CN102861580A - Preparation method for conversing catalyst by synthetic gas - Google Patents
Preparation method for conversing catalyst by synthetic gas Download PDFInfo
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Abstract
The invention relates to a preparation method for conversing a catalyst by synthetic gas, silica gel is taken as a carrier, an immersion method is used for dipping a metal auxiliary agent and an active component Co; wherein, the silica gel carrier dips the active component Co and is directly sealed and roasted, the roasting temperature is 280-600 DEG C, and the roasting time is 2-12 hours. According to the invention, acid, alkali and an organic solvent are not used for treating the carrier, the synthetic gas conversed by the prepared synthetic gas has high activity and good stability, and the preparation method is simple.
Description
Technical field
The present invention relates to a kind of preparation method of syngas conversion catalyst, relate in particular to a kind of preparation method of the Co based Fischer-Tropsch synthesis catalyst take silica gel as carrier.
Background technology
Synthetic synthesis gas (the CO+H that refers to of Fischer-Tropsch
2) catalyze and synthesize the reaction of liquid hydrocarbon fuel at catalyst.Day by day exhaustion 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 nearly 80 years fischer-tropsch catalysts, people have found that Fe, Co and Ru etc. are the effective active components of fischer-tropsch catalysts, the various auxiliary elements such as Ru, Zr, K and Cu play an important role to activity, the stability of fischer-tropsch catalysts, and the carrier of catalyst is generally with unformed SiO
2, TiO
2And Al
2O
3Be main.How active component, metal promoter and carrier are carried out effective and reasonable collocation, prepare have high activity, the fischer-tropsch synthetic catalyst of high selectivity and high stability is the focus of research.Use cobalt-base catalyst can not only generate to greatest extent heavy hydrocarbon, and cobalt-base catalyst carbon deposit tendency is low, active high, therefore significant take cobalt-base catalyst as the research on basis.But metallic cobalt generates cobaltous silicate, cobalt titanate and cobalt aluminate compounds with above-mentioned carrier generation chemical action easily in the cobalt-base catalyst, has reduced the activity and selectivity of catalyst, so that the content of methane in product increases considerably C
5 +Selective decrease.When catalyst in slurry attitude bed and fixed bed during long time running, hydrothermal meeting further promotes the reaction of active component cobalt and carrier, affects life-span and the activity of catalyst.Therefore, mostly adopt at present acid, alkali and organic solvent etc. that carrier is carried out modification, reduce the interaction between carrier and catalyst activity component, improve life-span and the activity of catalyst.
CN1509816A has reported a kind of SiO
2The processing method of carrier is with one or more mixed solution treatment S iO of carbonate, bicarbonate, formates and the acetate of solution, alkali metal and the ammonia of the hydroxide of alkali metal and ammonia
2Then carrier makes modification SiO after drying, the roasting
2Carrier.Use the ammonia spirit of 1%-25% to SiO among the CN1454714A
2Carrier aged at room temperature 6-150 hour, 100-150 ℃ of lower baking carried out surface modification in 8-24 hour, improved the activity of Co based Fischer-Tropsch synthesis catalyst, and at 220 ℃, under the 2MPa, the CO conversion ratio is 90.1%, C
5 +Selectively be 85.7%.The hydroxide of alkali metal and ammonia can have to the surface of catalyst carrier obvious destruction, and some modifier also may be introduced 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 ~ 304 " research of the absorption of chemical modification alumina load cobalt-base catalyst and reflex action "
2O
3The reactivity worth of the fischer-tropsch synthetic catalyst of carrier loaded cobalt.Point out that ammonia modification alumina load Co catalysts can promote activity and C
5 +The raising of hydrocarbon-selective, and acetic acid is modified activity and carbon chain growth that aluminium oxide can be restrained Co catalysts.But experiment shows that ammonia destroys obviously the pore structure of carrier, and the carrier of sour modification has strengthened the interaction between cobalt and the carrier.
CN200480041633.1 discloses a kind of fischer-tropsch synthetic catalyst support modification method, processes with single silicate solution at alumina carrier surface, improving the intensity of catalyst, but does not improve the interaction between reactive metal and the carrier.
Shi Lihong etc. utilize the silanization effect to make alkyl-modified SiO in " catalysis journal " the 28th 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 the organic group modification, improved the activity of catalyst, reduced methane selectively, but because sterically hindered effect can affect the product distribution.
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 to burning, burn off organic cosolvent under oxygen-containing atmosphere, obtain a kind of powder product, at last in the presence of air, with roasting 0.5-36 hour the method preparation in 100-1000 ℃ of described powder product.Use therein organic cosolvent is one or more in organic amine, organic acid, the 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
2Preparation method for the syngas conversion catalyst of carrier.The inventive method need not to use acid, alkali and organic solvent etc. that carrier surface is processed, and the syngas conversion catalyst of preparation is not only active high, good stability, and also the preparation method is simple.
A kind of preparation method of syngas conversion catalyst comprises following process: take silica gel as carrier, adopt infusion process impregnating metal auxiliary agent and active component Co; Wherein directly seal roasting behind the silica-gel carrier dipping active component Co, sintering temperature is 280-600 ℃, and roasting time is 2-12h.
Sealing roasting described in the inventive method is the roasting process of pressurization, and described roasting 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 such as 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 syngas conversion catalyst of the present invention, metal promoter is one or more among Ni, Mo, W, Re, Zr, Hf, Ce and the Th etc., the dipping process of metal promoter adopts conventional dipping method, for example adopt equi-volume impregnating or cross the volume infusion process, when used metal promoter can adopt step impregnation method during for two or more, also total immersion stain method can be adopted, drying steps and calcination steps can be comprised behind the dipping.Drying steps descended dry 8-24 hour at 50-150 ℃, and calcination steps was at 500-1000 ℃ of lower roasting 2-10 hour.The weight percentage of metal promoter is 0.5%-6% in the catalyst of preparation, preferred 1%-3%.
Among the preparation method of syngas conversion catalyst of the present invention, the weight percentage of cobalt is 5%-35% in the final catalyst.
Syngas conversion catalyst of the present invention is take silica gel as carrier, take cobalt as active component, as metal promoter, adopts said method preparation of the present invention with among Re, Zr, Hf, Ce, Ni, Mo and the W one or more.
Compared with prior art, the preparation method of syngas conversion catalyst of the present invention and catalyst have following advantage:
1, directly seal roasting behind the silica-gel carrier dipping active component Co in the inventive method, not only simplified preparation process but also syngas conversion catalyst is placed the acid atmosphere (decomposition of steam and active component nitrate) with certain pressure, when carrying out roasting, silica-gel carrier is carried out surface modification and reaming processing, in addition, because the existence of steam partial pressure, can promote active component and metal promoter with the interaction between silica-gel carrier, generate the silicate compound of indissoluble, the effect on active component cobalt and silica-gel carrier surface in the reduction Fischer-Tropsch synthesis process, the stability of raising catalyst;
2, the inventive method need not silica-gel carrier is carried out special preliminary treatment, avoid strong acid used in the preprocessing process, strong base solution to the corrosion on catalyst carrier surface and to the damage of carrier surface structure, also avoided a large amount of waste liquids that generate in the preprocessing process to the pollution of environment simultaneously;
3, the inventive method is directly carried out behind load active component in the process of roasting, can play to carrier surface the effect of hydrothermal treatment consists, improves the decentralization of the rear active component Co of reduction, and the catalyst that makes has high stability and high activity.
The specific embodiment
Further specify 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 by weighing 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.By final catalyst zirconium content 1wt%, take by weighing nitrate trihydrate zirconium 1.41g, adding distil water is treated to dissolve fully to 48g, add in the carrier silica gel to flood, aging 3 hours, 150 ℃ lower dry 8 hours, roasting is 10 hours in 600 ℃.By final catalyst cobalt content 5wt%, take by weighing cobalt nitrate hexahydrate 7.41g, adding distil water is treated to dissolve fully to 48g, adds in the sample behind the above-mentioned dipping zirconium, aging directly sealing roasting 10 hours in 280 ℃ after 3 hours.The gained catalyst is designated as CFT-1.
The evaluating catalyst test is in the high pressure CSTR, and as solvent, with 350 ℃ of lower reduction of pure hydrogen 12 hours, pressure was 1.0MPa with paraffin.Switching synthesis gas after the 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).The result is as shown in table 1 for CFT-1 catalyst Fischer-Tropsch synthesis.
Example 2
Take by weighing commercially available silica gel 30g, drip distilled water to just moistening, the volume that consumes water is 48ml.By final catalyst zirconium content 3wt%, take by weighing nitrate trihydrate zirconium 4.23g, adding distil water is treated to dissolve fully to 48g, add in the carrier silica gel to flood, aging 3 hours, 100 ℃ lower dry 10 hours, roasting is 2 hours in 900 ℃.By final catalyst cobalt content 35wt%, take by weighing cobalt nitrate hexahydrate 25.94, adding distil water, wears out and directly seal roasting 2 hours after 3 hours in 600 ℃ in the sample that dissolves fully after adding above-mentioned dipping zirconium to 48g.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.
Example 3
Take by weighing commercially available silica gel 30g, drip distilled water to just moistening, the volume that consumes water is 48ml.By final catalyst zirconium content 2wt%, take by weighing nitrate trihydrate zirconium 2.82g, adding distil water is treated to dissolve fully to 48g, add in the carrier silica gel to flood, aging 3 hours, 150 ℃ lower dry 24 hours, roasting is 4 hours in 800 ℃.By final catalyst cobalt content 20wt%, take by weighing cobalt nitrate hexahydrate 29.64g, adding distil water is treated to dissolve fully to 48g, adds in the sample behind the above-mentioned dipping zirconium, aging directly sealing roasting 4 hours in 350 ℃ after 3 hours.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.
Example 4
Take by weighing commercially available silica gel 30g, drip distilled water to just moistening, the volume that consumes water is 48ml.By final catalyst W content 2wt%, take by weighing ammonium metatungstate 0.86g, adding distil water is treated to dissolve fully to 48g, add in the silica-gel carrier, aging 3 hours, 90 ℃ lower dry 18 hours, roasting is 6 hours in 700 ℃.By final catalyst cobalt content 20wt%, take by weighing cobalt nitrate hexahydrate 29.64g, adding distil water is treated to dissolve fully to 48g, adds in the sample behind the above-mentioned dipping tungsten, aging directly roasting 4 hours in 350 ℃ after 3 hours.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.
Example 5
Take by weighing commercially available silica gel 30g, drip distilled water to just moistening, the volume that consumes water is 48ml.By final catalyst molybdenum content 2wt%, take by weighing ammonium molybdate 1.1g, adding distil water is treated to dissolve fully to 48g, add in the silica-gel carrier, aging 3 hours, 60 ℃ lower dry 20 hours, roasting is 4 hours in 800 ℃.By final catalyst cobalt content 20wt%, take by weighing cobalt nitrate hexahydrate 29.64g, adding distil water is treated to dissolve fully to 48g, adds in the sample behind the above-mentioned dipping molybdenum, aging directly roasting 4 hours in 350 ℃ after 3 hours.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.
Example 6
Take by weighing commercially available silica gel 30g, drip distilled water to just moistening, the volume that consumes water is 48ml.By final catalyst n i content 2%, take by weighing six water nickel nitrate 2.96g, adding distil water is treated to dissolve fully to 48g, add in the carrier silica gel to flood, aging 3 hours, 80 ℃ lower dry 12 hours, roasting is 4 hours in 800 ℃.By final catalyst cobalt content 20wt%, take by weighing cobalt nitrate hexahydrate 29.64g, adding distil water is treated to dissolve fully to 48g, adds in the sample behind the above-mentioned dipping nickel, aging directly roasting 4 hours in 350 ℃ after 3 hours.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.
The reactivity worth of table 1 catalyst.
| Catalyst | 100h, CO conversion ratio (%) | 100h, CH 4Selectively (wt%) | 200h, CO conversion ratio (%) | 200h ,CH 4Selectively (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 by weighing commercially available silica gel 30g, drip distilled water to just moistening, the volume that consumes water is 48ml.By final catalyst n i content 2%, take by weighing six water nickel nitrate 2.96g, adding distil water is treated to dissolve fully to 48g, adds in the carrier silica gel to flood, aging 3 hours, 80 ℃ of dryings 12 hours, roasting is 4 hours in 350 ℃.By final catalyst cobalt content 20wt%, take by weighing cobalt nitrate hexahydrate 29.64g, adding distil water is treated to dissolve fully to 48g, adds in the sample behind the above-mentioned dipping nickel, 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.
Claims (7)
1. the preparation method of a syngas conversion catalyst comprises following process: take silica gel as carrier, adopt infusion process impregnating metal auxiliary agent and active component Co; It is characterized in that: directly seal roasting behind the described silica-gel carrier dipping active component Co, sintering temperature is 280-600 ℃, 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 among Ni, Mo, W, Re, Zr, Hf, Ce or the Th, and the dipping process of metal promoter adopts equi-volume impregnating or crosses the volume infusion process.
3. it is characterized in that in accordance with the method for claim 1: the weight percentage of metal promoter in the catalyst of preparation is 0.5%-6%.
4. it is characterized in that in accordance with the method for claim 1: the weight percentage of metal promoter in the catalyst of preparation is 1%-3%.
5. it is characterized in that in accordance with the method for claim 1: described silica-gel carrier adopts the prior art preparation or adopts commercially available silica-gel carrier.
6. it is characterized in that in accordance with the method for claim 1: the weight percentage of described active component Co in the catalyst of preparation is 5%-35%.
7. a syngas conversion catalyst take silica gel as carrier, take cobalt as active component, is characterized in that: the described method preparation of arbitrary claim in the syngas conversion catalyst employing 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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