CN105597772A - Cobalt-based catalyst having core-shell structure, and preparation method thereof - Google Patents
Cobalt-based catalyst having core-shell structure, and preparation method thereof Download PDFInfo
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Abstract
The present invention discloses a preparation method of a cobalt-based catalyst having a core-shell structure. The preparation method comprises: 1) selecting an industrially molded composite oxide as a carrier; 2) dissolving a soluble cobalt salt and a metal auxiliary agent salt in an alcohol and water mixing solvent to prepare an impregnating solution; 3) at the high speed flipping state of the composite oxide carrier, rapidly and uniformly mixing the impregnating solution and the composite oxide carrier to prepare a solid catalyst precursor; and 4) drying, and calcining to obtain the cobalt-based catalyst having the core-shell structure. The present invention further discloses the cobalt-based catalyst having the core-shell structure and prepared through the method. According to the present invention, the industrially molded composite oxide is selected as the carrier, and the cobalt salt and the metal auxiliary agent salt adopted as the active components are uniformly impregnated on the outer surface of the carrier by using the rapid rolling of the carrier, such that the defect that the traditional impregnating method cannot accurately control the active species distribution appearance is broken through, the efficient utilization of the cobalt metal is achieved, the catalyst preparation cost is reduced, and the activity and the operation stability of the catalyst are improved.
Description
Technical field
The present invention relates to support type heterogeneous catalyst, particularly relate to cobalt-base catalyst synthetic for Fischer-Tropsch and preparation method thereof.
Background technology
Face the feature of approaching and China's energy consumption structure of energy crisis, utilize Fischer-Tropsch synthetic by coal, natural gas or living beingsTurn to liquid fuel through synthetic cyclostrophic and become a practicable path of China's solution energy crisis. Fischer-Tropsch is synthetic is syntheticGas (CO and H2Mist) generate hydro carbons and a small amount of containing oxidation in the upper reaction of transition-metal catalyst (as iron system, cobalt system)The polymerization process of compound. Product can obtain high-quality liquid fuel (as gasoline, diesel oil, aviation kerosine etc.), these fuel through deep processingIn not sulfur compound and nitride, be very clean automotive fuel. At present, iron-based and cobalt-base catalyst are that Fischer-Tropsch is synthetic conventionalCatalyst. Compared with ferrum-based catalyst, cobalt-base catalyst has following features: (1) cobalt-base catalyst knot carbon tendency is low, aliveProperty is high, and byproduct methane is selectively low, and the life-span is relatively long, and the hard wax that cobalt-based technique also can attached product high added value; (2) cobaltBased catalyst in water-gas shift reaction activity is low, is applicable to high H2The natural gas base synthesis gas of/CO ratio transforms. Considering insteadAnswer on the basis of several respects factors such as activity, life-span and selectivity of product, cobalt-base catalyst becomes the focus of current research. ButThe ferrum-based catalyst of comparing, the shortcoming of cobalt-base catalyst is that the price of cobalt salt is more expensive, and then causes being prepared into of catalystThis is higher. Therefore, in order to save the preparation cost of catalyst, realize the efficient utilization of cobalt active metal in catalyst, need be at cobaltIn catalyst based process, expensive cobalt metal controllable load, at carrier outer surface, is not only beneficial to synthesis gas and active goldThe abundant contact belonging to and utilize reactant and the diffusion mass transfer of product, is also beneficial to and reacts effectively the shifting out of Heat of Formation.
At present, the preparation method of industrial cobalt-base catalyst adopts in two ways substantially, and one is co-precipitation method, anotherPlant as equi-volume impregnating. Although cobalt-base catalyst catalytic activity and oily wax that co-precipitation legal system is standby are selectively higher,The complicated process of preparation of catalyst, preparation cost is higher, and a large amount of waste water of by-product. And the catalyst after moulding is at slurry reactorThe easy efflorescence of middle particle, mechanical strength is poor, is unfavorable for separating of catalyst and product. And cobalt-base catalyst prepared by infusion process byIn the catalyst carrier of directly selecting industrial moulding, so its preparation technology is simple, preparation cost is low, does not have washes to produceRaw, environmental friendliness. But because prepared catalyst particle size is larger, synthesis gas easily produces diffusion limit in course of reactionSystem, causes being difficult in the cobalt activated centre of catalyst granules core position fully contact with synthesis gas, and H2With CO diffusion velocityDifference and cause in the Co at core position place active sites surface H2/ CO ratio raises, and then causes CH4Optionally increase.In addition, larger catalyst particle size also causes formed hydrocarbon products to be difficult to spread out in time, is adsorbed in metallic cobalt activityOn position and reduce the actual active sites number that participates in catalytic reaction, and then reduce catalytic reaction activity. In addition, if Fischer-Tropsch is syntheticThe heat of reaction generating, as can not be effectively shifted out, easily causes the generation of hot localised points, thereby causes the sintering of catalyst, causesThe inactivation of catalyst.
Summary of the invention
One of the technical problem to be solved in the present invention is to provide a kind of preparation method of core-shell structure cobalt-base catalyst, the method techniqueSimply, cost is low, reproducible, and gained catalyst mechanical strength is high, and anti-sintering property is good.
For solving the problems of the technologies described above, the preparation method of core-shell structure cobalt-base catalyst of the present invention, step comprises:
1) composite oxides of choosing industrial moulding are as carrier;
2) solubility cobalt salt and soluble metal builder salts are dissolved in alcohol water mixed solvent, make maceration extract;
3) allow composite oxide carrier in stirring state at a high speed, rapidly maceration extract mixed with composite oxide carrier,Obtain solid catalyst precursor body;
4) to solid catalyst precursor body be dried, roasting, make core-shell structure cobalt-base catalyst.
Described composite oxides can be selected from zirconium dioxide, silica, aluminium oxide, titanium oxide two or moreCombination. The specific area of composite oxide carrier is 100～500m2/ g, pore volume is 0.5～1.5cm3/ g, average pore size distributesBe 5～20nm. The shape of composite oxide carrier can be microspheroidal, cloverleaf pattern, cylindrical or pentalpha. Wherein,Microspheroidal composite oxide carrier can adopt spray drying forming legal system standby, and particle size range is 50～1000 μ m; Cloverleaf pattern,Cylindrical and pentalpha composite oxide carrier can adopt extruded moulding legal system standby, and the length of bar shaped particle is at 2～10mmIn scope, diameter is within the scope of 0.5～5mm.
Described solubility cobalt salt can be selected from two or more the combination in cobalt nitrate, carbonyl cobalt, cobalt acetate.
Described soluble metal builder salts can be selected from nitric acid ruthenium, lanthanum nitrate, manganese nitrate, cerous nitrate, niobium oxalate, nickel nitrate,The combination of two or more in ferric nitrate.
Described alcohol water mixed solvent can use the mixed solvent of ethanol and water, and in mixed solvent, the volume ratio of ethanol and water is1:10～10:1。
Described step 3), the charging rate of every 1g carrier impregnation liquid is 1～4mL/s.
Two of the technical problem to be solved in the present invention is to provide the cobalt-base catalyst of preparing with said method, and this cobalt-base catalyst is coreShell structure, its main active metal cobalt and promoter metal are evenly distributed on the outer surface of composite oxide carrier.
In this cobalt-base catalyst, active metal cobalt content is 5～25%, and promoter metal content is 0.5～5%, and composite oxides carryBody burden is 70～95%.
Above-mentioned core-shell structure cobalt-base catalyst can be in the reaction of the synthetic prepare liquid fuel of Fischer-Tropsch, and reaction condition is: syntheticGas H2: the mol ratio 1.8～2.2 of CO, 200～270 DEG C of the temperature of catalytic reaction, the stagnation pressure 1～4Mpa of synthesis gas; Air speed 1000～10000h-1。
The present invention carries out the structural design of catalyst from the angle of commercial Application, utilize the composite oxide carrier of industrial mouldingQuick rolling, cobalt salt, metal promoter salt as active component evenly be impregnated in to the outer surface of carrier, thereby have broken through biographySystem infusion process cannot accurately be controlled the deficiency of active specy distribution. Compared with the cobalt-base catalyst of having reported at present, with thisCore-shell structure cobalt-base catalyst prepared by bright method, has the following advantages and beneficial effect:
1. select the composite oxides that carry out after industrial moulding as carrier, therefore preparation technology is simple, reproducible, producesCost is lower, be easy to industry and amplify, and the mechanical strength of the catalyst preparing is high, and anti-sintering property is good;
2. active metal cobalt gets the efficient use, and has reduced the consumption of cobalt precursor, thereby has reduced the production cost of catalyst;
3. reduce diffusion, the mass transfer limit of synthesis gas and product, be conducive to effectively shifting out and temperature of Fischer-Tropsch synthesis Heat of FormationDegree is stable, and CO conversion ratio is high, and oily wax is selectively high, and byproduct of reaction is selectively low, and catalyst is stable and the life-span is long.
Detailed description of the invention
Below in conjunction with specific embodiment, technical scheme of the present invention is described in detail.
Embodiment 1
Co:MnO by mass percentage2:ZrO2/Al2O3The ratio of composite oxide carrier=10:1:89 is cobalt group catalyst synthesized. SpecificallyStep is as follows:
Step 1, by the mass percent of above-mentioned 10:1:89, first weighs 5g microspheroidal ZrO2/Al2O3Composite oxide carrier(adopt the preparation of spray drying forming technology, particle diameter is 500 μ m, and specific area is 230m2/ g, pore volume is 1.1cm3/g，Average pore size is distributed as 15nm).
Step 2, takes 2.77g cobalt nitrate and 0.16g manganese nitrate, is dissolved in 5mL alcohol water (VEthanol:VWater=1:1) in, be mixed withMaceration extract.
Step 3, by 5g microspheroidal ZrO2/Al2O3Composite oxide carrier is put into Rotary Evaporators, and at the bar of rapid stirringUnder part, at every 1gZrO2/Al2O3Under the rate of addition of composite oxide carrier 1mL/s, the dipping of rapidly step 2 being preparedLiquid utilizes peristaltic pump to pump into, and with microspheroidal ZrO2/Al2O3Composite oxide carrier mixes equably, gained solid catalystPresoma after 60 DEG C of dry 12h, 300 DEG C of roasting 4h, programming rate is 1 DEG C/min, makes core-shell structure cobalt-base catalyst(called after Cat-1).
Embodiment 2
Co:La by mass percentage2O3:SiO2/Al2O3The ratio of composite oxide carrier=15:0.5:84.5 is cobalt group catalyst synthesized.Concrete steps are as follows:
Step 1, by the mass percent of above-mentioned 15:0.5:84.5, first weighs 5g trifolium-shaped SiO2/Al2O3Combined oxidation(utilize the preparation of extruded moulding technology, particle diameter length is within the scope of 10mm, and diameter is 5mm, and specific area is 260m for thing carrier2/g，Pore volume is 1.0cm3/ g, average pore size is distributed as 14nm).
Step 2, takes 4.38g cobalt nitrate and 0.08g lanthanum nitrate, is dissolved in 5mL alcohol water (VEthanol:VWater=2:1) in, be mixed withMaceration extract.
Step 3, by 5g trifolium-shaped SiO2/Al2O3Composite oxide carrier is put into Rotary Evaporators, and at rapid stirringUnder condition, at every 1gSiO2/Al2O3Under the rate of addition of composite oxide carrier 1.5mL/s, rapidly step 2 is preparedMaceration extract utilizes peristaltic pump to pump into, and and SiO2/Al2O3Composite oxide carrier mixes equably, before gained solid catalystDrive body after 60 DEG C of dry 12h, 300 DEG C of roasting 4h, programming rate is 1 DEG C/min, makes core-shell structure cobalt-base catalyst (lifeCat-2 by name).
Embodiment 3
Co:NiO:TiO by mass percentage2/Al2O3The ratio of composite oxide carrier=20:0.5:79.5 is cobalt group catalyst synthesized.Concrete steps are as follows:
Step 1, by the mass percent of above-mentioned 20:0.5:79.5, first weighs 5g column type TiO2/Al2O3Composite oxides(utilize the preparation of extruded moulding technology, particle diameter length is within the scope of 8mm, and diameter is 4mm, and specific area is 250m for carrier2/g，Pore volume is 0.9cm3/ g, average pore size is distributed as 12nm).
Step 2, takes 6.21g cobalt nitrate and 0.12g nickel nitrate, is dissolved in 4.5mL alcohol water (VEthanol:VWater=5:1) in, be mixed withMaceration extract.
Step 3, by 5g column type TiO2/Al2O3Composite oxide carrier is put into Rotary Evaporators, and at the bar of rapid stirringUnder part, at every 1gTiO2/Al2O3Under the rate of addition of composite oxide carrier 2mL/s, the dipping of rapidly step 2 being preparedLiquid utilizes peristaltic pump to pump into, and and TiO2/Al2O3Composite oxide carrier mixes equably, gained solid catalyst precursor bodyAfter 60 DEG C of dry 12h, 300 DEG C of roasting 4h, programming rate is 1 DEG C/min, makes core-shell structure cobalt-base catalyst (nameFor Cat-3).
Embodiment 4
Co:CeO by mass percentage2:ZrO2/SiO2/Al2O3The ratio of composite oxide carrier=25:1:74 is cobalt group catalyst synthesized.Concrete steps are as follows:
Step 1, by the mass percent of above-mentioned 25:1:74, first weighs 5g pentagon ZrO2/SiO2/Al2O3Composite oxides(utilize the preparation of extruded moulding technology, particle diameter length is within the scope of 5cm, and diameter is 2.5mm, and specific area is 150m for carrier2/g，Pore volume is 1.0cm3/ g, average pore size is distributed as 17nm).
Step 2, takes 8.34g cobalt nitrate and 0.17g cerous nitrate, is dissolved in 4mL alcohol water (VEthanol:VWater=1:2) in, be mixed with and soakStain liquid.
Step 3, by 5g pentagon ZrO2/SiO2/Al2O3Composite oxide carrier is put into Rotary Evaporators, and at rapid stirringCondition under, at every 1gZrO2/SiO2/Al2O3Under the rate of addition of composite oxide carrier 3mL/s, rapidly by above-mentioned preparationMaceration extract utilize peristaltic pump to pump into, and and ZrO2/SiO2/Al2O3Composite oxide carrier mixes equably, gained solidCatalyst precursor after 60 DEG C of dry 12h, 300 DEG C of roasting 4h, programming rate is 1 DEG C/min, makes core-shell structure cobalt-baseCatalyst (called after Cat-4).
Embodiment 5
Co:CeO by mass percentage2:La2O3:ZrO2/SiO2/Al2O3The ratio of composite oxide carrier=5:1:1:93 is synthesis cobalt-basedCatalyst. Concrete steps are as follows:
Step 1, by the mass percent of above-mentioned 5:1:1:93, first weighs 5g microspheroidal ZrO2/SiO2/Al2O3Composite oxides(adopt the preparation of spray drying forming technology, particle diameter is 600 μ m to carrier, and specific area is 280m2/ g, pore volume is 1.2cm3/g，Average pore size is distributed as 16nm).
Step 2, takes 1.33g cobalt nitrate, 0.14g cerous nitrate and 0.14g lanthanum nitrate, is dissolved in 5mL alcohol water (VEthanol:VWater＝1:5)In, be mixed with maceration extract.
Step 3, by 5g microspheroidal ZrO2/SiO2/Al2O3Composite oxide carrier is put into Rotary Evaporators, and at rapid stirringCondition under, at every 1gZrO2/SiO2/Al2O3Under the rate of addition of composite oxide carrier 3mL/s, rapidly step 2 is joinedThe maceration extract of system utilizes peristaltic pump to pump into, and and ZrO2/SiO2/Al2O3Composite oxide carrier mixes equably, and gained is solidBody catalyst presoma after 60 DEG C of dry 12h, 300 DEG C of roasting 4h, programming rate is 1 DEG C/min, makes nucleocapsid structure cobaltCatalyst based (called after Cat-5).
The core-shell structure cobalt-base catalyst of preparing in above each embodiment is carried out to the synthetic performance of Fischer-Tropsch on 5mL fixed bed reactorsEvaluate. The first pressure lower sheeting at 20MPa by cobalt-base catalyst before reaction, is broken for 60～80 orders, afterwards then by 2mL cobaltThe quartz sand of catalyst based and same order number packs in fixed bed reactors after mixing with the ratio of volume ratio 1:1, at 1MPaH2PressTemperature programmed reduction 8h at power and 400 DEG C, hydrogen flow rate is 33mL/min, after reduction finishes, is cooled to room temperature, then will be anti-Answer pressure to be increased to 2MPa, switch to synthesis gas (CO and H2Mist), temperature programming is reacted, online gas phase lookAnalysis of spectrum tail gas composition. Collect wax phase product with hot trap, cold-trap is collected oil-phase product, off-line gas chromatographic analysis oil wax composition.Result is as shown in table 1:
The synthetic performance evaluation of Fischer-Tropsch of cobalt-base catalyst prepared by the each embodiment of table 1
Reaction condition: T=230 DEG C, P=2.0MPa, H2/CO＝2.0，GHSV＝1000h-1。
Claims (13)
1. the preparation method of core-shell structure cobalt-base catalyst, is characterized in that, step comprises:
1) composite oxides of choosing industrial moulding are as carrier;
2) solubility cobalt salt and soluble metal builder salts are dissolved in alcohol water mixed solvent, make maceration extract;
3) allow composite oxide carrier in stirring state at a high speed, rapidly maceration extract mixed with composite oxide carrier,Obtain solid catalyst precursor body;
4) to solid catalyst precursor body be dried, roasting, make core-shell structure cobalt-base catalyst.
2. method according to claim 1, is characterized in that, described composite oxides be selected from zirconium dioxide, silica,The combination of two or more in aluminium oxide, titanium oxide.
3. method according to claim 1, is characterized in that, the specific area of composite oxide carrier is 100～500m2/g，Pore volume is 0.5～1.5cm3/ g, average pore size is distributed as 5～20nm.
4. method according to claim 1, is characterized in that, the shape of composite oxide carrier comprises microspheroidal, three leavesGrass shape, cylindrical and pentalpha.
5. method according to claim 4, is characterized in that, microspheroidal composite oxide carrier adopts spray drying formingLegal system is standby, and particle size range is 50～1000 μ m.
6. method according to claim 4, is characterized in that, cloverleaf pattern, cylindrical and pentalpha combined oxidationThing carrier adopts extruded moulding legal system standby, and the length of bar shaped particle is 2～10mm, and diameter is 0.5～5mm.
7. method according to claim 1, is characterized in that, described cobalt salt is selected from cobalt nitrate, carbonyl cobalt, cobalt acetateTwo or more combination.
8. method according to claim 1, is characterized in that, described metal promoter salt is selected from nitric acid ruthenium, lanthanum nitrate, nitreThe combination of two or more in acid manganese, cerous nitrate, niobium oxalate, nickel nitrate, ferric nitrate.
9. method according to claim 1, is characterized in that step 2), described alcohol water mixed solvent is ethanol and waterMixed solvent, the volume ratio of ethanol and water is 1:10～10:1.
10. method according to claim 1, is characterized in that step 3), the charging rate of every 1g carrier impregnation liquidBe 1～4mL/s.
11. methods according to claim 1, is characterized in that step 4) in gained cobalt-base catalyst, active metalCobalt content is 5～25%, and promoter metal content is 0.5～5%, and composite oxide carrier content is 70～95%.
The core-shell structure cobalt-base catalyst that described in 12. use claim 1 to 11 any one prepared by method, is characterized in that, shouldCobalt-base catalyst is nucleocapsid structure, and main active metal cobalt and promoter metal are evenly distributed on the outer surface of composite oxide carrier.
13. according to the cobalt-base catalyst described in right 12, it is characterized in that, in this cobalt-base catalyst, active metal cobalt content is5～25%, promoter metal content is 0.5～5%, and composite oxide carrier content is 70～95%.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106698528A (en) * | 2017-01-25 | 2017-05-24 | 中国科学院新疆理化技术研究所 | Composite oxide material with core-shell structure, and preparation method and application thereof |
| CN106984318A (en) * | 2017-04-27 | 2017-07-28 | 山西大学 | A kind of bimetallic cobalt-base catalyst and preparation method and application |
| CN108126701A (en) * | 2017-12-27 | 2018-06-08 | 厦门大学 | A kind of syngas catalytic conversion catalyst and preparation method thereof |
| CN109718774A (en) * | 2017-10-27 | 2019-05-07 | 中国石油化工股份有限公司 | A kind of catalyst and its preparation method and application and Fischer-Tropsch synthesis method |
| CN109718772A (en) * | 2017-10-27 | 2019-05-07 | 中国石油化工股份有限公司 | A kind of loaded catalyst and its preparation method and application and Fischer-Tropsch synthesis method |
| CN109718783A (en) * | 2017-10-27 | 2019-05-07 | 中国石油化工股份有限公司 | A kind of stable ultra-fine FT synthetic catalyst and its preparation method and application and Fischer-Tropsch synthesis method |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1398951A (en) * | 2002-07-19 | 2003-02-26 | 中国科学院山西煤炭化学研究所 | Co/TiO2 catalyst for Fischer-Tropsch synthesis of heavy hydrocarbon and its prepn |
| CN101224425A (en) * | 2008-01-30 | 2008-07-23 | 中国科学院山西煤炭化学研究所 | Co catalyst with controllable Fischer-Tropsch product distribution, preparing and applications thereof |
| 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 |
| CN103203249A (en) * | 2012-01-12 | 2013-07-17 | 中国科学院大连化学物理研究所 | Preparation method of H type beta molecular sieve membrane packaged capsule catalyst |
-
2014
- 2014-11-04 CN CN201410613569.5A patent/CN105597772B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1398951A (en) * | 2002-07-19 | 2003-02-26 | 中国科学院山西煤炭化学研究所 | Co/TiO2 catalyst for Fischer-Tropsch synthesis of heavy hydrocarbon and its prepn |
| CN101224425A (en) * | 2008-01-30 | 2008-07-23 | 中国科学院山西煤炭化学研究所 | Co catalyst with controllable Fischer-Tropsch product distribution, preparing and applications thereof |
| 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 |
| CN103203249A (en) * | 2012-01-12 | 2013-07-17 | 中国科学院大连化学物理研究所 | Preparation method of H type beta molecular sieve membrane packaged capsule catalyst |
Non-Patent Citations (2)
| Title |
|---|
| 中国石油化工集团公司人事部等: "《催化剂制造工》", 30 November 2010, 中国石化出版社 * |
| 李大东: "《加氢处理工艺与工程》", 31 December 2004, 中国石化出版社 * |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106698528A (en) * | 2017-01-25 | 2017-05-24 | 中国科学院新疆理化技术研究所 | Composite oxide material with core-shell structure, and preparation method and application thereof |
| CN106984318A (en) * | 2017-04-27 | 2017-07-28 | 山西大学 | A kind of bimetallic cobalt-base catalyst and preparation method and application |
| CN106984318B (en) * | 2017-04-27 | 2020-01-03 | 山西大学 | Bimetal cobalt-based catalyst, preparation method and application |
| CN109718774A (en) * | 2017-10-27 | 2019-05-07 | 中国石油化工股份有限公司 | A kind of catalyst and its preparation method and application and Fischer-Tropsch synthesis method |
| CN109718772A (en) * | 2017-10-27 | 2019-05-07 | 中国石油化工股份有限公司 | A kind of loaded catalyst and its preparation method and application and Fischer-Tropsch synthesis method |
| CN109718783A (en) * | 2017-10-27 | 2019-05-07 | 中国石油化工股份有限公司 | A kind of stable ultra-fine FT synthetic catalyst and its preparation method and application and Fischer-Tropsch synthesis method |
| CN109718783B (en) * | 2017-10-27 | 2022-03-11 | 中国石油化工股份有限公司 | Stable superfine FT synthesis catalyst, preparation method and application thereof, and Fischer-Tropsch synthesis method |
| CN109718772B (en) * | 2017-10-27 | 2022-03-11 | 中国石油化工股份有限公司 | Supported catalyst, preparation method and application thereof, and Fischer-Tropsch synthesis method |
| CN108126701A (en) * | 2017-12-27 | 2018-06-08 | 厦门大学 | A kind of syngas catalytic conversion catalyst and preparation method thereof |
| CN108126701B (en) * | 2017-12-27 | 2019-07-26 | 厦门大学 | A kind of syngas catalytic conversion catalyst and preparation method thereof |
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