CN115337930B - Preparation method of graphitized carbon modified shell-core Co-based catalyst and application of graphitized carbon modified shell-core Co-based catalyst in carbon monoxide hydrogenation catalysis - Google Patents
Preparation method of graphitized carbon modified shell-core Co-based catalyst and application of graphitized carbon modified shell-core Co-based catalyst in carbon monoxide hydrogenation catalysis Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 77
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 21
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 229910002091 carbon monoxide Inorganic materials 0.000 title claims abstract description 13
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 11
- 238000006555 catalytic reaction Methods 0.000 title abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 72
- 230000003197 catalytic effect Effects 0.000 claims abstract description 27
- 239000000126 substance Substances 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims description 34
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 29
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 24
- 238000001354 calcination Methods 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 13
- 150000001868 cobalt Chemical class 0.000 claims description 12
- 239000007789 gas Substances 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- 235000019441 ethanol Nutrition 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 238000006460 hydrolysis reaction Methods 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 8
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 7
- 239000012046 mixed solvent Substances 0.000 claims description 7
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 claims description 6
- 238000009210 therapy by ultrasound Methods 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 5
- 239000012266 salt solution Substances 0.000 claims description 4
- 230000007062 hydrolysis Effects 0.000 claims description 3
- GFHNAMRJFCEERV-UHFFFAOYSA-L cobalt chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Co+2] GFHNAMRJFCEERV-UHFFFAOYSA-L 0.000 claims description 2
- MEYVLGVRTYSQHI-UHFFFAOYSA-L cobalt(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Co+2].[O-]S([O-])(=O)=O MEYVLGVRTYSQHI-UHFFFAOYSA-L 0.000 claims description 2
- ZBYYWKJVSFHYJL-UHFFFAOYSA-L cobalt(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Co+2].CC([O-])=O.CC([O-])=O ZBYYWKJVSFHYJL-UHFFFAOYSA-L 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 239000005416 organic matter Substances 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 16
- 229910017052 cobalt Inorganic materials 0.000 abstract description 13
- 239000010941 cobalt Substances 0.000 abstract description 13
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 abstract description 13
- 239000002028 Biomass Substances 0.000 abstract description 6
- 239000011257 shell material Substances 0.000 abstract description 5
- 150000001336 alkenes Chemical class 0.000 abstract description 4
- 239000011258 core-shell material Substances 0.000 abstract description 4
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 4
- 230000008901 benefit Effects 0.000 abstract description 3
- 239000003795 chemical substances by application Substances 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 3
- 239000007795 chemical reaction product Substances 0.000 abstract description 2
- 229920000642 polymer Polymers 0.000 abstract description 2
- 230000036632 reaction speed Effects 0.000 abstract description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 19
- 239000006004 Quartz sand Substances 0.000 description 16
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 16
- 229910052751 metal Inorganic materials 0.000 description 12
- 239000002184 metal Substances 0.000 description 12
- 238000000034 method Methods 0.000 description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- 238000011156 evaluation Methods 0.000 description 8
- 238000000634 powder X-ray diffraction Methods 0.000 description 8
- 150000002430 hydrocarbons Chemical class 0.000 description 6
- 239000011148 porous material Substances 0.000 description 6
- 230000009467 reduction Effects 0.000 description 6
- 229910004298 SiO 2 Inorganic materials 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 230000035484 reaction time Effects 0.000 description 5
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 4
- 239000012159 carrier gas Substances 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
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- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000013335 mesoporous material Substances 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000027756 respiratory electron transport chain Effects 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N 1H-pyrrole Natural products C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000002156 adsorbate Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
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- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000011943 nanocatalyst Substances 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/396—Distribution of the active metal ingredient
- B01J35/398—Egg yolk like
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
- C07C1/04—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen
- C07C1/0425—Catalysts; their physical properties
- C07C1/043—Catalysts; their physical properties characterised by the composition
- C07C1/0435—Catalysts; their physical properties characterised by the composition containing a metal of group 8 or a compound thereof
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
- C07C1/04—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen
- C07C1/0425—Catalysts; their physical properties
- C07C1/0445—Preparation; Activation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C11/00—Aliphatic unsaturated hydrocarbons
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- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention provides a preparation method of graphitized carbon modified shell-core Co-based catalyst and application thereof in carbon monoxide hydrogenation catalysis. By modifying the microstructure of the core-shell material, the finite field reaction function of the core-shell catalytic material is realized, and the C of the reaction product is improved 5+ The directional selectivity, the template agent in the mesoporous shell layer can be replaced by a polymer generated by biomass conversion, and the preparation method is simple and can be produced in a large scale. The final cobalt-based catalyst prepared in the invention is filled with CO and H 2 Can prepare high-value chemicals such as olefin, and has the advantages of high reaction speed, high catalytic efficiency, good circulating effect and the like.
Description
Technical Field
The invention belongs to the field of new material preparation technology and application, and particularly relates to a preparation method and application of an elemental cobalt-based catalyst material.
Background
Environmental pollution and energy shortage caused by massive consumption of fossil energy seriously affect the sustainable development of society and threaten the health of human beings. Biomass gasification converted synthesis gas (co+h) 2 ) The clean liquid hydrocarbon fuel which can be converted into sulfur-free, nitrogen-free compounds and aromatic hydrocarbon-free liquid hydrocarbon fuel through Fischer-Tropsch synthesis (FTS) is a clean production route for replacing the traditional petrochemical industry. The distribution of products of the directional conversion of biomass CO hydrogenation is mainly concentrated on C 1 -C 20 Hydrocarbon compound and meets Anderson-Schulz-Flory (ASF) distribution rule, C 5 -C 20 Hydrocarbon compounds (including C 5 -C 20 Olefins and C 5 -C 20 Alkane) selectivity can reach about 63%. Therefore, the method is more accurate and effective in realizing the hydrogenation directional conversion of biomass CO and can improve C 5+ The selectivity of hydrocarbon products is an ideal requirement for scientists in the future catalysis field. To achieve this goal, the adsorption capacity of CO to the catalyst is improved and H is weakened by modifying the physical structural characteristics and reaction process of the catalyst 2 Finally realizes the breakthrough of ASF distribution rule. In actual industrial processes, the reaction process is quite mature, only by developing advanced functional materials to address these challenges. Many researchers in the catalytic field have begun to consider the application of carbon materials as specific modifiers on mesoporous materials to solve some of the problems described above. The Li Xiaonian subject group of Zhejiang university of Industrial science, inc. uses carbon nitride doped with dicyandiamide (DCDA) precursor to SiO 2 Co-based catalyst (Co/SiO) 2 -CN). Meanwhile, the characterization result shows that Co/SiO 2 Pyrrole N atoms formed on the-CN catalyst are more prone to transfer their electrons to the adjacent Co 0 On the particles, this electron transfer improves the electron defect state, enhancing Co/SiO 2 CO adsorption dissociation capability of the CN catalyst. However, the metal in the catalyst with the supported structure is exposed in the air and is easily oxidized, and meanwhile, the metal is easily agglomerated and carbon deposited in the Fischer-Tropsch catalytic reaction process. In the existing cobalt-based Fischer-Tropsch catalyst, the metal active component is higher. And various metals are required to be doped with each other, hydrogenation reduction is required before application, the process is complex, and the cost is high. And the reaction speed is slow, the catalytic efficiency is low, and longer catalytic time is needed.
Therefore, how to dispense with multi-metal doping can obviously improve the catalytic activity and efficiently hydrogenate and directionally convert the CO into the cobalt-based catalyst.
Disclosure of Invention
In order to solve the problems in the background technology, the invention aims to provide the cobalt-based catalyst which is suitable for the hydrogenation catalysis of carbon monoxide and finally obtains high-value chemicals, and the gel method is adopted, so that the operation is simple and controllable. Specifically, a graphitized carbon modified porous shell-core structure catalyst is used for constructing a high-efficiency thermocatalytic system (shown in figure 1) which can be used for the hydrogenation directional conversion of biomass CO.
The invention also provides a preparation method of the cobalt-based catalyst material, which has good catalytic performance.
The invention provides a preparation method of a cobalt-based catalyst material, which comprises the following steps:
A. and dissolving soluble cobalt salt in deionized water and stirring until the soluble cobalt salt is completely dissolved to obtain a cobalt salt solution.
B. And pouring the P123 nonionic surfactant into absolute ethyl alcohol, and mixing and stirring until the solution is uniform.
C. And (3) titrating the cobalt salt solution in the step (A) into the uniform solution in the step (B), stirring, and carrying out ultrasonic treatment on the obtained clear solution for 2 hours. (if clear solution can not be obtained after long-time stirring in the step A.B.C, heating in water bath at 35 ℃ and placing the mixture into a reaction kettle after ultrasonic treatment is finished for hydrothermal reaction; the hydrothermal reaction conditions are as follows: the reaction condition is 80-200 ℃, and the reaction is kept for 2-48 h;
D. after the reaction is finished, cooling the reaction kettle completely, collecting a reaction liquid, dropwise adding a tetraethyl orthosilicate solution into the reaction liquid for hydrolysis, stirring for 1h to form a solution, wherein the content of the tetraethyl orthosilicate (in terms of SiO 2 Content meter>28.4；
E. After the hydrolysis reaction is finished, standing the solution at normal temperature, and naturally airing the solution at the standing temperature to remove the mixed solvent consisting of ethanol and deionized water on the surface.
F. And (3) placing the sample with the solvent removed into an oven for heating and heat-preserving reaction under the reaction condition of 80-200 ℃ for 2-48 h.
G. The reacted substances are put into a tubular furnace for calcining operation, the reaction is performed under the nitrogen state, the temperature is kept between 200 ℃ and 1000 ℃ for 4 hours to 8 hours, the speed is 1 ℃/min to 20 ℃/mi, and the mesoporous silica-Co-based catalyst with the carbon doped shell-core structure is finally prepared after the calcining.
Further, the soluble cobalt salt in the step A is one or more of cobalt chloride hexahydrate, cobalt nitrate hexahydrate, cobalt sulfate heptahydrate and cobalt acetate tetrahydrate. The mass ratio of cobalt salt to P123 is about 1-1.5: 1. the mass ratio of the metal cobalt (calculated by cobalt oxide) in the catalyst is about 15-30%.
Further, the preferred calcination temperature is 600 ℃, and temperatures above 600 ℃ are too high, resulting in too severe graphitization, which is detrimental to CO conversion and selectivity enhancement of various species.
The cobalt-based catalyst material provided by the invention is prepared by adopting the method.
The invention provides an application of a cobalt-based catalyst material in chemical catalysis, in particular to an application of preparing high-value chemicals, in particular to obtaining olefin, through carbon monoxide and hydrogen at high temperature and high pressure.
Which is used as a catalyst in the hydrogenation of carbon monoxide. The catalyst is directly put into a catalytic reactor without hydrotreating and is introduced with CO/H 2 /N 2 And (3) carrying out hydrogenation on the mixed gas at the temperature of 230 ℃, the pressure of 2MPa and the space velocity of 800 ml/(g.multidot.h) to prepare an olefin product, wherein the reaction time is 2h. Wherein CO/H 2 /N 2 The volume ratio of the mixed gas is 30-33/60-66/4-10.
The prepared shell-core structure has the following characteristics:
according to the invention, a copolycondensation method is adopted, TEOS (silicon source precursor) and P123 (organic template agent) are mixed and condensed together, and P123 organic matters are calcined at high temperature to form graphitized carbon which is remained in silicon dioxide and forms disordered pore channels, so that graphitized carbon modified shell-core Co-based catalyst is obtained; 1. the method has the characteristics of protecting the metal in the core and avoiding the phenomena of oxidation reaction, sintering, agglomeration, inactivation and the like in the reaction process; 2. the structural strength and the hydrothermal stability are enhanced by modifying the pore canal of the mesoporous material, so that the metal exposure caused by collapse of the shell structure in the reaction process is prevented; 3. the metal compound produced by improving the bonding action between the original shell layer and the metal by adding graphitized carbon can enhance the metal reduction capability, thereby improving the catalytic activity; 4. the microstructure of the core-shell material is modified, so that the finite field reaction function of the core-shell catalytic material is realized, and the C5+ directional selectivity of a reaction product is improved; 5. the template agent in the mesoporous shell layer can be replaced by a polymer generated by biomass conversion, and the preparation method is simple and can be used for mass production. The unique design and preparation concept of the graphitized carbon modified shell-core Co-based catalyst are helpful for creating the design and preparation thought of the mesoporous shell-core catalyst with high stability, promoting the utilization of biomass, relieving the shortage of fossil resources and having potential economic and social benefits.
Compared with the prior art, the preparation method provided by the invention has the advantages that the catalyst is prepared by a gel method, the reaction condition is mild, and the reaction equipment is simple. The prepared catalyst material has good catalytic performance, and the cobalt-based catalyst has graphitized C and plays a role in electron transfer. The metal compound produced by improving the combination effect between the original shell and the metal by adding graphitized carbon can enhance the metal reduction capability, thereby enhancing the catalytic activity, the catalyst can be rapidly separated and prevented from being coagulated to be doped with quartz sand by utilizing a screen in a cyclic catalytic experiment, meanwhile, the catalyst can be recycled, the production cost is low, the flow is short, the equipment requirement is low, samples with the same properties can be obtained by changing the same proportion, the amplification experiment is easy, and the industrial production can be realized.
Drawings
FIG. 1 shows the catalytic conversion C of the modified mesoporous shell-core nano catalyst 5+ A hydrocarbon product schematic;
FIG. 2 is an X-ray powder diffraction (XRD) pattern of the samples obtained in example 1 and example 2;
FIG. 3 is an X-ray powder diffraction (XRD) pattern of the sample obtained in example 3;
FIG. 4 is an X-ray powder diffraction (XRD) pattern of the sample obtained in example 4;
FIG. 5 is a graph showing the isothermal desorption profile of the sample obtained in example 4
Detailed Description
The present invention will be described in detail with reference to examples.
Example 1
A. 2.5g of cobalt nitrate hexahydrate was weighed and placed into a 20ml deionized water beaker and stirred for 30 minutes.
B. 2.3g of P123 was added to 20ml of ethanol solution and stirred for 1h.
C. The solution in step a was titrated into the solution in step B, and stirring was continued for 2h.
D. The obtained solution was put into an ultrasonic cleaner and sonicated for 1h.
E. And after the ultrasonic treatment is finished, placing the mixture into a reaction kettle, and keeping the temperature at 180 ℃ for 3 hours to perform hydrothermal reaction.
F. After the reaction is finished, the reaction kettle is cooled completely, the solution is poured into a beaker, 4.46ml of tetraethyl orthosilicate is titrated into the beaker for hydrolysis reaction, and the hydrolysis reaction is stirred for 2 hours. (tetraethyl orthosilicate having a density of 1.18 g/cm) 3 )
G. After the reaction is finished, placing the solution into a reaction vessel, standing at normal temperature, and removing the mixed solvent consisting of ethanol and deionized water on the surface.
H. And (3) placing the sample with the surface solvent removed into an oven for heating reaction, heating to 110 ℃, and keeping the reaction for 12 hours.
I. And taking out the sample from the reaction vessel, placing the sample into a tubular furnace for calcining operation, and grinding to obtain the final catalyst material. Calcining under nitrogen state at 800 deg.c for 4 hr at 5 deg.c/min to obtain the catalyst. FIG. 2 shows the X-ray powder diffraction (XRD) patterns of the catalyst sample obtained in example 1, with distinct peaks around 45, 52 and 78 degrees, and a distinct peak around 20 degrees, respectively, as demonstrated by the reference and JADE software, with peaks of standard elemental cobalt around 45, 52 and 78, and carrier SiO around 20 degrees 2 The peaks of (2) are used as catalysts in the hydrogenation reaction of carbon monoxide, and the catalytic performance is evaluated:
firstly, weighing a certain amount of catalyst material and quartz sand, wherein the prepared catalyst needs to be easily separated through a mesh screen, then, firstly disassembling a reaction tube in a high-pressure catalysis evaluation system, firstly placing the quartz sand from top to bottom, placing the catalyst after the quartz sand reaches half of the height, and then placing the quartz sand until the top end of the reaction tube. The screws at each location were tightened and reconnected to the high pressure catalytic evaluation system. On the premise of determining that the whole system is airtight.
Firstly, reducing the catalyst by hydrogen, and specifically: first go through H 2 Reducing under the condition of 0.5MPa pressure, 400 ℃ and space velocity of 1702 ml/(g.h) (catalyst 0.5g, accurate space velocity obtained by measuring 5ml/21.14s and 5/21.14.3600/0.5) for 18h, and then using the catalyst for subsequent catalytic reaction.
Subsequent access to CO/H 2 /N 2 A mixing gas bottle (mixing volume ratio is 32/64/4), nitrogen is used as a standard gas, and argon is used as a carrier gas. Reaction conditions: temperature 230 ℃, pressure 2MPa, space velocity 800 ml/(g.multidot.h). The reaction time is 2h, and the conversion rate of CO, the selectivity of methane and C are obtained through a chromatograph and related devices 2 -C 4 ,C 5+ Is selected from the group consisting of (1).
Multiple sets of data were collected and the average calculated to be 6.79% CO conversion with 28.70% methane selectivity, C 2 -C 4 Has a selectivity of 16.64%, C 5+ The selectivity of (2) was 50.77%.
Example 2
The catalyst of example 2 is identical to that of example 1, with the difference that: no need of catalyst first reduction treatment.
The catalyst calcined under nitrogen in step I of example 1 was used in a carbon monoxide hydrogenation reaction, and its catalytic performance was evaluated:
firstly, weighing a certain amount of catalyst material and quartz sand, wherein the prepared catalyst needs to be easily separated through a mesh screen, then, firstly disassembling a reaction tube in a high-pressure catalysis evaluation system, firstly placing the quartz sand from top to bottom, placing the catalyst after the quartz sand reaches half of the height, and then placing the quartz sand until the top end of the reaction tube. The screws at each location were tightened and reconnected to the high pressure catalytic evaluation system. On the premise of determining that the whole system is airtight, the CO/H is subsequently accessed 2 /N 2 A mixing gas bottle (mixing ratio is 32/64/4), nitrogen is used as a standard gas, and argon is used as a carrier gas. Reaction conditions: temperature 230 ℃, pressure 2MPa, space velocity 800 ml/(g.multidot.h). The reaction time is 2h, and the reaction time is 2h through a chromatograph and related devicesObtaining the conversion rate of CO, the selectivity of methane and C 2 -C 4 ，C 5+ Is selected from the group consisting of (1).
Namely, the conversion of CO was 10.7%, the selectivity for methane was 29.61%, and C 2 -C 4 The selectivity of (C) was 18.35% 5+ The selectivity of (2) was 52.09%.
The catalyst for Fischer-Tropsch synthesis generally needs to undergo the step of hydrogen reduction, but the catalyst of the invention only needs to be calcined under nitrogen, so that the cobalt simple substance can be obtained, and the activity of the catalyst is higher.
Example 3
A. Dissolving cobalt nitrate hexahydrate and P123 in a mixed solvent formed by ethanol and deionized water under stirring, and vigorously stirring for two hours to form a uniform solution; the mass ratio of the P123 to the cobalt nitrate hexahydrate is 2.75g and 3g respectively, and the volume ratio of the ethanol deionized water in 40ml of mixed solvent is 1:1;
B. 4.46ml of tetraethyl orthosilicate is added into the solution of the previous step dropwise through a separating constant pressure funnel for hydrolysis, and the mixture is stirred for 1h to form a solution, wherein the content of the tetraethyl orthosilicate (in terms of SiO 2 Meter (C)>28.4
C. After the reaction is finished, placing the solution into a reaction vessel for standing, and removing a mixed solvent consisting of ethanol and deionized water on the surface;
D. and (3) placing the sample with the surface solvent removed into an oven for heating and heat preservation. Heating to 110 ℃, and keeping for 12 hours;
E. and taking out the sample from the reaction vessel, placing the sample into a tubular furnace for calcining operation, and grinding to obtain the final catalyst material. Calcination was carried out under nitrogen at 800℃for 4h at a rate of 5℃per minute.
Furthermore, we used it as a catalyst in the hydrogenation of carbon monoxide, and evaluated its catalytic performance: firstly, weighing a certain amount of catalyst material and quartz sand, wherein the prepared catalyst is required to be easily separated by a mesh screen, then, firstly disassembling a reaction tube in a high-pressure catalysis evaluation system, firstly placing the quartz sand from top to bottom, placing the catalyst after the quartz sand reaches half of the height, and thenQuartz sand was placed until the top of the reaction tube. The screws at each location were tightened and reconnected to the high pressure catalytic evaluation system. On the premise of determining that the whole system is airtight, the whole system is firstly subjected to H 2 Reducing under the condition of 0.5MPa pressure, 400 ℃ temperature and 1702 ml/(g.h) airspeed, and finishing the 18h reduction experiment. Subsequent access to CO/H 2 /N 2 A mixing gas bottle (mixing ratio is 32/64/4), nitrogen is used as a standard gas, and argon is used as a carrier gas. Reaction conditions: temperature 230 ℃, pressure 2MPa, space velocity 800 ml/(g.multidot.h). Obtaining the conversion rate of CO, the selectivity of methane and C by a chromatograph and related devices 2 -C 4 ,C 5+ Is selected from the group consisting of (1).
Namely, the conversion rate of CO is 22.78%, the selectivity of methane is 34.77%, C 2 -C 4 Has a selectivity of 15.20%, C 5+ The selectivity of (2) was 50.05%. The comparative example did not undergo hydrothermal treatment, so that tetraethyl orthosilicate and P123 did not mix and aggregate together, and the subsequent shell-core structure and graphitized carbon were difficult to succeed, and the catalytic activity of the catalyst was deteriorated.
Example 4
Example 4 differs from example 2 in that: the sample after the reaction of step H was calcined at 600℃under nitrogen.
A. 2.5g of cobalt nitrate hexahydrate was weighed and placed into a 20ml deionized water beaker and stirred for 30 minutes.
B. 2.3g of P123 was added to 20ml of ethanol solution and stirred for 1h.
C. The solution in step a was titrated into the solution in step B, and stirring was continued for 2h.
D. The obtained solution was put into an ultrasonic cleaner and sonicated for 1h.
E. And after the ultrasonic treatment is finished, placing the mixture into a reaction kettle, and keeping the temperature at 180 ℃ for 3 hours to perform hydrothermal reaction.
F. After the reaction is finished, the reaction kettle is cooled completely, the solution is poured into a beaker, 4.46ml of tetraethyl orthosilicate is titrated into the beaker for hydrolysis reaction, and the hydrolysis reaction is stirred for 2 hours. (tetraethyl orthosilicate having a density of 1.18 g/cm) 3 )
G. After the reaction is finished, placing the solution into a reaction vessel, standing at normal temperature, and removing the mixed solvent consisting of ethanol and deionized water on the surface.
H. And (3) placing the sample with the surface solvent removed into an oven for heating reaction, heating to 110 ℃, and keeping the reaction for 12 hours.
I. And taking out the sample from the reaction vessel, placing the sample into a tubular furnace for calcining operation, and grinding to obtain the final catalyst material. Calcination was carried out under nitrogen at 600℃for 4h at a rate of 5℃per minute.
The catalyst is used as a catalyst in the hydrogenation reaction of carbon monoxide, and the catalytic performance of the catalyst is evaluated:
and weighing a certain amount of catalyst material and quartz sand, wherein the prepared catalyst is required to be easily separated through a mesh screen, then, firstly disassembling a reaction tube in the high-pressure catalysis evaluation system, firstly placing the quartz sand from top to bottom, placing the catalyst after the quartz sand reaches half of the height, and then, placing the quartz sand until the top end of the reaction tube. The screws at each location were tightened and reconnected to the high pressure catalytic evaluation system. On the premise of determining that the whole system is airtight, the CO/H is subsequently accessed 2 /N 2 A mixed gas bottle (volume ratio is 32/64/4), nitrogen is used as a standard gas, and argon is used as a carrier gas. Reaction conditions: temperature 230 ℃, pressure 2MPa, space velocity 800 ml/(g.multidot.h). The reaction time is 2h, and the conversion rate of CO, the selectivity of methane and C are obtained through a chromatograph and related devices 2 -C 4 ,C 5+ Is selected from the group consisting of (1).
Namely, the conversion rate of CO is 75.42 percent, the selectivity of methane is 19.56 percent, and C 2 -C 4 Selectivity of 5.66%, C 5+ The selectivity of (C) was 74.84%, C 12+ The selectivity of (2) was 61.94%.
Experiments prove that the catalyst has very good catalytic effect and extraordinary cyclic catalytic activity, and the catalyst still maintains good catalytic activity after a long time (100 h), so that the catalyst has great potential application in the field. The sample has a BET test, a sample mass of 0.1683g and an adsorbate of N 2 Test temperature-195.850 ℃ and specific surface area of 137.8304m 2 Per g, BET specific surface area of 138.8841m 2 /g, sheetThe total pore volume/pore volume of the dot method is 0.195828cm 3 Per g, mesoporous volume of 0.167248cm 3 And/g, the average pore diameter is 5.64003nm, the mesoporous structure can be determined, and the average pore diameter of the mesopores is 7.7169nm.
Example 4 has a greatly improved CO conversion compared with examples 1,2, and 3, and C 2+ ,C 5+ The selectivity of the catalyst is also improved slightly, so that the optimal catalyst preparation method of the series of catalysts is obtained.
The foregoing is only illustrative of the present invention and all changes and modifications that come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Claims (3)
1. The application of graphitized carbon modified shell-core Co-based catalyst is characterized by that the catalyst is directly placed into catalytic reactor, and introduced with CO/H 2 /N 2 Carrying out carbon monoxide hydrogenation reaction on the mixed gas at the temperature of 230 ℃ and the pressure of 2MPa for 2 hours;
the preparation method of the catalyst comprises the following steps:
(1) Dissolving soluble cobalt salt in deionized water and stirring until the soluble cobalt salt is completely dissolved to obtain a cobalt salt solution; pouring the P123 organic matter into absolute ethyl alcohol, and mixing and stirring until the solution is uniform to obtain a P123 solution;
(2) Dropwise adding cobalt salt solution into the P123 solution, stirring, performing ultrasonic treatment on the obtained clear solution, and placing the solution into a reaction kettle after ultrasonic treatment is finished for hydrothermal reaction; the hydrothermal reaction conditions are as follows: the reaction condition is 80-200 ℃, and the reaction is kept for 2-48 h;
(3) After the hydrothermal reaction is finished, cooling completely, collecting a reaction solution, dropwise adding a tetraethyl orthosilicate solution into the reaction solution for hydrolysis, and stirring to form a solution;
(4) After the hydrolysis reaction is finished, standing the solution at normal temperature, removing a mixed solvent consisting of ethanol and deionized water on the surface, putting a sample after the solvent is removed into a baking oven, heating and preserving the temperature for reaction, and keeping the reaction condition at 80-200 ℃ for 2-48 h;
(5) The reacted substances are put into a tubular furnace for calcination, the reaction is carried out under the nitrogen state, the calcination temperature is 600 ℃, the calcination is kept for 4-8 hours, the speed is 1 ℃/min-20 ℃/min, and the graphitized carbon modified mesoporous silica-Co-based catalyst with the shell-core structure is finally prepared after the calcination.
2. The application of the graphitized carbon modified shell-core Co-based catalyst according to claim 1, wherein the soluble cobalt salt is one or more of cobalt chloride hexahydrate, cobalt nitrate hexahydrate, cobalt sulfate heptahydrate and cobalt acetate tetrahydrate.
3. The application of the graphitized carbon modified shell-core Co-based catalyst according to claim 1, wherein the mass ratio of the soluble cobalt salt to the P123 is 1-1.5: 1..
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| CN103920496A (en) * | 2014-04-22 | 2014-07-16 | 武汉凯迪工程技术研究总院有限公司 | Mesoporous material coated cobalt-based fischer-tropsch synthesis catalyst and preparation method thereof |
| CN110152669A (en) * | 2019-05-20 | 2019-08-23 | 天津大学 | A kind of cobalt-base catalyst and preparation method thereof of carbon silicon composite carrier load that directly producing low-carbon alcohols applied to synthesis gas |
| CN111111666A (en) * | 2020-01-06 | 2020-05-08 | 江南大学 | Cobalt-based Fischer-Tropsch catalyst and preparation method and application thereof |
| WO2021121088A1 (en) * | 2019-12-20 | 2021-06-24 | 常州工学院 | Mesoporous carbon material loaded cobalt-based catalyst and preparation method therefor |
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| CN103920496A (en) * | 2014-04-22 | 2014-07-16 | 武汉凯迪工程技术研究总院有限公司 | Mesoporous material coated cobalt-based fischer-tropsch synthesis catalyst and preparation method thereof |
| CN110152669A (en) * | 2019-05-20 | 2019-08-23 | 天津大学 | A kind of cobalt-base catalyst and preparation method thereof of carbon silicon composite carrier load that directly producing low-carbon alcohols applied to synthesis gas |
| WO2021121088A1 (en) * | 2019-12-20 | 2021-06-24 | 常州工学院 | Mesoporous carbon material loaded cobalt-based catalyst and preparation method therefor |
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