CN103769100A - Fischer-Tropsch synthetic catalyst, and preparation method and applications thereof - Google Patents
Fischer-Tropsch synthetic catalyst, and preparation method and applications thereof Download PDFInfo
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- CN103769100A CN103769100A CN201210408285.3A CN201210408285A CN103769100A CN 103769100 A CN103769100 A CN 103769100A CN 201210408285 A CN201210408285 A CN 201210408285A CN 103769100 A CN103769100 A CN 103769100A
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Abstract
The invention discloses a cobalt-based Fischer-Tropsch synthetic catalyst, and a preparation method and applications thereof. According to the cobalt-based Fischer-Tropsch synthetic catalyst, silica gel is taken as a carrier; the cobalt-based Fischer-Tropsch synthetic catalyst comprises, by weight, 0.5 to 6% of a metal auxiliary agent, and 5 to 35% of active component cobalt; the metal auxiliary agent is one or more selected from Re, Zr, Hf, Ce, and Th; the silica gel carrier is processed with hot hydrogen with a temperature of 350 to 650 DEG C for 1 to 30h, wherein speed of the hot hydrogen ranges from 1000/h to 2000/h. Processes of the preparation method are simple; and the Fischer-Tropsch synthetic catalyst possesses activity stability in a long term and under high speed operation conditions, and is suitable for industrialized application.
Description
Technical field
The present invention relates to a kind of Co based Fischer-Tropsch synthesis catalyst and its preparation method and application, relate in particular to one take modified silica-gel as carrier, add the preparation method of the Co based Fischer-Tropsch synthesis catalyst of the high-activity stable of metal promoter modification.
Background technology
Along with the exhaustion day by day of petroleum resources, be more subject to the attention of countries in the world with 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 effective active components of fischer-tropsch catalysts, activity, the stability of various auxiliary elements to fischer-tropsch catalysts such as Zr, K and Cu play an important role, and the carrier of catalyst is with unformed SiO
2, TiO
2and Al
2o
3be main.How active component, metal promoter and carrier are carried out to effective and reasonable collocation, prepare there is 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, take cobalt-base catalyst as basic research 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
2carrier aged at room temperature 6-150 hour, dries at 100-150 ℃ and carries out surface modification in 8-24 hour, has improved the activity of Co based Fischer-Tropsch synthesis catalyst, and at 220 ℃, under 2MPa, CO conversion ratio is 90.1%, C
5 +be selectively 85.7%.The hydroxide of alkali metal and ammonia can have certain destruction to the surface of catalyst carrier, and some modifier also may be introduced 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 oxygen-containing atmosphere to burning, burn off organic cosolvent, obtain a kind of powder product, finally under air exists, by the method preparation of roasting 0.5-36 hour in 100-1000 ℃ of described powder product.The organic cosolvent wherein using is one or more in organic amine, organic acid, organic hydrazine.The method preparation process complexity.
In the preparation method of CN200910011990.8, CN200910011989.5, the disclosed Co based Fischer-Tropsch synthesis catalyst of CN200910011988.0, take silica gel as carrier, first silica-gel carrier is carried out to surface modification, then adopt infusion process carried metal auxiliary agent and active component Co; Wherein the surface modifying method of silica-gel carrier adopts respectively the acid solution of cushioning liquid, organic compounds containing nitrogen solution and the sugar of ammonium salt-containing to carry out impregnation process.Said method strong acid or the corrosion of strong alkali solution to its surface and damage to carrier hole structure in reducing Fischer-Tropsch synthesis temperature, avoiding support modification process, improves the aspect such as catalyst life and activity and has obtained 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 at long period and high-speed, Co based Fischer-Tropsch synthesis catalyst 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 good 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, the metal promoter that contains 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 that hot hydrogen was processed, the temperature of hot hydrogen is 350-650 ℃, processing time 1-30h, and the air speed of hot hydrogen is 1000 h
-1-2000 h
-1.
The metal promoter that contains 1%-3% by the weight content of catalyst 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 that hot hydrogen was processed, and in processing procedure, pressure 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 silica-gel carrier is carried out to pretreatment, then adopt infusion process carried metal auxiliary agent and active component Co; Wherein the preprocess method of silica-gel carrier is that in silica-gel carrier, to pass into temperature be the hot hydrogen of 350-650 ℃, 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 that in silica-gel carrier, to pass into temperature be the hot hydrogen of 400-600 ℃, 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, pressure control is 0.5-2.5 MPa, preferably 1.0-2.0 MPa.
In the inventive method, hot hydrogen preprocessing process can carry out in fixed bed reactors, and passing into hot hydrogen needs to carry out before gas displacement, guarantees 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 be by existing method preparation.
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., preferably Zr.The preferred first impregnating metal auxiliary agent of carrying method of metal promoter and active component Co, then floods 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 containing auxiliary element salt, then adopt the solution impregnation containing active metal component Co salt, after every step dipping, can comprise drying steps and calcination steps.Drying steps is dry 8-24 hour at 50-150 ℃, and calcination steps is roasting 2-10 hour at 280-600 ℃.In the catalyst of preparation, the weight percentage of metal promoter zirconium is 0.5%-6%, preferably 1%-3%, and 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 conventionally use sulfuric acid in preparation process, at this moment inevitably has 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 are likely had an effect with active component in dipping process or when long time running, affect decentralization, reduction degree and the activity stability of metal active constituent on silica-gel carrier.
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 particularly sulfate ion of anion that the inventive method can effectively be reduced the oxidisability group of Silica Surface and be introduced while preparing silica-gel carrier, reduce kind and the quantity of Silica Surface oxidisability group and anion, reduce Silica Surface oxidisability group and the anion strong interaction to active component in load active component cobalt and long-time course of reaction, improved decentralization, reproducibility and the activity stability of catalyst;
2, the inventive method is little to the structural deterioration of silica-gel carrier, has substantially retained original physical property of silica-gel carrier, and preparation is simple, and technology maturation is conducive to the industrial production of catalyst;
3, the catalyst that prepared by the inventive method, under high-speed and macrocyclic operating condition, demonstrates good activity stability, and result of the test shows, is 2000 h in synthesis gas air speed
-1, device running 500 hours, the conversion ratio of CO still, up to more than 50%, has improved more than 10% than prior art.
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, the every 10 grams of dropping distilled water of this silica gel consume water volume while extremely just profit is 16ml, following examples are all used this silica gel) 30g, pack in fixed bed reactors, through gas displacement to guarantee passing into hot hydrogen after the volumetric concentration of fixing in-bed oxygen is less than 99.9%, the hot hydrogen temperature that comes from hydrogen heating furnace is 500 ℃, and volume space velocity is 1500 h
-1, the processing time is 15h, system pressure is 1.5MPa.By final catalyst zirconium content 3wt%, take zirconium nitrate and be dissolved in 48ml, add in the carrier silica gel after above-mentioned modification and flood, aging 3 hours, 80 ℃ were dried 8 hours, roasting 4 hours in 350 ℃.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 ℃ were dried 8 hours, roasting 4 hours in 350 ℃.Gained catalyst is designated as C-1.
Evaluating catalyst is tested in high pressure CSTR, using paraffin as solvent, reduces 12 hours with at 350 ℃ of pure hydrogen, and pressure is 1.0MPa.After cooling, switching synthesis gas reacts.Reaction effluent is collected by hot trap, cold-trap respectively.Reaction condition is 220 ℃, 2000h
-1, 2.0MPa, H
2/ CO=2(mol ratio).When be 500h the duration of runs, C-1 catalyst Fischer-Tropsch synthesis result is as shown in table 1.
Example 2
Take commercially available silica gel 30g, pack in fixed bed reactors, through gas displacement, to guarantee passing into hot hydrogen after the volumetric concentration of fixing in-bed oxygen is less than 99.9%, the hot hydrogen temperature that comes from hydrogen heating furnace is 350 ℃, and volume space velocity is 1200 h
-1, the processing time is 10h, system pressure is 1.0MPa.By final catalyst zirconium content 1wt%, take zirconium nitrate and be dissolved in 48ml, add in the carrier silica gel after above-mentioned modification and flood, aging 3 hours, 80 ℃ were dried 8 hours, roasting 4 hours in 350 ℃.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 ℃ were dried 8 hours, roasting 4 hours in 350 ℃.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 commercially available silica gel 30g, pack in fixed bed reactors, through gas displacement, to guarantee passing into hot hydrogen after the volumetric concentration of fixing in-bed oxygen is less than 99.9%, the hot hydrogen temperature that comes from hydrogen heating furnace is 400 ℃, and volume space velocity is 1600 h
-1, the processing time is 20h, system pressure is 1.5MPa.By final catalyst zirconium content 6wt%, take zirconium nitrate and be dissolved in 48ml, add in the carrier silica gel after above-mentioned modification and flood, aging 3 hours, 80 ℃ were dried 8 hours, roasting 4 hours in 350 ℃.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 ℃ were dried 8 hours, roasting 4 hours in 350 ℃.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 commercially available silica gel 30g, pack in fixed bed reactors, through gas displacement, to guarantee passing into hot hydrogen after the volumetric concentration of fixing in-bed oxygen is less than 99.9%, the hot hydrogen temperature that comes from hydrogen heating furnace is 450 ℃, and volume space velocity is 1800 h
-1, the processing time is 25h, system pressure is 2MPa.By final catalyst zirconium content 4wt%, take zirconium nitrate and be dissolved in 48ml, add in the carrier silica gel after above-mentioned modification and flood, aging 3 hours, 80 ℃ were dried 8 hours, roasting 4 hours in 350 ℃.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 ℃ were dried 8 hours, roasting 4 hours in 350 ℃.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 commercially available silica gel 30g, pack in fixed bed reactors, through gas displacement, to guarantee passing into hot hydrogen after the volumetric concentration of fixing in-bed oxygen is less than 99.9%, the hot hydrogen temperature that comes from hydrogen heating furnace is 550 ℃, and volume space velocity is 2000 h
-1, the processing time is 30h, system pressure is 2.5MPa.By final catalyst zirconium content 5wt%, take zirconium nitrate and be dissolved in 48ml, add in the carrier silica gel after above-mentioned modification and flood, aging 3 hours, 80 ℃ were dried 8 hours, roasting 4 hours in 350 ℃.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 ℃ were dried 8 hours, roasting 4 hours in 350 ℃.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 commercially available silica gel 30g, pack in fixed bed reactors, through gas displacement, to guarantee passing into hot hydrogen after the volumetric concentration of fixing in-bed oxygen is less than 99.9%, the hot hydrogen temperature that comes from hydrogen heating furnace is 600 ℃, and volume space velocity is 1500 h
-1, the processing time is 20h, system pressure is 1.5MPa.By final catalyst zirconium content 2wt%, take zirconium nitrate and be dissolved in 48ml, add in the carrier silica gel after above-mentioned modification and flood, aging 3 hours, 80 ℃ were dried 8 hours, roasting 4 hours in 350 ℃.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 ℃ were dried 8 hours, roasting 4 hours in 350 ℃.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 commercially available silica gel 30g, pack in fixed bed reactors, through gas displacement, to guarantee passing into hot hydrogen after the volumetric concentration of fixing in-bed oxygen is less than 99.9%, the hot hydrogen temperature that comes from hydrogen heating furnace is 450 ℃, and volume space velocity is 1000 h
-1, the processing time is 15h, system pressure is 2MPa.By final catalyst zirconium content 1.5wt%, take zirconium nitrate and be dissolved in 48ml, add in the carrier silica gel after above-mentioned modification and flood, aging 2 hours, 50 ℃ were dried 24 hours, roasting 10 hours in 280 ℃.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 ℃ were dried 8 hours, roasting 4 hours in 350 ℃.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 +Selectively (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, the metal promoter that contains 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 that hot hydrogen was processed, the temperature of hot hydrogen is 350-650 ℃, 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: the metal promoter that contains 1%-3% by the weight content of catalyst in described Co based Fischer-Tropsch synthesis catalyst, 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, pressure control is 0.5-2.5 MPa.
4. the preparation method of Co based Fischer-Tropsch synthesis catalyst claimed in claim 1, comprises following process: take silica gel as carrier, first silica-gel carrier is carried out to pretreatment, then adopt infusion process carried metal auxiliary agent and active component Co; It is characterized in that: wherein the preprocess method of silica-gel carrier is that in silica-gel carrier, to pass into temperature be the hot hydrogen of 350-650 ℃, 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 that in silica-gel carrier, to pass into temperature be the hot hydrogen of 400-600 ℃, 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, pressure 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, before passing into hot hydrogen, need to carry out gas displacement, guarantee 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 flood the step impregnation method of active component Co.
10. the application of the catalyst described in the arbitrary claim of claims 1 to 3 in Fischer-Tropsch synthesis.
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| 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 |
| WO2008147014A2 (en) * | 2007-05-29 | 2008-12-04 | Korea Research Institute Of Chemical Technology | Synthetic methods for liquid hydrocarbons from syngas over alumina-silica based catalysts and preparation methods thereof |
| US20090282975A1 (en) * | 2008-05-16 | 2009-11-19 | Matheson Tri-Gas, Inc. | Removal of impurities from hydrogen-containing materials |
| 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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- 2012-10-24 CN CN201210408285.3A patent/CN103769100B/en active Active
Patent Citations (6)
| 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 |
| WO2008147014A2 (en) * | 2007-05-29 | 2008-12-04 | Korea Research Institute Of Chemical Technology | Synthetic methods for liquid hydrocarbons from syngas over alumina-silica based catalysts and preparation methods thereof |
| 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 |
| US20090282975A1 (en) * | 2008-05-16 | 2009-11-19 | Matheson Tri-Gas, Inc. | Removal of impurities from hydrogen-containing materials |
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