CN101920200B - Method for preparing long-life cobalt-based catalyst for Fischer-Tropsch synthesis - Google Patents
Method for preparing long-life cobalt-based catalyst for Fischer-Tropsch synthesis Download PDFInfo
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- CN101920200B CN101920200B CN 200910011988 CN200910011988A CN101920200B CN 101920200 B CN101920200 B CN 101920200B CN 200910011988 CN200910011988 CN 200910011988 CN 200910011988 A CN200910011988 A CN 200910011988A CN 101920200 B CN101920200 B CN 101920200B
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Abstract
The invention discloses a method for preparing a long-life cobalt-based catalyst for Fischer-Tropsch synthesis. The method comprises the following steps of: performing surface modification on a silica gel carrier; and loading a metal aid and an active ingredient Co by adopting an immersion method, wherein the surface modification method for the silica gel carrier is to perform immersion treatment by using acid solution of sugar. Compared with similar catalysts, the catalyst for Fischer-Tropsch synthesis prepared by the method has the advantages of reducing the reaction between the carrier and the active ingredient in the processes of preparing and using the catalyst, and showing better stability in the reaction process, along with long service life.
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 is carrier with the modified silica-gel, adds the preparation method of the high-activity cobalt-based fischer-tropsch synthetic catalyst of metal promoter modification.
Background technology
Synthetic synthesis gas (the CO+H that is meant of Fischer-Tropsch
2) reaction of catalysis synthetic hydrocarbon liquid fuel on catalyst.Exhaustion day by day along with petroleum resources has received 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; 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 with unformed SiO
2, Al
2O
3And TiO
2Be 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 heavy hydrocarbon to greatest extent, and cobalt-base catalyst carbon deposit tendency is low, active high, therefore is that the research on basis is significant with the cobalt-base catalyst.
Yet the common carrier SiO of cobalt-base catalyst
2, Al
2O
3, TiO
2Deng being easy to make active component form the compound that is difficult to reduce, like CoSiO
4, CoAl
2O
4, CoTiO
3Thereby, make catalyst activity reduce, and after taking place to react, catalyst regeneration must can be regenerated through high temperature (being higher than 700 ℃) reduction.Under this reducing condition, be prone to cause that thereby catalyst active center's gathering causes catalyst activity to reduce (AppliedCatalysis A:General 348 (2008) 1-15) significantly.And catalyst based for the Co more expensive than ferrum-based catalyst, improve life of catalyst, the running life cycle that prolongs catalyst becomes the selection that reduces industrial cost.
Summary of the invention
To the deficiency of prior art, the invention provides a kind of is carrier with the modified silica-gel, the long-life cobalt-based Preparation of catalysts method of high activity.The silica-gel carrier that the present invention adopts has overcome the reaction between the carrier and active component in preparation and course of reaction after modification.The catalyst of the inventive method preparation and similar catalyst relatively under the suitable situation of activity, have the service life longer than existing catalyst.
The preparation method of Co based Fischer-Tropsch synthesis catalyst of the present invention comprises following process: be carrier with silica gel, at first silica-gel carrier carried out surface modification, adopt infusion process carried metal auxiliary agent and active component Co then; Wherein the surface modifying method of silica-gel carrier carries out impregnation process for the acid solution that adopts sugar.
Among the preparation method of Co based Fischer-Tropsch synthesis catalyst of the present invention, catalyst carrier can adopt existing product, and like macropore or pore dry silica gel microballoon etc., carrier can adopt commercially available silica gel on demand, also can be by existing method preparation.
Among the preparation method of Co based Fischer-Tropsch synthesis catalyst of the present invention; The steamed bun stuffed with sugar that the acid solution of used sugar uses is drawn together various water-soluble sugar of fitting; Like various monose or disaccharide, specifically comprise the aqueous solution such as fructose, glucose, sucrose, maltose, the preferably sucrose acid solution.Concrete method of modifying to silica-gel carrier is that the acid solution of a certain amount of silica gel with sugar mixed, and fully stirs back drying, roasting.Silica gel is 1: 1.5～1: 15 with the mass ratio that adopts the acid solution contain sugar to mix, and is preferably 1: 4～1: 12.The mass concentration of sugar is 1%-35% in the acid solution of sugar, preferred 5%-20%.The acid solution pH that contains sugar is 0.1-6.5, and preferred pH value is 1-3, can use the pH value of inorganic acid arbitrarily or organic acid regulator solution, is preferably hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, formic acid, acetate etc.Silica gel is 50-95 ℃ with the acid solution mixing temperature that contains sugar, is preferably 60～80 ℃, and the mixed processing time is 0.5-10h, preferred 2-5h.Mixing the back baking temperature is 50-150 ℃, and be 0.5-36h drying time, preferably dry 8-24h under 60-120 ℃.Roasting is at 600-1200 ℃ of following roasting 2-15 hour, preferably at 800-1000 ℃ of following roasting 4-10 hour.Wherein silica gel mixes with the acid solution that contains sugar and follow-up drying and roasting can be carried out once, also can carry out repeatedly repeatedly, as 2～5 times.Roasting process adopts vacuum condition or under inert gas atmosphere, carries out.
Among the preparation method of Co based Fischer-Tropsch synthesis catalyst of the present invention, metal promoter can be one or more among Re, Zr, Hf, Ce and the Th etc., preferred Zr.The preferred first impregnating metal auxiliary agent of the carrying method of metal promoter and active component Co floods the step impregnation method of active component Co then.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: adopt the solution impregnation modified silica-gel carrier that contains auxiliary element salt earlier, adopt the solution impregnation that contains active metal component Co salt then, can comprise drying steps and calcination steps behind per step dipping.Drying steps descended dry 8-24 hour at 50-150 ℃, and calcination steps was at 280-600 ℃ of following roasting 2-10 hour.The weight percentage of metal promoter is 0.5%-6% in the catalyst of preparation, preferred 1%-3%, and the weight percentage of cobalt is 5%-35%.
Co based Fischer-Tropsch synthesis catalyst of the present invention is carrier to use the silica gel that contains after the saccharic acid property solution-treated, is active component with the cobalt, is auxiliary agent with among Re, Zr, Hf, Ce and the Th one or more, adopts method for preparing of the present invention.
Compared with prior art, the catalyst that obtains of the preparation method of the inventive method Co based Fischer-Tropsch synthesis catalyst has following advantage:
1, silica-gel carrier surface is through after handling with the acid solution of sugar, can effectively be suppressed at the reaction in activated centre and carrier in the preparation process, suppresses carrier and generates the compound that difficulty is reduced with the activated centre.
2, in course of reaction, silica-gel carrier surface is through after handling with the acid solution of sugar, can effectively be suppressed at the reaction in activated centre and carrier in the course of reaction, suppresses the inactivation of the more difficult life of catalyst generation.
3, Preparation of Catalyst is simple, and technology is ripe, helps the commercial production of catalyst.
The specific embodiment
Further specify the process and the effect of the inventive method below in conjunction with embodiment.
Instance 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 of consume water is 48ml.Be that 5% the aqueous solution equals 3 with the sulphur acid for adjusting pH value with the sucrose mass concentration; And make that the mass ratio of silica gel and mixed solution is 1: 4; In temperature is under 60 ℃ silica gel and sucrose acid solution fully to be mixed stirring 2 hours; In 60 ℃ dry 24 hours, roasting 10 hours in vacuum or the nitrogen atmosphere in 800 ℃ then.
By final catalyst zirconium content 3wt%, take by weighing zirconium nitrate and be dissolved in 48ml, add in the carrier silica gel after the above-mentioned modification and flood, aging 3 hours, 80 ℃ of dryings 8 hours, roasting is 4 hours in 350 ℃.By final catalyst cobalt content 15wt%, take by weighing cobalt nitrate and be dissolved in 48ml, add in the sample behind the above-mentioned dipping zirconium, aging 3 hours, 80 ℃ of dryings 8 hours, roasting is 4 hours in 350 ℃.The gained catalyst is designated as C-1.
The evaluating catalyst test, was reduced 12 hours down for 350 ℃ with pure hydrogen as solvent with paraffin in the high pressure CSTR, and pressure is 1.0MPa.The cooling back is switched synthesis gas and is reacted.Reaction effluent is collected by hot trap, cold-trap respectively.Reaction condition is 220 ℃, 1000h
-1, 2.0MPa, H
2/ CO=2 (mol ratio).The result is as shown in table 1 for C-1 catalyst Fischer-Tropsch synthesis.
Instance 2
Take by weighing commercially available silica gel, drip distilled water to just moistening, the volume of consume water is 48ml.Be that 15% the aqueous solution equals 2 with the salt acid for adjusting pH value with the sucrose mass concentration; And make that the mass ratio of silica gel and mixed solution is 1: 9; In temperature is under 70 ℃ silica gel and sucrose acid solution fully to be mixed stirring 3.5 hours; In 100 ℃ dry 16 hours, vacuum baking 8 hours in 900 ℃ then.
By final catalyst zirconium content 3wt%, take by weighing zirconium nitrate and be dissolved in 48ml, add in the carrier silica gel after the above-mentioned modification and flood, aging 3 hours, 80 ℃ of dryings 8 hours, roasting is 4 hours in 350 ℃.By final catalyst cobalt content 15wt%, take by weighing cobalt nitrate and be dissolved in 48ml, add in the sample behind the above-mentioned dipping zirconium, aging 3 hours, 80 ℃ of dryings 8 hours, roasting is 4 hours in 350 ℃.The gained catalyst is designated as C-2.Catalyst activity evaluation experimental condition is with embodiment 1.The result is as shown in table 1 for C-2 catalyst Fischer-Tropsch synthesis.
Instance 3
Take by weighing commercially available silica gel, drip distilled water to just moistening, the volume of consume water is 48ml.Be that 20% the aqueous solution equals 1 with the sulphur acid for adjusting pH value with the sucrose mass concentration; And make that the mass ratio of silica gel and mixed solution is 1: 12; In temperature is under 80 ℃ silica gel and sucrose acid solution fully to be mixed stirring 5 hours; In 120 ℃ dry 8 hours, vacuum baking 4 hours in 1000 ℃ then.
By final catalyst zirconium content 3wt%, take by weighing zirconium nitrate and be dissolved in 48ml, add in the carrier silica gel after the above-mentioned modification and flood, aging 3 hours, 80 ℃ of dryings 8 hours, roasting is 4 hours in 350 ℃.By final catalyst cobalt content 15wt%, take by weighing cobalt nitrate and be dissolved in 48ml, add in the sample behind the above-mentioned dipping zirconium, aging 3 hours, 80 ℃ of dryings 8 hours, roasting is 4 hours in 350 ℃.The gained catalyst is designated as C-3.Catalyst activity evaluation experimental condition is with embodiment 1.The result is as shown in table 1 for C-3 catalyst Fischer-Tropsch synthesis.
Instance 4
Take by weighing commercially available silica gel 30g, drip distilled water to just moistening, the volume of consume water is 48ml.Be that 5% the aqueous solution equals 3 with the second acid for adjusting pH value with the sucrose mass concentration; And make that the mass ratio of silica gel and mixed solution is 1: 4; In temperature is under 60 ℃ silica gel and sucrose acid solution fully to be mixed stirring 2 hours; In 60 ℃ dry 24 hours, roasting 10 hours in vacuum or the nitrogen atmosphere in 800 ℃ then.
By final catalyst zirconium content 3wt%, take by weighing zirconium nitrate and be dissolved in 48ml, add in the carrier silica gel after the above-mentioned modification and flood, aging 3 hours, 80 ℃ of dryings 8 hours, roasting is 4 hours in 350 ℃.By final catalyst cobalt content 15wt%, take by weighing cobalt nitrate and be dissolved in 48ml, add in the sample behind the above-mentioned dipping zirconium, aging 3 hours, 80 ℃ of dryings 8 hours, roasting is 4 hours in 350 ℃.The gained catalyst is designated as C-4.Catalyst activity evaluation experimental condition is with embodiment 1.The result is as shown in table 1 for C-4 catalyst Fischer-Tropsch synthesis.
Instance 5
Take by weighing commercially available silica gel, drip distilled water to just moistening, the volume of consume water is 48ml.Be that 15% the aqueous solution equals 2 with the sulphur acid for adjusting pH value with glucose quality concentration; And make that the mass ratio of silica gel and mixed solution is 1: 9; In temperature is under 70 ℃ silica gel and the acid solution of glucose fully to be mixed stirring 3.5 hours; In 100 ℃ dry 16 hours, vacuum baking 8 hours in 900 ℃ then.
By final catalyst zirconium content 3wt%, take by weighing zirconium nitrate and be dissolved in 48ml, add in the carrier silica gel after the above-mentioned modification and flood, aging 3 hours, 80 ℃ of dryings 8 hours, roasting is 4 hours in 350 ℃.By final catalyst cobalt content 15wt%, take by weighing cobalt nitrate and be dissolved in 48ml, add in the sample behind the above-mentioned dipping zirconium, aging 3 hours, 80 ℃ of dryings 8 hours, roasting is 4 hours in 350 ℃.The gained catalyst is designated as C-5.Catalyst activity evaluation experimental condition is with embodiment 1.The result is as shown in table 1 for C-5 catalyst Fischer-Tropsch synthesis.
Instance 6
Take by weighing commercially available silica gel, drip distilled water to just moistening, the volume of consume water is 48ml.Be that 15% the aqueous solution equals 2 with the sulphur acid for adjusting pH value with the fructose mass concentration; And make that the mass ratio of silica gel and mixed solution is 1: 9; In temperature is under 70 ℃ silica gel and fructose acid solution fully to be mixed stirring 3.5 hours; In 100 ℃ dry 16 hours, vacuum baking 8 hours in 900 ℃ then.
By final catalyst zirconium content 3wt%, take by weighing zirconium nitrate and be dissolved in 48ml, add in the carrier silica gel after the above-mentioned modification and flood, aging 3 hours, 80 ℃ of dryings 8 hours, roasting is 4 hours in 350 ℃.By final catalyst cobalt content 15wt%, take by weighing cobalt nitrate and be dissolved in 48ml, add in the sample behind the above-mentioned dipping zirconium, aging 3 hours, 80 ℃ of dryings 8 hours, roasting is 4 hours in 350 ℃.The gained catalyst is designated as C-6.Catalyst activity evaluation experimental condition is with embodiment 1.The result is as shown in table 1 for C-6 catalyst Fischer-Tropsch synthesis.
Instance 7
Take by weighing commercially available silica gel, drip distilled water to just moistening, the volume of consume water is 48ml.Be that 15% the aqueous solution equals 2 with the sulphur acid for adjusting pH value with the maltose mass concentration; And make that the mass ratio of silica gel and mixed solution is 1: 9; In temperature is under 70 ℃ silica gel and the acid solution of maltose fully to be mixed stirring 3.5 hours; In 100 ℃ dry 16 hours, vacuum baking 8 hours in 900 ℃ then.
By final catalyst zirconium content 3wt%, take by weighing zirconium nitrate and be dissolved in 48ml, add in the carrier silica gel after the above-mentioned modification and flood, aging 3 hours, 80 ℃ of dryings 8 hours, roasting is 4 hours in 350 ℃.By final catalyst cobalt content 15wt%, take by weighing cobalt nitrate and be dissolved in 48ml, add in the sample behind the above-mentioned dipping zirconium, aging 3 hours, 80 ℃ of dryings 8 hours, roasting is 4 hours in 350 ℃.The gained catalyst is designated as C-7.Catalyst activity evaluation experimental condition is with embodiment 1.The result is as shown in table 1 for C-7 catalyst Fischer-Tropsch synthesis.
Instance 8
Take by weighing commercially available silica gel, drip distilled water to just moistening, the volume of consume water is 48ml.Be that 15% the aqueous solution equals 2 with the sulphur acid for adjusting pH value with the sucrose mass concentration; And make that the mass ratio of silica gel and mixed solution is 1: 9; In temperature is under 70 ℃ silica gel and sucrose acid solution fully to be mixed stirring 3.5 hours; In 100 ℃ dry 16 hours, vacuum baking 8 hours in 900 ℃ then.With above-mentioned sucrose acid solution handle with dry, calcination process after silica gel be 15% with mass concentration once more; The sucrose acidic aqueous solution of pH=2 mixes; And make that the mass ratio of silica gel and mixed solution is 1: 9; In temperature is under 70 ℃ silica gel and sucrose acid solution fully to be mixed to stir 3.5 hours, in 100 ℃ dry 16 hours, and vacuum baking 8 hours in 900 ℃ then.
By final catalyst zirconium content 1wt%, take by weighing zirconium nitrate and be dissolved in 48ml, add in the carrier silica gel after the above-mentioned modification and flood, aging 2 hours, 50 ℃ of dryings 24 hours, roasting is 10 hours in 280 ℃.By final catalyst cobalt content 15wt%, take by weighing cobalt nitrate and be dissolved in 48ml, add in the sample behind the above-mentioned dipping zirconium, aging 3 hours, 80 ℃ of dryings 8 hours, roasting is 4 hours in 350 ℃.The gained catalyst is designated as C-8.Catalyst activity evaluation experimental condition is with embodiment 1.The result is as shown in table 1 for C-8 catalyst Fischer-Tropsch synthesis.
Comparative example 1
By final catalyst zirconium content 3wt%, take by weighing zirconium nitrate and be dissolved in 48ml, add in the carrier silica gel after the above-mentioned modification and flood, aging 3 hours, 80 ℃ of dryings 8 hours, roasting is 4 hours in 350 ℃.By final catalyst cobalt content 15wt%, take by weighing cobalt nitrate and be dissolved in 48ml, add in the sample behind the above-mentioned dipping zirconium, aging 3 hours, 80 ℃ of dryings 8 hours, roasting is 4 hours in 350 ℃.The gained catalyst is designated as C-B.Catalyst activity evaluation experimental condition is with embodiment 1.The result is as shown in table 1 for C-B catalyst Fischer-Tropsch synthesis.
The reactivity worth of table 1 catalyst
| 20h CO conversion ratio (%) | 120h CO conversion ratio (%) | Deactivation rate *(h -1) | |
| C-1 | 73.5 | 69.1 | 0.044 |
| C-2 | 74.8 | 70.6 | 0.042 |
| C-3 | 71.1 | 66.8 | 0.043 |
| C-4 | 67.8 | 62.3 | 0.055 |
| C-5 | 70.4 | 65.5 | 0.049 |
| C-6 | 71.2 | 65.8 | 0.054 |
| C-7 | 70.6 | 65.4 | 0.052 |
| C-8 | 69.4 | 63.9 | 0.055 |
| C-B | 70.8 | 63.7 | 0.071 |
*Deactivation rate computational methods: deactivation rate=(20h CO conversion ratio-120h CO conversion ratio)/100h
Claims (9)
1. the preparation method of a long-life cobalt-based catalyst for Fischer-Tropsch synthesis is a carrier with silica gel, at first silica-gel carrier is carried out surface modification, adopts infusion process carried metal auxiliary agent and active component Co then; It is characterized in that: the surface modifying method of silica-gel carrier carries out impregnation process for the acid solution that adopts sugar; Concrete method of modifying to silica-gel carrier is that the acid solution of silica gel with sugar mixed, and fully stirs back drying, roasting, and roasting process adopts vacuum condition or under inert gas atmosphere, carries out.
2. according to the described method of claim 1, it is characterized in that: the steamed bun stuffed with sugar that the acid solution of said sugar uses is drawn together monose or disaccharide.
3. according to the described method of claim 1, it is characterized in that: silica gel is 1: 1.5～1: 15 with the mass ratio that the acid solution of sugar mixes, and the mass concentration of sugar is 1%-35% in the acid solution of sugar, and the acid solution pH that contains sugar is 0.1-6.5.
4. according to the described method of claim 1, it is characterized in that: silica gel is 1: 4～1: 12 with the mass ratio that the acid solution of sugar mixes, and the mass concentration of sugar is 5%-20% in the acid solution of sugar, and the acid solution pH of sugar is 1-3.
5. according to the described method of claim 1; It is characterized in that: silica gel is 50-95 ℃ with the acid solution mixing temperature that contains sugar, and the mixed processing time is 0.5-10h, and mixing the back baking temperature is 50-150 ℃; Be 0.5-36h drying time, and roasting was at 600-1200 ℃ of following roasting 2-15 hour.
6. according to the described method of claim 1; It is characterized in that: silica gel is 60～80 ℃ with the acid solution mixing temperature that contains sugar, and the mixed processing time is 2-5h, and mixing the back baking temperature is 60-120 ℃; Be 8-24h drying time, and roasting was at 800-1000 ℃ of following roasting 4-10 hour.
7. according to the described method of claim 1, it is characterized in that: silica gel mixes with the acid solution that contains sugar and follow-up drying and roasting are carried out 2～5 times repeatedly.
8. according to the described method of claim 1, it is characterized in that: the carrying method of metal promoter and active component Co adopts first impregnating metal auxiliary agent, floods the step impregnation method of active component Co then.
9. according to the described method of claim 1, it is characterized in that: metal promoter is one or more among Re, Zr, Hf, Ce and the Th, and the weight percentage of metal promoter is 0.5%-6% in the catalyst, and the weight percentage of cobalt is 5%-35%.
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| CN104815660A (en) * | 2015-04-09 | 2015-08-05 | 中国科学院山西煤炭化学研究所 | Fischer-Tropsch synthesis cobalt-based catalyst and preparation method and application thereof |
| CN104815661A (en) * | 2015-04-09 | 2015-08-05 | 中国科学院山西煤炭化学研究所 | Catalyst by taking modified alumina as carrier and preparation method thereof |
| CN106277414B (en) * | 2015-05-18 | 2018-08-14 | 中国石油化工股份有限公司 | A kind of method that oily wastewater eliminates foam |
| CN105833883A (en) * | 2016-05-03 | 2016-08-10 | 华东理工大学 | Previous metal modified catalyst for fischer-tropsch synthesis and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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Non-Patent Citations (1)
| Title |
|---|
| 石利红等.有机改性二氧化硅及其负载钴催化剂的费托合成反应性能.《催化学报》.2007,第28卷(第11期),第1000页第1节实验部分. * |
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