CN103769100B - A kind of fischer-tropsch synthetic catalyst and its preparation method and application - Google Patents
A kind of fischer-tropsch synthetic catalyst and its preparation method and application Download PDFInfo
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- CN103769100B CN103769100B CN201210408285.3A CN201210408285A CN103769100B CN 103769100 B CN103769100 B CN 103769100B CN 201210408285 A CN201210408285 A CN 201210408285A CN 103769100 B CN103769100 B CN 103769100B
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Abstract
The present invention discloses a kind of Co based Fischer-Tropsch synthesis catalyst and its preparation method and application.Co based Fischer-Tropsch synthesis catalyst take silica gel as carrier, by the weight content of catalyst, metal promoter containing 0.5%-6%, the active component cobalt of 5%-35%, described metal promoter is one or more in Re, Zr, Hf, Ce and Th etc., and described silica-gel carrier is the silica-gel carrier of hot hydrogen process, and the temperature of hot hydrogen is 350-650 DEG C, processing time 1-30h, the air speed of hot hydrogen is 1000h
-1-2000h
-1.The method preparation process is simple, and catalyst demonstrates excellent activity stability under the operating condition of long period and high-speed, is suitable for commercial Application.
Description
Technical field
The present invention relates to a kind of Co based Fischer-Tropsch synthesis catalyst and its preparation method and application, relating in particular to a kind of is carrier with modified silica-gel, adds the preparation method of the Co based Fischer-Tropsch synthesis catalyst of the high-activity stable that metal promoter is modified.
Background technology
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 Zr, K and Cu plays an important role to the activity of fischer-tropsch catalysts, stability, and the carrier of catalyst is 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, therefore, the research based on cobalt-base catalyst is significant.
CN1454714A discloses a kind of preparation method of Co based Fischer-Tropsch synthesis catalyst, and the method adopts the ammonia spirit of 1%-25% to SiO
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 certain destruction to the surface of catalyst carrier, and some modifier also may introduce some impurity metal ions.
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.
In the preparation method of Co based Fischer-Tropsch synthesis catalyst disclosed in CN200910011990.8, CN200910011989.5, CN200910011988.0, take silica gel as carrier, first surface modification is carried out to silica-gel carrier, then adopt infusion process carried metal auxiliary agent and active component Co; Wherein the surface modifying method of silica-gel carrier adopts the acid solution of the cushioning liquid of ammonium salt-containing, organic compounds containing nitrogen solution and sugar to carry out impregnation process respectively.Said method is reducing Fischer-Tropsch synthesis temperature, is avoiding strong acid or strong alkali solution in support modification process to the corrosion on its surface and the damage to carrier hole structure, to improve the aspect such as catalyst life and activity and achieve significant progress.But along with deeply carrying out of research, find that catalyst that above-mentioned preparation method obtains is under the operating condition of long period and high-speed, the activity stability of catalyst still needs further to be improved.
Summary of the invention
For the deficiencies in the prior art, particularly under the operating condition of long period and high-speed, Co based Fischer-Tropsch synthesis catalyst also exists the undesirable problem of activity stability, the present invention discloses a kind of Co based Fischer-Tropsch synthesis catalyst and its preparation method and application, the method preparation process is simple, catalyst demonstrates excellent activity stability under the operating condition of long period and high-speed, is suitable for commercial Application.
A kind of Co based Fischer-Tropsch synthesis catalyst, take silica gel as carrier, by the weight content of catalyst, metal promoter containing 0.5%-6%, the active component cobalt of 5%-35%, described metal promoter is one or more in Re, Zr, Hf, Ce and Th etc., described silica-gel carrier is the silica-gel carrier of hot hydrogen process, the temperature of hot hydrogen is 350-650 DEG C, processing time 1-30h, and the air speed of hot hydrogen is 1000 h
-1-2000 h
-1.
By the metal promoter of the weight content of catalyst containing 1%-3% in Co based Fischer-Tropsch synthesis catalyst of the present invention, described auxiliary agent is zirconium.
In Co based Fischer-Tropsch synthesis catalyst of the present invention, silica-gel carrier is the silica-gel carrier of hot hydrogen process, and in processing procedure, Stress control is 0.5-2.5 MPa.
A preparation method for Co based Fischer-Tropsch synthesis catalyst, comprises following process: take silica gel as carrier, first carries out pretreatment to silica-gel carrier, then adopts infusion process carried metal auxiliary agent and active component Co; Wherein the preprocess method of silica-gel carrier is in silica-gel carrier, pass into the hot hydrogen that temperature is 350-650 DEG C, processing time 1-30h, and the air speed of hot hydrogen is 1000 h
-1-2000 h
-1.
The preprocess method of the silica-gel carrier described in the inventive method is in silica-gel carrier, pass into the hot hydrogen that temperature is 400-600 DEG C, and the processing time is no less than 10h, and the air speed of hot hydrogen is 1200 h
-1-1800 h
-1.
In the inventive method, in processing procedure, Stress control is 0.5-2.5 MPa, preferred 1.0-2.0 MPa.
In the inventive method, hot hydrogen preprocessing process can carry out in fixed bed reactors, needs to carry out gas displacement before passing into hot hydrogen, ensures that the volumetric concentration of fixing in-bed oxygen is less than 99.9%.Hot hydrogen comes from hydrogen heating furnace.
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 the dry microspheres of macropore or pore, silica gel can adopt commodity on demand, also can prepare by existing method.
In the preparation method of Co based Fischer-Tropsch synthesis catalyst of the present invention, metal promoter can be one or more in Re, Zr, Hf, Ce and Th etc., preferred Zr.The preferred first impregnating metal auxiliary agent of carrying method of metal promoter and active component Co, the then step impregnation method of impregnated activated component Co.The dipping process of metal promoter and active component Co can adopt method well known to those skilled in the art.As adopted following process: first adopt the solution impregnation modified silica gel carrier containing auxiliary element salt, then adopting the solution impregnation containing active metal component Co salt, often can comprise drying steps and calcination steps after step dipping.Drying steps is dry 8-24 hour at 50-150 DEG C, and calcination steps is roasting 2-10 hour at 280-600 DEG C.In the catalyst of preparation, the weight percentage of metal promoter zirconium is 0.5%-6%, and preferred 1%-3%, the weight percentage of cobalt is 5%-35%.
The application of above-mentioned Co based Fischer-Tropsch synthesis catalyst in Fischer-Tropsch synthesis.
Find through research, the rich surface of silica-gel carrier is containing abundant organic group, and in these organic groups, some may belong to the organic group of oxidisability; In addition, silica gel can be introduced industrial production silica gel in some anion, particularly prior art and usually use sulfuric acid in preparation process, and at this moment inevitable have a large amount of sulfate ions at silica-gel carrier remained on surface.The effect of above-described oxidation organic group and anion and metal active constituent is stronger, therefore, these oxidisability organic groups and anion likely in dipping process or long time running time have an effect with active component, affect the decentralization of metal active constituent on silica-gel carrier, reduction degree and activity stability.
Compared with prior art, first the present invention adopts the hydrogen of high temperature to carry out pretreatment to silica-gel carrier, and then preparation method's tool of carried metal auxiliary agent and active component cobalt has the following advantages:
1, the inventive method can effectively reduce Silica Surface reactive species and prepare silica-gel carrier time the anion particularly sulfate ion introduced, reduce kind and the quantity of Silica Surface reactive species and anion, decrease Silica Surface reactive species and the strong interaction of anion to active component in load active component cobalt and long-time course of reaction, improve the decentralization of catalyst, reproducibility and activity stability;
2, the structural deterioration of the inventive method to silica-gel carrier is little, substantially remains original physical property of silica-gel carrier, and preparation is simple, and mature technology, is conducive to the industrial production of catalyst;
3, the catalyst prepared of the inventive method is under high-speed and macrocyclic operating condition, and demonstrate excellent activity stability, result of the test shows, is 2000 h in synthesis gas air speed
-1, device operates 500 hours, and the conversion ratio of CO, still up to more than 50%, improves more than 10% than prior art.
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, the every 10 grams of volumes dripping consumption water when distilled water extremely just moistens of this silica gel are 16ml, following examples all use this silica gel) 30g, load in fixed bed reactors, through gas displacement to ensure that the volumetric concentration of fixing in-bed oxygen passes into hot hydrogen after being less than 99.9%, the hot hydrogen temperature coming from hydrogen heating furnace is 500 DEG C, and volume space velocity is 1500 h
-1, the processing time is 15h, and system pressure is 1.5MPa.By final catalyst zirconium content 3wt%, take zirconium nitrate and be dissolved in 48ml, add in above-mentioned modified carrier silica gel and flood, aging 3 hours, 80 DEG C of dryings 8 hours, roasting 4 hours in 350 DEG C.By final catalyst cobalt content 20wt%, take cobalt nitrate and be dissolved in 48ml, add in the sample after above-mentioned dipping zirconium, aging 3 hours, 80 DEG C of dryings 8 hours, roasting 4 hours in 350 DEG C.Gained catalyst is designated as C-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 220 DEG C, 2000h
-1, 2.0MPa, H
2/ CO=2(mol ratio).When the duration of runs is 500h, C-1 catalyst Fischer-Tropsch synthesis result is as shown in table 1.
Example 2
Take commercial silica gel 30g, load in fixed bed reactors, through gas displacement to ensure that the volumetric concentration of fixing in-bed oxygen passes into hot hydrogen after being less than 99.9%, the hot hydrogen temperature coming from hydrogen heating furnace is 350 DEG C, and volume space velocity is 1200 h
-1, the processing time is 10h, and system pressure is 1.0MPa.By final catalyst zirconium content 1wt%, take zirconium nitrate and be dissolved in 48ml, add in above-mentioned modified carrier silica gel and flood, aging 3 hours, 80 DEG C of dryings 8 hours, roasting 4 hours in 350 DEG C.By final catalyst cobalt content 10wt%, take cobalt nitrate and be dissolved in 48ml, add in the sample after above-mentioned dipping zirconium, aging 3 hours, 80 DEG C of dryings 8 hours, roasting 4 hours in 350 DEG C.Gained catalyst is designated as C-2.Catalyst activity evaluation experimental condition is with embodiment 1.C-2 catalyst Fischer-Tropsch synthesis result is as shown in table 1.
Example 3
Take commercial silica gel 30g, load in fixed bed reactors, through gas displacement to ensure that the volumetric concentration of fixing in-bed oxygen passes into hot hydrogen after being less than 99.9%, the hot hydrogen temperature coming from hydrogen heating furnace is 400 DEG C, and volume space velocity is 1600 h
-1, the processing time is 20h, and system pressure is 1.5MPa.By final catalyst zirconium content 6wt%, take zirconium nitrate and be dissolved in 48ml, add in above-mentioned modified carrier silica gel and flood, aging 3 hours, 80 DEG C of dryings 8 hours, roasting 4 hours in 350 DEG C.By final catalyst cobalt content 5wt%, take cobalt nitrate and be dissolved in 48ml, add in the sample after above-mentioned dipping zirconium, aging 3 hours, 80 DEG C of dryings 8 hours, roasting 4 hours in 350 DEG C.Gained catalyst is designated as C-3.Catalyst activity evaluation experimental condition is with embodiment 1.C-3 catalyst Fischer-Tropsch synthesis result is as shown in table 1.
Example 4
Take commercial silica gel 30g, load in fixed bed reactors, through gas displacement to ensure that the volumetric concentration of fixing in-bed oxygen passes into hot hydrogen after being less than 99.9%, the hot hydrogen temperature coming from hydrogen heating furnace is 450 DEG C, and volume space velocity is 1800 h
-1, the processing time is 25h, and system pressure is 2MPa.By final catalyst zirconium content 4wt%, take zirconium nitrate and be dissolved in 48ml, add in above-mentioned modified carrier silica gel and flood, aging 3 hours, 80 DEG C of dryings 8 hours, roasting 4 hours in 350 DEG C.By final catalyst cobalt content 15wt%, take cobalt nitrate and be dissolved in 48ml, add in the sample after above-mentioned dipping zirconium, aging 3 hours, 80 DEG C of dryings 8 hours, roasting 4 hours in 350 DEG C.Gained catalyst is designated as C-4.Catalyst activity evaluation experimental condition is with embodiment 1.C-4 catalyst Fischer-Tropsch synthesis result is as shown in table 1.
Example 5
Take commercial silica gel 30g, load in fixed bed reactors, through gas displacement to ensure that the volumetric concentration of fixing in-bed oxygen passes into hot hydrogen after being less than 99.9%, the hot hydrogen temperature coming from hydrogen heating furnace is 550 DEG C, and volume space velocity is 2000 h
-1, the processing time is 30h, and system pressure is 2.5MPa.By final catalyst zirconium content 5wt%, take zirconium nitrate and be dissolved in 48ml, add in above-mentioned modified carrier silica gel and flood, aging 3 hours, 80 DEG C of dryings 8 hours, roasting 4 hours in 350 DEG C.By final catalyst cobalt content 25wt%, take cobalt nitrate and be dissolved in 48ml, add in the sample after above-mentioned dipping zirconium, aging 3 hours, 80 DEG C of dryings 8 hours, roasting 4 hours in 350 DEG C.Gained catalyst is designated as C-5.Catalyst activity evaluation experimental condition is with embodiment 1.C-5 catalyst Fischer-Tropsch synthesis result is as shown in table 1.
Example 6
Take commercial silica gel 30g, load in fixed bed reactors, through gas displacement to ensure that the volumetric concentration of fixing in-bed oxygen passes into hot hydrogen after being less than 99.9%, the hot hydrogen temperature coming from hydrogen heating furnace is 600 DEG C, and volume space velocity is 1500 h
-1, the processing time is 20h, and system pressure is 1.5MPa.By final catalyst zirconium content 2wt%, take zirconium nitrate and be dissolved in 48ml, add in above-mentioned modified carrier silica gel and flood, aging 3 hours, 80 DEG C of dryings 8 hours, roasting 4 hours in 350 DEG C.By final catalyst cobalt content 30wt%, take cobalt nitrate and be dissolved in 48ml, add in the sample after above-mentioned dipping zirconium, aging 3 hours, 80 DEG C of dryings 8 hours, roasting 4 hours in 350 DEG C.Gained catalyst is designated as C-6.Catalyst activity evaluation experimental condition is with embodiment 1.C-6 catalyst Fischer-Tropsch synthesis result is as shown in table 1.
Example 7
Take commercial silica gel 30g, load in fixed bed reactors, through gas displacement to ensure that the volumetric concentration of fixing in-bed oxygen passes into hot hydrogen after being less than 99.9%, the hot hydrogen temperature coming from hydrogen heating furnace is 450 DEG C, and volume space velocity is 1000 h
-1, the processing time is 15h, and system pressure is 2MPa.By final catalyst zirconium content 1.5wt%, take zirconium nitrate and be dissolved in 48ml, add in above-mentioned modified carrier silica gel and flood, aging 2 hours, 50 DEG C of dryings 24 hours, roasting 10 hours in 280 DEG C.By final catalyst cobalt content 35wt%, take cobalt nitrate and be dissolved in 48ml, add in the sample after above-mentioned dipping zirconium, aging 3 hours, 80 DEG C of dryings 8 hours, roasting 4 hours in 350 DEG C.Gained catalyst is designated as C-7.Catalyst activity evaluation experimental condition is with embodiment 1.C-7 catalyst Fischer-Tropsch synthesis result is as shown in table 1.
Comparative example 1
According to the method for preparing catalyst of CN200910011988.0, obtain catalyst and be designated as C-B1, the composition of this catalyst is with example 1, and catalyst activity evaluation experimental condition is with embodiment 1.Evaluation result is in table 1.
Than example 2
According to the method for preparing catalyst of CN200910011989.5, obtain catalyst and be designated as C-B2, the composition of this catalyst is with example 1, and catalyst activity evaluation experimental condition is with embodiment 1.Evaluation result is in table 1.
Table 1
| Catalyst | CO conversion ratio (%) | C 5 +Selective (wt%) |
| C-1 | 56.5 | 84.8 |
| C-B1 | 42.2 | 82.5 |
| C-B2 | 44.5 | 81.7 |
| C-2 | 57.1 | 83.9 |
| C-3 | 53.4 | 84.9 |
| C-4 | 52.5 | 85.5 |
| C-5 | 51.5 | 83.7 |
| C-6 | 54.5 | 83.2 |
| C-7 | 58.5 | 84.7 |
Claims (10)
1. a Co based Fischer-Tropsch synthesis catalyst, take silica gel as carrier, by the weight content of catalyst, metal promoter containing 0.5%-6%, the active component cobalt of 5%-35%, described metal promoter is one or more in Re, Zr, Hf, Ce and Th, it is characterized in that: described silica-gel carrier is the silica-gel carrier of hot hydrogen process, the temperature of hot hydrogen is 350-650 DEG C, processing time 1-30h, and the air speed of hot hydrogen is 1000 h
-1-2000 h
-1.
2. catalyst according to claim 1, is characterized in that: by the metal promoter of the weight content of catalyst containing 1%-3% in described Co based Fischer-Tropsch synthesis catalyst, and described auxiliary agent is zirconium.
3. catalyst according to claim 1, is characterized in that: in described Co based Fischer-Tropsch synthesis catalyst, in silica-gel carrier hot hydrogen processing procedure, Stress control is 0.5-2.5 MPa.
4. the preparation method of Co based Fischer-Tropsch synthesis catalyst according to claim 1, comprises following process: take silica gel as carrier, first carry out pretreatment to silica-gel carrier, then adopts infusion process carried metal auxiliary agent and active component Co; It is characterized in that: wherein the preprocess method of silica-gel carrier is in silica-gel carrier, pass into the hot hydrogen that temperature is 350-650 DEG C, processing time 1-30h, the air speed of hot hydrogen is 1000h
-1-2000h
-1.
5. method according to claim 4, is characterized in that: the preprocess method of described silica-gel carrier is in silica-gel carrier, pass into the hot hydrogen that temperature is 400-600 DEG C, and the processing time is no less than 10h, and the air speed of hot hydrogen is 1200h
-1-1800h
-1.
6. method according to claim 4, is characterized in that: in hot hydrogen processing procedure, Stress control is 0.5-2.5 MPa.
7. method according to claim 4, it is characterized in that: hot hydrogen preprocessing process carries out in fixed bed reactors, need before passing into hot hydrogen to carry out gas displacement, ensure that the volumetric concentration of fixing in-bed oxygen is less than 99.9%, hot hydrogen comes from hydrogen heating furnace.
8. in accordance with the method for claim 4, it is characterized in that: described metal promoter is one or more in Re, Zr, Hf, Ce and Th, the weight percentage of metal promoter is 0.5%-6%; The weight percentage of described active component cobalt is 5%-35%.
9. in accordance with the method for claim 4, it is characterized in that: metal promoter and active component Co adopt first impregnating metal auxiliary agent, then the step impregnation method of impregnated activated component Co.
10. the application of catalyst in Fischer-Tropsch synthesis described in the arbitrary claim of claims 1 to 3.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1031375A2 (en) * | 1999-02-24 | 2000-08-30 | CPC Cellular Process Chemistry Systems GmbH | Microreactor |
| US6765025B2 (en) * | 2002-01-17 | 2004-07-20 | Dalian Institute Of Chemical Physics, Chinese Academy Of Science | Process for direct synthesis of diesel distillates with high quality from synthesis gas through Fischer-Tropsch synthesis |
| WO2008147014A3 (en) * | 2007-05-29 | 2009-03-19 | Korea Res Inst Chem Tech | Synthetic methods for liquid hydrocarbons from syngas over alumina-silica based catalysts and preparation methods thereof |
| CN101920200A (en) * | 2009-06-09 | 2010-12-22 | 中国石油化工股份有限公司 | Method for preparing long-life cobalt-based catalyst for Fischer-Tropsch synthesis |
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| US8268046B2 (en) * | 2008-05-16 | 2012-09-18 | Matheson Tri-Gas | Removal of impurities from hydrogen-containing materials |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1031375A2 (en) * | 1999-02-24 | 2000-08-30 | CPC Cellular Process Chemistry Systems GmbH | Microreactor |
| US6765025B2 (en) * | 2002-01-17 | 2004-07-20 | Dalian Institute Of Chemical Physics, Chinese Academy Of Science | Process for direct synthesis of diesel distillates with high quality from synthesis gas through Fischer-Tropsch synthesis |
| WO2008147014A3 (en) * | 2007-05-29 | 2009-03-19 | Korea Res Inst Chem Tech | Synthetic methods for liquid hydrocarbons from syngas over alumina-silica based catalysts and preparation methods thereof |
| CN101920200A (en) * | 2009-06-09 | 2010-12-22 | 中国石油化工股份有限公司 | Method for preparing long-life cobalt-based catalyst for Fischer-Tropsch synthesis |
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