CN1417292A - Catalyst for preparing alkane of diesel oil fraction from synthetic gas and its prepn - Google Patents
Catalyst for preparing alkane of diesel oil fraction from synthetic gas and its prepn Download PDFInfo
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- CN1417292A CN1417292A CN 01136889 CN01136889A CN1417292A CN 1417292 A CN1417292 A CN 1417292A CN 01136889 CN01136889 CN 01136889 CN 01136889 A CN01136889 A CN 01136889A CN 1417292 A CN1417292 A CN 1417292A
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- gac
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Abstract
The catalyst consists of three parts including active component, assistant and carrier. The main active component is metal Co. The first assistant element is group IVB metal element, such as Ti and Zr or group IIIB metal element, such as La and Ce; and the second ssistant element is group VIII metal element, such as Rh, Ru and Pt. The carrier is active carbon of apricot kernel, coconut shell, oil palm or coal; has specific surface area of 200-2000 sq mg, pore volume of 0.5-2.0 cu cm/g and pore distribution of 4-1000 angstrom. Of the catalyst weight, metal Co accounts for 4-50 %, the first assistant element 0.01-20.0% and the second assistant element 0.01-50 %. The catalyst may be used in the Fischer-Tropsch reaction of synthetic gas to prepare high-quality diesel oil as clean liquid fuel.
Description
Invention field
The invention provides that a kind of to be used for by synthetic gas be the material choice carbon number for preparing straight-chain paraffin mainly concentrates on the catalyzer of diesel oil distillate section 20 with interior and hydro carbons carbon number.
Background technology
(Fischer-Tropsch Synthesis FTS) is the core process that coal/natural gas via synthetic gas is converted into clean fuel (as gasoline, diesel oil, alcohols etc.) to Fischer-Tropsch synthesis.In recent years, the continuous increase of coal/Sweet natural gas proven reserve, the exhaustion day by day of petroleum resources makes the research in this field very active.Yet its efficient core that transforms remains and the relevant catalysis problem of fischer-tropsch synthetic catalyst research.In the research of nearly 80 years FTS catalyzer, people have found that Fe, Co and Ru are the effective active ingredients of FTS catalyzer, auxiliary elements such as Ru, Zr, K and Cu play an important role to FTS activity of such catalysts, stability, and the characteristics of these a few class catalyzer are synthetic gas can be converted into the hydro carbons of wide region products distribution (as C under the FTS operational condition
100More than).At present, precipitated iron FTS catalyzer and cobalt zirconium/silicon-dioxide FTS catalyzer adopts slurry attitude bed or fixed-bed process successfully to realize industrialization in the FTS factory of the FTS of South Africa Sosal factory and Dutch Shell company respectively, and FTS high-carbon hydrocarbon-wax product that the parallel-series hydroeracking unit is fastened iron system or cobalt is cracked into gasoline, diesel oil or lubricated wet goods related fluid fluid fuel and chemical.The rarer products distribution of research on laboratory or the pilot scale FTS fischer-tropsch synthetic catalyst drops in the narrow carbon number (as C
20In) reported in literature, once the someone attempted making carrier loaded cobalt-base catalyst with molecular sieve, was used for synthetic oil product fuel, but found to have a large amount of aromatic hydrocarbons in oil-phase product, therefore, reduced the quality of petrol and diesel oil greatly.But select for use gac to make the synthetic C of carrier
20The research of interior hydrocarbon also end appears in the newspapers and leads.Thereby, utilize two-stage method or multiple process that coal/natural gas via synthetic gas is converted into the complex process of liquid fuel, cost is higher, thus because difficult and petroleum resources competition has to a certain degree limited coal/Sweet natural gas prepares the technology of gasoline or diesel oil by FTS realization.The directly synthetic or directed directly catalyzer of synthetic middle distillate section hydro carbons (diesel component) is selected in research, make synthetic gas be converted into liquid hydrocarbon fuel, simple for process, might develop earlier in 21st century produce coal/natural gas energy resource substitutes the catalyzer and the technology of petroleum resources.
It is that unstripped gas generates lower carbon number hydrocarbons (＜C through the FTS reaction with the synthetic gas that USP.4478954 has reported a kind of
4) starch FTS catalyzer mutually with the iron/gac of alcohol.Done following explanation about catalyzer: vector contg 20～90%, active ingredient iron level 5～50%, selection of auxiliary chromium, magnesium, its content 5～40%, reaction conditions are typical FTS synthesis condition.
It is that feedstock production is mainly C with methyl alcohol or synthetic gas that USP.4542122 has invented a kind of
10 +Co～the Th/TiO of cut
2Catalyzer.This patent also introduced by the high-carbon hydrocarbon that makes by FTS reaction on this catalyzer further hydrotreatment make the diesel oil of middle runnings or aviation diesel oil etc.Done following explanation about catalyzer: carrier is about 3: 2～100: 1, Primary Catalysts Co:2～25% by Rutile: Anatase, Th:0.1～10%.Patent research is the result show, the working conditions of this catalyzer, 140～400psig, H
2: CO=2: 1～3: 1, V
SP=300～1500h
-1, 190～260 ℃, it is active and with high C that this catalyzer has very high methanol hydrogenation and co hydrogenation
10 +The advantage of selectivity of product.
It is that unstripped gas generates the Co-Zr/SiO that pyroparaffine is the master through the FTS reaction with the synthetic gas that USP.4579986 has reported a kind of
2The FTS catalyzer, this catalyzer is C under typical FTS condition
5 +Selectivity can reach more than 82%.
Venter and Vannice are that the fischer-tropsch synthetic catalyst of carrier had research (J.Catal. to gac, 1987,103:450, Catal.Lett., 1990,7:219, J.Phys.Chem., 1992,96:9944), behind the carbonyl compound of dipping a certain amount of Fe, Mn, K on the gac, and behind hydrogen reducing, find that catalyzer has higher CO hydrogenation activity and C under typical FTS condition
2 =～C
4 =The selectivity of hydrocarbon studies show that simultaneously the adding of Mn/K auxiliary agent has improved the selective power of catalyzer to alkene significantly.But, do not see as yet at present relating to that to be used for by synthetic gas be the synthetic C of material choice
20With interior and be mainly the report of the catalyzer of diesel oil distillate section alkane.
Summary of the invention
The object of the invention is to provide that a kind of to be used for by synthetic gas be the material choice carbon number for preparing straight-chain paraffin mainly concentrates on the catalyzer of diesel oil distillate section 20 with interior and hydro carbons carbon number.This catalyzer is made up of active ingredient, auxiliary agent and carrier three parts, and active ingredient is the VIII element, and only is cobalt metal; Auxiliary agent is made up of one or both type auxiliary elements, and the first category auxiliary element is from IVB family metallic element, and as Ti, Zr or IIIB family metallic element, as La, Ce etc., second auxiliary element is from group VIII metallic element such as Rh, Ru, Pt etc.Carrier is selected almond gac, cocoanut active charcoal, oil palm gac or coal activated carbon for use, and the specific surface area of gac is 200m
2/ g～2000m
2/ g, pore volume are 0.3～2.0cm
3/ g, pore size distribution are 4～1000 .In addition, cobalt metal accounts for 4～50% (weight) in total catalyst weight, first auxiliary element (IVB family metallic element, as Ti, Zr or IIIB family metallic element, as La, Ce etc.) in total catalyst weight, account for 0.01～20.0%, second auxiliary element (group VIII metallic element such as Rh, Ru, Pt etc.) and in total catalyst weight, account for 0.01～5.0% (weight).
In the catalyzer of the invention described above, will have macromolecule hydrocarbon and generate active cobalt active substance and introduce the gac system and make the FTS catalyzer, its FTS control of product is at C
20In; And carbon number distribution concentrates on the diesel product of middle runnings section.Its principle one is to have utilized the shape effect of selecting in absorbent charcoal carrier duct, the 2nd, utilized CO and H on the cobalt catalyst
2To the advantage of macromole generation, thus the C that acquisition is wished
20Concentrate on the hydrocarbon products of diesel oil distillate section with interior and component.
In addition, in above-mentioned catalyzer, weight content as the active ingredient cobalt is less than at 4% o'clock, the catalytic activity that is used for the FTS reaction is not high enough, but when surpassing 50%, the content of cobalt can not increase the transformation efficiency of building-up reactions, the Preparation of catalysts process becomes more numerous simultaneously, needs repeatedly with containing cobalt soluble salt solution impregnating carrier.Therefore, be limited to below 50% on it, and the weight content of better cobalt is the 5-25% of catalyzer.
In addition, as adjuvant component,, as Ti, Zr, La, Ce etc., or VIII family metallic element such as Rh, Ru, Pt etc., improved the reactivity worth and the stability of catalyzer effectively if in catalyzer, introduce IVB or IIIB family metallic element.Wherein, can add the first kind auxiliary element or the second analog assistant element separately.In addition, also can introduce two kinds of auxiliary elements of first and second class simultaneously.As first kind auxiliary element, for example the addition of Ti, Zr, Ca or Ce etc. did not then have the effect of the reactivity worth of improving catalyzer less than 0.01% o'clock, and when the introducing amount surpassed 20%, the above-mentioned effect of auxiliary agent there is no considerable change.Therefore, the introducing amount of first kind auxiliary agent is no more than 20% usually.Introducing amount to second analog assistant also should be controlled in the scope of 0.01-5% equally.And the best addition of first kind auxiliary agent is the 0.1-10% of catalyzer, and the best addition of second analog assistant is that catalyzer is below 0.5%.Too much interpolation second analog assistant will increase the Preparation of catalysts cost.
Carrier as catalyzer of the present invention uses gac, can select almond, coconut husk, oil palm or coal activated carbon, particularly almond or coconut husk preparing active carbon for use.And in the present invention,, therefore require gac to have certain specific surface area, pore size distribution and pore volume owing to utilize the shape effect of selecting of gac.
When the specific surface area of gac less than 200m
2During/g,, do not utilize the active ingredient and the adjuvant component that support necessary amount, make the catalytic activity of catalyzer low, surpass 2000m but work as specific surface area because specific surface area is little
2During/g, the ratio of small-bore carrier increases, and also is difficult for dipping active ingredient and adjuvant component.Because specific surface area is chosen as 200-2000m
2During/g, and be preferably 500-1200m
2/ g.In addition, the pore volume of gac is 0.3-2.0cm
3/ g, and be preferably 0.32-1.0cm
3/ g.And the pore size distribution of gac is at 4-1000 , and is preferably 50-500 .In the present invention, the specific surface area of above-mentioned gac, pore volume and pore size distribution are to carry out adsorption method by N2 under 77K constant temperature to measure (ASAP2010 specific surface and pore size determination instrument that U.S. Micromeritics company produces) and calculate.
Above-mentioned Preparation of catalysts method of the present invention, be that drying is used hydrogen reducing with the aqueous solution normal pressure or the negative pressure impregnation gac carrier of nitrate, carbonate or the carbonyl compound of cobalt metal and all auxiliary elements, reduction temperature is 100-700 ℃, and the recovery time is 1-50 hour.
In addition, can use the aqueous solution dipping of the soluble salt of containing metal cobalt or auxiliary element respectively, also can obtain catalyzer with the mixing soluble salt solution impregnation gac of containing metal cobalt and auxiliary element.And, be active ingredient and the auxiliary agent that supports necessary amount, also can flood repeatedly and preferably under negative pressure, carry out.Added negative pressure is not had special requirement, and considering from preparation can be below 80KPa.
Use catalyzer of the present invention to carry out the FTS building-up reactions, can be at fixed-bed process, or carry out in the slurry attitude bed process.Its typical operational condition is: slurry attitude bed reductive condition, 250～400 ℃, 0.3～1.5MPa, 300～1500h
-1(V/V), 300～1200rps, H
2Or synthetic gas atmosphere; Slurry attitude bed reaction conditions: 120～300 ℃, 0.1～10.0MPa, 300～1500h
-1(V/V).The fixed bed reductive condition, 200～500 ℃, 0.3～1.0MPa, 300～1500h
-1(V/V), H
2Or synthetic gas atmosphere; The fixed bed reaction condition: 120～300 ℃, 0.5～10.0MPa, 300～1500h
-1(V/V).Catalyzer is test shows in fixed bed and slurry attitude bed, and the FTS catalyzer of this patent invention has very high conversion and C
11-20Selectivity, carbon number distribution is at C
1-C
20In.Below further be described by example:
Embodiment example 1.
Take by weighing 20 gram almond gac (specific surface area 1182m
2/ g, pore volume 0.45cm
3/ g, flat footpath aperture 26.5 , the place of production, brilliance timber mill, Beijing) the back 180 ℃ of dryings of washing are stand-by after 12 hours.Configuration contains the Co (NO of 2.222 gram Co
3)
2.6H
230 milliliters of the O aqueous solution flood above-mentioned almond gac with this aqueous solution under negative pressure, seasoning, and it is 15% catalyzer 1 that 120 ℃ of oven dryings obtained containing cobalt in 8 hours.Example 2.
Take by weighing 15 gram cocoanut active charcoal (specific surface area 939m
2/ g, pore volume 0.35cm
3/ g, flat footpath aperture 26.6 , the place of production, brilliance timber mill, Beijing), take by weighing 1.67 gram Zr (NO
3)
45H
2O is dissolved in 24 ml waters, floods the almond gac that weighs up with this aqueous solution.110 ℃ of oven dry.Take by weighing 13.39 gram Co (NO
3)
2.6H
2O is dissolved in 17 ml waters, and this aqueous solution floods above-mentioned almond gac under negative pressure, seasoning, and 120 ℃ of oven dryings obtained containing that cobalt is 15% in 8 hours, Zr is 2% catalyzer 2.Example 3.
Take by weighing the almond gac of 15 gram embodiment 1.Take by weighing 1.12 gram Ce (NO
3)
36H
2O is dissolved in 25 ml waters, floods the almond gac that weighs up with this aqueous solution.110 ℃ of oven dry.Take by weighing 13.40 gram Co (NO
3)
2.6H
2O is dissolved in 17 ml waters, and this aqueous solution floods above-mentioned almond gac under negative pressure, seasoning, and 120 ℃ of oven dryings obtained containing that cobalt is 15% in 8 hours, Ce is 2% catalyzer 3.Example 4.
Take by weighing the almond gac of 15 gram embodiment 1.Take by weighing 10.159 gram Co (NO
3)
2.6H
2O and 0.22 gram KNO
3Be dissolved in 19 ml waters, this aqueous solution floods above-mentioned almond gac under negative pressure, seasoning, and 120 ℃ of oven dryings obtained catalyzer 4 in 8 hours.Example 5.
Take by weighing the almond gac of 15 gram embodiment 1.Take by weighing 1.71 gram Zr (NO
3)
45H
2O is dissolved in 24 ml waters, floods the almond gac that weighs up with this aqueous solution.110 ℃ of oven dry.Take by weighing 13.46 gram Co (NO
3)
2.6H
2O and 0.187 gram RuCl
3Be dissolved in 17 ml waters, this aqueous solution floods above-mentioned almond gac under negative pressure, seasoning, and 120 ℃ of oven dryings obtained containing that cobalt is 15% in 8 hours, Zr is 2%, Ru is 0.5% catalyzer 5.Example 6.
Get the above catalyzer of 200 orders in the example 1 12 grams, put into 1 liter slurry reactor, put into boiling range simultaneously and be 350 ℃ analytical pure liquid olefin medium 450ml, at H
2Reduce in slurry reactor under the air-flow, reductive condition is 380 ℃, 4.0MPa, 1000h
-1(V/V), 700r/min, 20h.Reduction is slowly reduced to 200 ℃ with temperature of reaction kettle after finishing, and feeds H
2: CO=2: 1 synthetic gas, and reaction pressure transferred to 2.5MPa, rotating speed transfers to 800r/min, air speed 500h
-1Simultaneously temperature of reaction is slowly risen to 240 ℃.Reaction result is listed in the table 1..Example 7.
Get the above catalyzer of 200 orders in the example 2 12 grams, put into 1 liter slurry reactor, put into boiling range simultaneously and be 350 ℃ analytical pure liquid olefin medium 450ml, at H
2Reduce in slurry reactor under the air-flow, reductive condition is 380 ℃, 6.4MPa, 1000h
-1(V/V), 700r/min, 20h.Reduction is slowly reduced to 200 ℃ with temperature of reaction kettle after finishing, and feeds H
2: CO=2: 1 synthetic gas, and reaction pressure transferred to more than the 2.5MPa, rotating speed transfers to 800r/min, air speed 500h
-1Simultaneously temperature of reaction is slowly risen to 240 ℃.Reaction result is listed in the table 1..
Get catalyzer 3 grams in the example 2, put into the stainless steel fixed-bed reactor (a certain amount of quartz sand with sizes such as catalyzer is adorned at the reactor two ends) of Φ 30 * 6 * 420.At H
2Reduce under the air-flow, reductive condition is 400 ℃, 0.5MPa, 1000h
-1(V/V), 10h.Reduction is slowly reduced to 240 ℃ with temperature of reactor, 2.50MPa, 500h after finishing
-1H
2: CO=2: 1.Reaction result is listed in the table 1..Example 8.
Get catalyzer 3 grams in the example 3, put into the stainless steel fixed-bed reactor (a certain amount of quartz sand with sizes such as catalyzer is adorned at the reactor two ends) of Φ 30 * 6 * 420.At H
2Reduce under the air-flow, reductive condition is 400 ℃, 0.5MPa, 1000h
-1(V/V), 10h.Reduction is slowly reduced to 240 ℃ with temperature of reaction after finishing, and feeds H
2: CO=2: 1 synthetic gas, and reaction pressure transferred to 2.5MPa, air speed 500h
-1Reaction result is listed in the table 1..Example 9.
Get catalyzer 3 grams in the example 4, put into the stainless steel fixed-bed reactor (a certain amount of quartz sand with sizes such as catalyzer is adorned at the reactor two ends) of Φ 30 * 6 * 420.At H
2Reduce under the air-flow, reductive condition is 400 ℃, 0.5MPa, 1000h
-1(V/V), 10h.Reduction is slowly reduced to 240 ℃ with temperature of reaction after finishing, and feeds H
2: CO=2: 1 synthetic gas, and reaction pressure transferred to 2.5MPa, air speed 500h
-1Reaction result is listed in table 1. example 10.
Get the above catalyzer of 200 orders in the example 5 12 grams, put into 1 liter slurry reactor, put into boiling range simultaneously and be 350 ℃ analytical pure liquid olefin medium 450ml, at H
2Reduce in slurry reactor under the air-flow, reductive condition is 380 ℃, 6.4MPa, 1000h
-1(V/V), 700r/min, 20h.Reduction is slowly reduced to 200 ℃ with temperature of reaction kettle after finishing, and feeds H
2: CO=2: 1 synthetic gas, and reaction pressure transferred to more than the 2.5MPa, rotating speed transfers to 800r/min, air speed 500h
-1Simultaneously temperature of reaction is slowly risen to 240 ℃.Reaction result is listed in the table 1..
Get catalyzer 3 grams in the example 5, put into the stainless steel fixed-bed reactor (a certain amount of quartz sand with sizes such as catalyzer is adorned at the reactor two ends) of Φ 30 * 6 * 420.At H
2Reduce under the air-flow, reductive condition is 400 ℃, 0.5MPa, 1000h
-1(V/V), 10h.Reduction is slowly reduced to 240 ℃ with temperature of reaction after finishing, and the synthetic gas increasing temperature and pressure is reacted.Reaction conditions is 240 ℃, 2.5MPa, 800r/min, 500h
-1H
2: CO=2: 1.Reaction result is listed in the table 1..
As shown in Table 1 we the development activated carbon supported cobalt-base catalyst in fixed bed and paste state bed reactor directly the synthetic gas selectivity produce diesel oil distillate section alkane.
Table 1. test-results
| Catalyzer | Reaction conditions | The CO transformation efficiency, % | Yield, g/NM 3sys | Total hydrocarbon distributes, % | Hydrocarbon distributes in the oil phase, % |
| ?C 1 +??C 5 + | ??C 1??C 2-4?C 5 + | ??C 4-9?C 10-20 | |||
| Example 6. | 240℃，2.5MPa，500h -1, fixed bed | 55.6 | ?120.2??96.0 | ??8.4??11.6??80.0 | ??34.3??65.7 |
| Example 7 | 240℃，2.5MPa，500h -1, 240 ℃ on fixed bed, 2.5MPa, 500h -1, slurry attitude bed | 64.1 85.7 | ?138.4??111.6 ?169.4??138.7 | ??8.5??10.8??80.7 ??8.8??9.3???81.9 | ??37.1??62.8 ??34.3??65.7 |
| Example 8. | 240℃，2.5MPa，500h -1, fixed bed | 78.3 | ?162.5??108.7 | ??18.1?15.0??66.9 | ??60.8??39.2 |
| Example 9 | 240℃，2.5MPa，500h -1, fixed bed | 41.6 | ?84.3???66.3 | ??4.1??18.1??77.8 | ??62.8??37.2 |
| Example 10. | 240℃，2.5MPa，500h -1, 240 ℃ on fixed bed, 2.5MPa, 500h -1, slurry attitude bed | 67.3 83.5 | ?132.3??105.8 ?169.6??140.9 | ??9.1??10.9??80.0 ??7.8??9.1???83.1 | ??35.9??64.1 ??32.5??67.5 |
Claims (8)
1. a catalyzer that is used for by synthesis gas preparation diesel oil distillate section alkane is made up of active ingredient, auxiliary agent and carrier three parts, it is characterized in that active ingredient is a cobalt metal; Auxiliary agent is made up of one or both type auxiliary elements, and first kind auxiliary element is Ti, Zr, La or Ce, and the second analog assistant element is Rh, Ru or Pt; Carrier is selected gac for use; Cobalt metal accounts for 4-50% in total catalyst weight, first auxiliary element accounts for 0.01-20.0% in total catalyst weight, and second auxiliary element accounts for 0.01-5.0% in total catalyst weight.
2. according to the described catalyzer of claim 1, it is characterized in that: carrier is selected almond gac, cocoanut active charcoal, oil palm gac or coal activated carbon for use, and the specific surface area of gac is 200m
2/ g-2000m
2/ g, pore volume are 0.3-2.0cm
3/ g, and pore size distribution is 4-1000 .
3. according to the described catalyzer of claim 1, it is characterized in that: described active ingredient is the 5%-25% of total catalyst weight.
4. according to the described catalyzer of claim 1, it is characterized in that: described first auxiliary element accounts for 0.1-10.0% in total catalyst weight.
5. according to the described catalyzer of claim 1, it is characterized in that: described second auxiliary element accounts for 0.01-0.5% in total catalyst weight.
6. described Preparation of catalysts method of claim 1, it is characterized in that: with aqueous solution Immesion active carbon carrier under normal pressure or negative pressure of nitrate, carbonate or the carbonyl compound of cobalt metal and all auxiliary elements, dry, use hydrogen reducing, reduction temperature is 100-700 ℃, and the recovery time is 1-50 hour.
7. according to the described preparation method of claim 6, below negative pressure 80kPa, carry out the Immesion active carbon carrier.
8. described catalyzer of claim 1, to be used for by synthetic gas be the material choice carbon number for preparing straight-chain paraffin mainly concentrates on the reaction process of diesel oil distillate section 20 with interior and hydro carbons carbon number.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011368896A CN1190267C (en) | 2001-11-06 | 2001-11-06 | Catalyst for preparing alkane of diesel oil fraction from synthetic gas and its prepn |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011368896A CN1190267C (en) | 2001-11-06 | 2001-11-06 | Catalyst for preparing alkane of diesel oil fraction from synthetic gas and its prepn |
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| Publication Number | Publication Date |
|---|---|
| CN1417292A true CN1417292A (en) | 2003-05-14 |
| CN1190267C CN1190267C (en) | 2005-02-23 |
Family
ID=4673979
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|---|---|---|---|
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|---|---|---|---|---|
| CN101310856B (en) * | 2007-05-24 | 2010-10-13 | 中国科学院大连化学物理研究所 | Catalyst for directly synthesizing high carbon primary alcohol using CO hydrogenation and preparation method thereof |
| CN102371151A (en) * | 2010-08-26 | 2012-03-14 | 中国石油化工股份有限公司 | Nano-precious metal catalyst and preparation method thereof |
| CN102059093B (en) * | 2009-11-18 | 2012-10-10 | 中国科学院生态环境研究中心 | Arsenic and fluorine removing nano-composite adsorbent |
| CN102863982A (en) * | 2011-07-04 | 2013-01-09 | 中国石油化工股份有限公司 | Work starting method for slurry bed Fisher-Tropsch synthesis |
| CN103157492A (en) * | 2011-12-15 | 2013-06-19 | 中国石油化工股份有限公司 | Shell distribution catalyst and preparation method thereof |
| CN103289824A (en) * | 2012-02-24 | 2013-09-11 | 中国科学院大连化学物理研究所 | Conversion process of grease |
| CN104874405A (en) * | 2015-05-20 | 2015-09-02 | 上海兖矿能源科技研发有限公司 | Fischer-Tropsch synthesis cobalt catalyst for slurry bed reactor and preparation and application of slurry bed reactor |
| CN106268816A (en) * | 2015-06-12 | 2017-01-04 | 中国科学院大连化学物理研究所 | Activated carbon supported cobalt-based synthetic oil catalyst and its preparation method and application |
| CN113145132A (en) * | 2021-04-26 | 2021-07-23 | 中国科学院上海高等研究院 | Ruthenium-based catalyst and preparation method and application thereof |
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2001
- 2001-11-06 CN CNB011368896A patent/CN1190267C/en not_active Expired - Lifetime
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| CN101310856B (en) * | 2007-05-24 | 2010-10-13 | 中国科学院大连化学物理研究所 | Catalyst for directly synthesizing high carbon primary alcohol using CO hydrogenation and preparation method thereof |
| CN102059093B (en) * | 2009-11-18 | 2012-10-10 | 中国科学院生态环境研究中心 | Arsenic and fluorine removing nano-composite adsorbent |
| CN102371151A (en) * | 2010-08-26 | 2012-03-14 | 中国石油化工股份有限公司 | Nano-precious metal catalyst and preparation method thereof |
| CN102371151B (en) * | 2010-08-26 | 2013-05-01 | 中国石油化工股份有限公司 | Nano-precious metal catalyst and preparation method thereof |
| CN102863982A (en) * | 2011-07-04 | 2013-01-09 | 中国石油化工股份有限公司 | Work starting method for slurry bed Fisher-Tropsch synthesis |
| CN102863982B (en) * | 2011-07-04 | 2015-05-13 | 中国石油化工股份有限公司 | Work starting method for slurry bed Fisher-Tropsch synthesis |
| CN103157492B (en) * | 2011-12-15 | 2015-07-29 | 中国石油化工股份有限公司 | A kind of Catalysts and its preparation method of shell distribution |
| CN103157492A (en) * | 2011-12-15 | 2013-06-19 | 中国石油化工股份有限公司 | Shell distribution catalyst and preparation method thereof |
| CN103289824A (en) * | 2012-02-24 | 2013-09-11 | 中国科学院大连化学物理研究所 | Conversion process of grease |
| CN104874405A (en) * | 2015-05-20 | 2015-09-02 | 上海兖矿能源科技研发有限公司 | Fischer-Tropsch synthesis cobalt catalyst for slurry bed reactor and preparation and application of slurry bed reactor |
| CN106268816A (en) * | 2015-06-12 | 2017-01-04 | 中国科学院大连化学物理研究所 | Activated carbon supported cobalt-based synthetic oil catalyst and its preparation method and application |
| CN113145132A (en) * | 2021-04-26 | 2021-07-23 | 中国科学院上海高等研究院 | Ruthenium-based catalyst and preparation method and application thereof |
| CN113145132B (en) * | 2021-04-26 | 2023-02-10 | 中国科学院上海高等研究院 | Ruthenium-based catalyst and preparation method and application thereof |
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|---|---|
| CN1190267C (en) | 2005-02-23 |
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