CN103769096B - Preparation method of cobalt-based Fischer-Tropsch synthesis catalyst - Google Patents
Preparation method of cobalt-based Fischer-Tropsch synthesis catalyst Download PDFInfo
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- CN103769096B CN103769096B CN201210408239.3A CN201210408239A CN103769096B CN 103769096 B CN103769096 B CN 103769096B CN 201210408239 A CN201210408239 A CN 201210408239A CN 103769096 B CN103769096 B CN 103769096B
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Abstract
The invention discloses a preparation method of a cobalt-based Fischer-Tropsch synthesis catalyst. The preparation method comprises following steps: (1) silicon dioxide is taken as a carrier, loading of auxiliary agent zirconium is carried out via immersion method, and the loaded carrier is dried for 8 to 24h at a temperature of 50 to 150 DEG C; (2) hydrogen/carbon monoxide mixed gas with a volume ratio of 5:1 to 3:1 is added for pre-treatment of the dried zirconium-containing silicon dioxide, wherein the temperature of the mixed gas ranges from 250 to 550 DEG C, volume space velocity ranges from 800 to 1500/h, and treatment time ranges from 1 to 20h; and (3), the zirconium-containing silicon dioxide pre-treated with the hydrogen/carbon monoxide mixed gas is taken as a carrier, loading of the active component cobalt is carried out via immersion method, and the zirconium-containing silicon dioxide carrier is dried and roasted so as to obtain the cobalt-based Fischer-Tropsch synthesis catalyst. Preparation processes are simple; and the cobalt-based Fischer-Tropsch synthesis catalyst possesses excellent activity and stability in long-period and high space velocity operation conditions, and is suitable for industrialized application.
Description
Technical field
The present invention relates to a kind of preparation method of Co based Fischer-Tropsch synthesis catalyst, relating in particular to a kind of take silica gel as the preparation method of the Co based Fischer-Tropsch synthesis catalyst of the high-activity stable of carrier.
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 preparation method of Co based Fischer-Tropsch synthesis catalyst, 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 preparation method for Co based Fischer-Tropsch synthesis catalyst, comprises the steps:
(1) take silica as carrier, adopt infusion process load auxiliary agent zirconium, dry 8-24 hour at 50-150 DEG C;
(2) dried in step (1) is that the hydrogen/carbon mono oxide mixture of 5:1-3:1 carries out pretreatment containing passing into volume ratio in zirconium silica, and mixture temperature is 250-550 DEG C, and volume space velocity is 800 h
-1-1500 h
-1, the processing time is 1-20h;
(3) with hydrogen/carbon mono oxide mixture pretreated containing zirconium silica for carrier, adopt infusion process load active component cobalt, drying, roasting obtain Co based Fischer-Tropsch synthesis catalyst.
In the inventive method step (1), described silica supports can adopt commercially available silica product on demand, also can prepare by existing method.Described auxiliary agent zirconium is zirconium nitrate, and the dipping process of zirconium can adopt method well known to those skilled in the art, incipient impregnation or excessively volume impregnation.The addition of zirconium in the weight percentage of zirconium in final Co based Fischer-Tropsch synthesis catalyst for 0.5%-6%.
In the inventive method step (2), described hydrogen/carbon mono oxide mixture temperature is 300-500 DEG C, and volume space velocity is 900h
-1-1300 h
-1, the processing time is no less than 8 h
-1.
In the inventive method step (2), hydrogen/carbon mono oxide mixture preprocessing process can carry out under suitable pressure, and the pressure of general control pretreatment system is 0.5-2.5 MPa, preferred 1.0-2.0 MPa.
In the inventive method step (2), hydrogen/carbon mono oxide mixture preprocessing process carries out in fixed bed reactors, need before passing into gaseous mixture to carry out gas displacement, ensure that the volumetric concentration of fixing in-bed oxygen is less than 99.9%, gaseous mixture comes from gas heating stove.
In the inventive method step (3), the dipping process of described Co adopts method well known to those skilled in the art.Drying steps dry 8-24 hour at 50-150 DEG C after dipping, calcination steps is roasting 2-10 hour at 280-600 DEG C.The addition of cobalt in cobalt weight percentage in the final catalyst for 5%-35%.
A kind of Co based Fischer-Tropsch synthesis catalyst is carrier with silica, and take cobalt as active component, zirconium is auxiliary agent, adopts said method of the present invention to prepare.
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 process 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.Containing oxidizing organic group and the silica-gel carrier of anion and the effect of metal active constituent 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, the present invention adopts the silica gel of the hydrogen/carbon mono oxide mixture of high temperature to load auxiliary agent zirconium to process, and then preparation method's tool of load active component cobalt has the following advantages:
1, the inventive method adopts the hydrogen/carbon mono oxide mixture of higher temperature to process it after silica gel load auxiliary agent zirconium, 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 carbon monoxide in the inventive method gaseous mixture can generate a small amount of carbon deposit at Silica Surface, form an efficient internal heat dissipating passage, and reduce the concentration of Silica Surface hydroxyl, reduce the strong interaction of active component and hydroxyl, improve the hydrothermal stability of catalyst, inhibit the generation of cobaltous silicate;
3, 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;
4, 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 59.5%, improves more than 15% 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, and following examples all use this silica gel) 30g, by final catalyst zirconium content 3wt%, take zirconium nitrate and be dissolved in 48ml, add in above-mentioned silica-gel carrier and flood, aging 3 hours, 80 DEG C of dryings 8 hours.Load in fixed bed reactors by above-mentioned containing zirconium silicate gel, pass into ensure that the volumetric concentration of fixing in-bed oxygen is less than after 99.9% the hydrogen/carbon mono oxide mixture that volume ratio is 4:1 through gas displacement, the hydrogen/carbon mono oxide mixture temperature coming from gaseous mixture 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 cobalt content 20wt%, take cobalt nitrate and be dissolved in 48ml, add after above-mentioned process containing in zirconium silicate gel carrier, 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, by final catalyst zirconium content 1wt%, take zirconium nitrate and be dissolved in 48ml, add in silica-gel carrier and flood, aging 3 hours, 80 DEG C of dryings 8 hours.Load in fixed bed reactors by above-mentioned containing zirconium silicate gel, pass into ensure that the volumetric concentration of fixing in-bed oxygen is less than after 99.9% the hydrogen/carbon mono oxide mixture that volume ratio is 5:1 through gas displacement, the hydrogen/carbon mono oxide mixture temperature coming from gaseous mixture heating furnace is 300 DEG C, and volume space velocity is 1300 h
-1, the processing time is 10h, system pressure 1.5MPa.By final catalyst cobalt content 30wt%, take cobalt nitrate and be dissolved in 48ml, add after above-mentioned process containing in zirconium silicate gel carrier, 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, 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.Load in fixed bed reactors by above-mentioned containing zirconium silicate gel, pass into ensure that the volumetric concentration of fixing in-bed oxygen is less than after 99.9% the hydrogen/carbon mono oxide mixture that volume ratio is 3:1 through gas displacement, the hydrogen/carbon mono oxide mixture temperature coming from gaseous mixture heating furnace is 500 DEG C, and volume space velocity is 900 h
-1, the processing time is 20h, system pressure 0.5MPa.By final catalyst cobalt content 10wt%, take cobalt nitrate and be dissolved in 48ml, add after above-mentioned process containing in zirconium silicate gel carrier, 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, 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.Load in fixed bed reactors by above-mentioned containing zirconium silicate gel, pass into ensure that the volumetric concentration of fixing in-bed oxygen is less than after 99.9% the hydrogen/carbon mono oxide mixture that volume ratio is 4:1 through gas displacement, the hydrogen/carbon mono oxide mixture temperature coming from gaseous mixture heating furnace is 400 DEG C, and volume space velocity is 1500 h
-1, the processing time is 8h, system pressure 1MPa.By final catalyst cobalt content 15wt%, take cobalt nitrate and be dissolved in 48ml, add after above-mentioned process containing in zirconium silicate gel carrier, 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.
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 identical with catalyst prepared by example 1, and catalyst composition and active appraisal experiment condition are 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 identical with catalyst prepared by example 1, and catalyst composition and active appraisal experiment condition are with embodiment 1.Evaluation result is in table 1.
Table 1
| Catalyst | CO conversion ratio (%) | C 5 +Selective (wt%) |
| C-1 | 59.5 | 84.8 |
| C-B1 | 42.2 | 82.5 |
| C-B2 | 43.9 | 81.7 |
| C-2 | 57.1 | 83.9 |
| C-3 | 52.4 | 84.9 |
| C-4 | 53.5 | 85.5 |
| C-5 | 51.5 | 83.7 |
| C-6 | 54.5 | 84.2 |
| C-7 | 53.5 | 84.7 |
Claims (9)
1. a preparation method for Co based Fischer-Tropsch synthesis catalyst, is characterized in that: comprise the steps:
(1) take silica as carrier, adopt infusion process load auxiliary agent zirconium, dry 8-24 hour at 50-150 DEG C;
(2) dried in step (1) is that the hydrogen/carbon mono oxide mixture of 5:1-3:1 carries out pretreatment containing passing into volume ratio in zirconium silica, and mixture temperature is 250-550 DEG C, and volume space velocity is 800 h
-1-1500 h
-1, the processing time is 1-20h;
(3) with hydrogen/carbon mono oxide mixture pretreated containing zirconium silica for carrier, adopt infusion process load active component cobalt, drying, roasting obtain Co based Fischer-Tropsch synthesis catalyst.
2. according to the method described in claim 1, it is characterized in that: described auxiliary agent zirconium is zirconium nitrate, the addition of zirconium is in the weight percentage 0.5%-6% of zirconium in final Co based Fischer-Tropsch synthesis catalyst.
3. according to the method described in claim 1, it is characterized in that: in step (2), described hydrogen/carbon mono oxide mixture temperature is 300-500 DEG C, and volume space velocity is 900h
-1-1300 h
-1, the processing time is no less than 8 h.
4. according to the method described in claim 1, it is characterized in that: in step (2), hydrogen/carbon mono oxide mixture preprocessing process carries out under pressure is 0.5-2.5 MPa.
5. according to the method described in claim 4, it is characterized in that: in step (2), hydrogen/carbon mono oxide mixture preprocessing process carries out under pressure is 1.0-2.0MPa.
6. according to the method described in claim 1, it is characterized in that: in step (2), hydrogen/carbon mono oxide mixture preprocessing process carries out in fixed bed reactors, need before passing into gaseous mixture to carry out gas displacement, ensure that the volumetric concentration of fixing in-bed oxygen is less than 99.9%, gaseous mixture comes from gas heating stove.
7. according to the method described in claim 1, it is characterized in that: drying steps dry 8-24 hour at 50-150 DEG C after step (3) dipping, calcination steps is roasting 2-10 hour at 280-600 DEG C.
8., according to the method described in claim 1, it is characterized in that: the addition of described cobalt in cobalt weight percentage in the final catalyst for 5%-35%.
9. a Co based Fischer-Tropsch synthesis catalyst, is characterized in that: this catalyst is carrier with silica, take cobalt as active component, and zirconium is auxiliary agent, adopts the arbitrary described method preparation of claim 1 to 8.
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| CN1785515A (en) * | 2005-12-14 | 2006-06-14 | 中国科学院山西煤炭化学研究所 | Catalyst used for synthesizing middle distillate from synthetic gas, its preparation method and application |
| CN101698152A (en) * | 2009-10-20 | 2010-04-28 | 武汉凯迪科技发展研究院有限公司 | Cobalt-based compounded catalyst and preparing method and application thereof |
| CN102310004A (en) * | 2010-07-07 | 2012-01-11 | 中国石油化工股份有限公司 | Method for reducing cobalt-base Fischer Tropsch synthesis catalyst |
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| FR2962664B1 (en) * | 2010-07-16 | 2014-03-14 | IFP Energies Nouvelles | COBALT CATALYST ON SILICA-ALUMINUM SUPPORT FOR FISCHER-TROPSCH SYNTHESIS |
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| CN1785515A (en) * | 2005-12-14 | 2006-06-14 | 中国科学院山西煤炭化学研究所 | Catalyst used for synthesizing middle distillate from synthetic gas, its preparation method and application |
| CN101698152A (en) * | 2009-10-20 | 2010-04-28 | 武汉凯迪科技发展研究院有限公司 | Cobalt-based compounded catalyst and preparing method and application thereof |
| CN102310004A (en) * | 2010-07-07 | 2012-01-11 | 中国石油化工股份有限公司 | Method for reducing cobalt-base Fischer Tropsch synthesis catalyst |
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