in addition, due to the existence of steam partial pressure, can promote that active component and metal promoter are with the interaction between silica-gel carrier, generate the silicate compound of indissoluble, reduce the effect on active component cobalt and silica-gel carrier surface in Fischer-Tropsch synthesis process, improve the stability of catalyst,
2, the inventive method is without the need to carrying out special pretreatment to silica-gel carrier, avoid strong acid used in preprocessing process, strong base solution to the corrosion of catalyst support surface and the damage to carrier surface structure thereof, it also avoid a large amount of waste liquids of generating in preprocessing process to the pollution of environment simultaneously;
3, the inventive method is directly carried out in the process of roasting after load active component, can play the effect of hydrothermal treatment consists to carrier surface, and improve the decentralization of the rear active component Co of reduction, obtained catalyst has high stability and high activity.
Detailed description of the invention
Process and the effect of the inventive method is further illustrated below in conjunction with embodiment.
Example 1
(pore volume is 1.06ml/g, and specific area is 386.81m to take commercial silica gel
2/ g, following examples all use this silica gel) 30g, drip distilled water to just moistening, the volume consuming water is 48ml.By final catalyst zirconium content 1wt%, take nitrate trihydrate zirconium 1.41g, adding distil water, to 48g, is treated to dissolve completely, is added in carrier silica gel and flood, aging 3 hours, drying 8 hours at 150 DEG C, roasting 10 hours in 600 DEG C.By final catalyst cobalt content 5wt%, take cobalt nitrate hexahydrate 7.41g, adding distil water, to 48g, is treated to dissolve completely, adds in the sample after above-mentioned dipping zirconium, directly in 280 DEG C, seals roasting 10 hours after aging 3 hours.Gained catalyst is designated as CFT-1.
Catalyst Evaluation Test is in high pressure CSTR, and using paraffin as solvent, to reduce 12 hours at pure hydrogen 350 DEG C, pressure is 1.0MPa.After cooling, switching and merging gas reacts.Reaction effluent is collected by hot trap, cold-trap respectively.Reaction condition is 180-250 DEG C, 2.5Nm
3/ h/kgcat., 2.0MPa, H
2/ CO=2(mol ratio).CFT-1 catalyst Fischer-Tropsch synthesis result is as shown in table 1.
Example 2
Take commercial silica gel 30g, drip distilled water to just moistening, the volume consuming water is 48ml.By final catalyst zirconium content 3wt%, take nitrate trihydrate zirconium 4.23g, adding distil water, to 48g, is treated to dissolve completely, is added in carrier silica gel and flood, aging 3 hours, drying 10 hours at 100 DEG C, roasting 2 hours in 900 DEG C.By final catalyst cobalt content 35wt%, take cobalt nitrate hexahydrate 25.94, adding distil water, to 48g, in the sample after dissolving add above-mentioned dipping zirconium completely, directly seals roasting 2 hours after aging 3 hours in 600 DEG C.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 commercial silica gel 30g, drip distilled water to just moistening, the volume consuming water is 48ml.By final catalyst zirconium content 2wt%, take nitrate trihydrate zirconium 2.82g, adding distil water, to 48g, is treated to dissolve completely, is added in carrier silica gel and flood, aging 3 hours, drying 24 hours at 150 DEG C, roasting 4 hours in 800 DEG C.By final catalyst cobalt content 20wt%, take cobalt nitrate hexahydrate 29.64g, adding distil water, to 48g, is treated to dissolve completely, adds in the sample after above-mentioned dipping zirconium, directly in 350 DEG C, seals roasting 4 hours after aging 3 hours.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 commercial silica gel 30g, drip distilled water to just moistening, the volume consuming water is 48ml.By final catalyst W content 2wt%, take ammonium metatungstate 0.86g, adding distil water, to 48g, is treated to dissolve completely, is added in silica-gel carrier, aging 3 hours, drying 18 hours at 90 DEG C, roasting 6 hours in 700 DEG C.By final catalyst cobalt content 20wt%, take cobalt nitrate hexahydrate 29.64g, adding distil water, to 48g, is treated to dissolve completely, adds in the sample after above-mentioned dipping tungsten, directly roasting 4 hours in 350 DEG C after aging 3 hours.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 commercial silica gel 30g, drip distilled water to just moistening, the volume consuming water is 48ml.By final catalyst molybdenum content 2wt%, take ammonium molybdate 1.1g, adding distil water, to 48g, is treated to dissolve completely, is added in silica-gel carrier, aging 3 hours, drying 20 hours at 60 DEG C, roasting 4 hours in 800 DEG C.By final catalyst cobalt content 20wt%, take cobalt nitrate hexahydrate 29.64g, adding distil water, to 48g, is treated to dissolve completely, adds in the sample after above-mentioned dipping molybdenum, directly roasting 4 hours in 350 DEG C after aging 3 hours.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
Take commercial silica gel 30g, drip distilled water to just moistening, the volume consuming water is 48ml.By final catalyst n i content 2%, take six water nickel nitrate 2.96g, adding distil water, to 48g, is treated to dissolve completely, is added in carrier silica gel and flood, aging 3 hours, drying 12 hours at 80 DEG C, roasting 4 hours in 800 DEG C.By final catalyst cobalt content 20wt%, take cobalt nitrate hexahydrate 29.64g, adding distil water, to 48g, is treated to dissolve completely, adds in the sample after above-mentioned dipping nickel, directly roasting 4 hours in 350 DEG C after aging 3 hours.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.
The reactivity worth of table 1 catalyst.
| Catalyst | 100h, CO conversion ratio (%) | 100h, CH 4Selective (wt%) | 200h, CO conversion ratio (%) | 200h ,CH 4Selective (wt%) |
| CFT-1 | 63.9 | 7.9 | 60.7 | 9.0 |
| CFT-2 | 64.6 | 7.2 | 62.6 | 8.7 |
| CFT-3 | 67.7 | 8.4 | 63.6 | 9.2 |
| CFT-4 | 63.9 | 8.7 | 59.8 | 9.8 |
| CFT-5 | 64.9 | 8.8 | 61.7 | 10.1 |
| CFT-6 | 66.5 | 8.3 | 62.8 | 9.4 |
| CB-1 | 58.7 | 10.7 | 50.9 | 12.8 |
Comparative example:
Take commercial silica gel 30g, drip distilled water to just moistening, the volume consuming water is 48ml.By final catalyst n i content 2%, take six water nickel nitrate 2.96g, adding distil water, to 48g, is treated to dissolve completely, is added in carrier silica gel and flood, aging 3 hours, 80 DEG C of dryings 12 hours, roasting 4 hours in 350 DEG C.By final catalyst cobalt content 20wt%, take cobalt nitrate hexahydrate 29.64g, adding distil water, to 48g, is treated to dissolve completely, adds in the sample after above-mentioned dipping nickel, aging 3 hours, 80 DEG C of dryings 12 hours, roasting 4 hours in 350 DEG C.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.
Claims (7)
1. a preparation method for syngas conversion catalyst, comprises following process: take silica gel as carrier, adopts impregnation metal promoter and active component Co; It is characterized in that: directly carry out sealing roasting after the impregnated activated component Co of described silica-gel carrier, sintering temperature is 280-600 DEG C, and roasting time is 2-12h.
2. in accordance with the method for claim 1, it is characterized in that: described metal promoter comprises one or more in Ni, Mo, W, Re, Zr, Hf, Ce or Th, the dipping process of metal promoter adopts equi-volume impregnating or crosses volume impregnation method.
3. in accordance with the method for claim 1, it is characterized in that: the weight percentage of metal promoter in the catalyst of preparation is 0.5%-6%.
4. in accordance with the method for claim 1, it is characterized in that: the weight percentage of metal promoter in the catalyst of preparation is 1%-3%.
5. in accordance with the method for claim 1, it is characterized in that: described silica-gel carrier adopts prior art preparation or adopts commercially available silica-gel carrier.
6. in accordance with the method for claim 1, it is characterized in that: the weight percentage of described active component Co in the catalyst of preparation is 5%-35%.
7. a syngas conversion catalyst is carrier with silica gel, is active component, it is characterized in that with cobalt: syngas conversion catalyst adopts method preparation described in arbitrary claim in claim 1 to 6.
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| CN1454714A (en) * | 2003-05-29 | 2003-11-12 | 中国科学院山西煤炭化学研究所 | Method of preparing cobalt-base Fischer-Tropsch synthetic catalyst |
| CN1508073A (en) * | 2002-12-19 | 2004-06-30 | 石油大学(北京) | Fluidized photo catalytic reactor and process for purifying waste water using same |
| CN101020137A (en) * | 2006-02-15 | 2007-08-22 | 中国石油天然气股份有限公司 | Catalyst for preparing heavy hydrocarbon with synthetic gas and its prepn process |
| CN101327442A (en) * | 2008-07-30 | 2008-12-24 | 中国科学院山西煤炭化学研究所 | Hydrocarbon catalyst containing high content isomeric hydrocarbon prepared from synthesis gas and preparation method and use |
| CN101920204A (en) * | 2009-06-09 | 2010-12-22 | 中国石油化工股份有限公司 | Preparation method of cobalt-based Fischer-Tropsch synthesis catalyst |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1508073A (en) * | 2002-12-19 | 2004-06-30 | 石油大学(北京) | Fluidized photo catalytic reactor and process for purifying waste water using same |
| CN1454714A (en) * | 2003-05-29 | 2003-11-12 | 中国科学院山西煤炭化学研究所 | Method of preparing cobalt-base Fischer-Tropsch synthetic catalyst |
| CN101020137A (en) * | 2006-02-15 | 2007-08-22 | 中国石油天然气股份有限公司 | Catalyst for preparing heavy hydrocarbon with synthetic gas and its prepn process |
| CN101327442A (en) * | 2008-07-30 | 2008-12-24 | 中国科学院山西煤炭化学研究所 | Hydrocarbon catalyst containing high content isomeric hydrocarbon prepared from synthesis gas and preparation method and use |
| CN101920204A (en) * | 2009-06-09 | 2010-12-22 | 中国石油化工股份有限公司 | Preparation method of cobalt-based Fischer-Tropsch synthesis catalyst |
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