CN112237936A - Liquid phase dehydrogenation catalyst - Google Patents
Liquid phase dehydrogenation catalyst Download PDFInfo
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- CN112237936A CN112237936A CN201910638290.5A CN201910638290A CN112237936A CN 112237936 A CN112237936 A CN 112237936A CN 201910638290 A CN201910638290 A CN 201910638290A CN 112237936 A CN112237936 A CN 112237936A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 202
- 238000006356 dehydrogenation reaction Methods 0.000 title claims abstract description 44
- 239000007791 liquid phase Substances 0.000 title claims abstract description 17
- 239000000243 solution Substances 0.000 claims abstract description 115
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 82
- 239000001257 hydrogen Substances 0.000 claims abstract description 79
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 76
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 75
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 75
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 73
- 238000002360 preparation method Methods 0.000 claims abstract description 40
- 230000004048 modification Effects 0.000 claims abstract description 22
- 238000012986 modification Methods 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 20
- 150000001875 compounds Chemical class 0.000 claims abstract description 15
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 15
- 229910052751 metal Inorganic materials 0.000 claims abstract description 14
- 239000002184 metal Substances 0.000 claims abstract description 14
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 11
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 11
- 229910052796 boron Inorganic materials 0.000 claims abstract description 10
- 150000003839 salts Chemical class 0.000 claims abstract description 10
- UPWOEMHINGJHOB-UHFFFAOYSA-N cobalt(III) oxide Inorganic materials O=[Co]O[Co]=O UPWOEMHINGJHOB-UHFFFAOYSA-N 0.000 claims abstract description 7
- 230000000737 periodic effect Effects 0.000 claims abstract description 5
- 239000012266 salt solution Substances 0.000 claims abstract description 5
- 229920006395 saturated elastomer Polymers 0.000 claims abstract description 4
- 238000005470 impregnation Methods 0.000 claims abstract description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000011259 mixed solution Substances 0.000 claims abstract 2
- 239000000203 mixture Substances 0.000 claims description 66
- 239000007789 gas Substances 0.000 claims description 38
- 239000012298 atmosphere Substances 0.000 claims description 35
- 239000002356 single layer Substances 0.000 claims description 35
- 238000001816 cooling Methods 0.000 claims description 31
- 238000002156 mixing Methods 0.000 claims description 30
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 29
- 238000006243 chemical reaction Methods 0.000 claims description 25
- 239000007788 liquid Substances 0.000 claims description 17
- 239000010410 layer Substances 0.000 claims description 10
- 239000011232 storage material Substances 0.000 claims description 9
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 7
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 claims description 7
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 4
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 4
- 239000003208 petroleum Substances 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- SBVSDAFTZIVQEI-UHFFFAOYSA-N 2,3,4,4a,4b,5,6,7,8,8a,9,9a-dodecahydro-1h-carbazole Chemical compound C1CCCC2C3CCCCC3NC21 SBVSDAFTZIVQEI-UHFFFAOYSA-N 0.000 claims description 3
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 claims description 3
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 claims description 3
- GNMCGMFNBARSIY-UHFFFAOYSA-N 1,2,3,4,4a,4b,5,6,7,8,8a,9,10,10a-tetradecahydrophenanthrene Chemical compound C1CCCC2C3CCCCC3CCC21 GNMCGMFNBARSIY-UHFFFAOYSA-N 0.000 claims description 2
- GVJFFQYXVOJXFI-UHFFFAOYSA-N 1,2,3,4,4a,5,6,7,8,8a,9,9a,10,10a-tetradecahydroanthracene Chemical compound C1C2CCCCC2CC2C1CCCC2 GVJFFQYXVOJXFI-UHFFFAOYSA-N 0.000 claims description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- 238000007598 dipping method Methods 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 238000003860 storage Methods 0.000 abstract description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 108
- 238000011156 evaluation Methods 0.000 description 38
- 238000012360 testing method Methods 0.000 description 33
- 238000001035 drying Methods 0.000 description 30
- 238000003756 stirring Methods 0.000 description 30
- 239000002253 acid Substances 0.000 description 27
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 24
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 18
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 18
- 238000005516 engineering process Methods 0.000 description 7
- 239000012528 membrane Substances 0.000 description 7
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 6
- 239000010970 precious metal Substances 0.000 description 5
- 150000002431 hydrogen Chemical class 0.000 description 4
- 230000003993 interaction Effects 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 150000002894 organic compounds Chemical class 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- 238000010499 C–H functionalization reaction Methods 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- KVSWZGISCXEZGZ-UHFFFAOYSA-N C(C)C1=CC=CC=2C3=CC=CC=C3NC12.[N] Chemical compound C(C)C1=CC=CC=2C3=CC=CC=C3NC12.[N] KVSWZGISCXEZGZ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000004931 aggregating effect Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000010574 gas phase reaction Methods 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000007086 side reaction 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- 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
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/394—Metal dispersion value, e.g. percentage or fraction
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
- C07C5/327—Formation of non-aromatic carbon-to-carbon double bonds only
- C07C5/333—Catalytic processes
- C07C5/3335—Catalytic processes with metals
- C07C5/3337—Catalytic processes with metals of the platinum group
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/32—Hydrogen storage
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a liquid phase dehydrogenation catalyst, a preparation method and application thereof, comprising the following contents: the catalyst is prepared by doping (a) at least one metal selected from noble metal elements in the VIII group of the periodic table of elements with Fe2O3Or Co2O30.1-6 parts of active metal; (b) b, N, S, P the compound formed by the modified element and graphene is used as a carrier, and the content is 68-99 parts. The dehydrogenation catalyst comprises the steps of 1) carrying out B, N, S, P modification element treatment on graphene to obtain a carrier; 2) will be firstThe salt solution of the VIII group noble metal element is mixed with the solution of Fe salt or Co salt, and the mixed solution is loaded on a carrier by adopting a saturated impregnation method to prepare the catalyst. When the catalyst is applied to the liquid-phase dehydrogenation of the hydrogen storage compound, the catalyst has higher stability.
Description
Technical Field
The invention discloses a liquid-phase dehydrogenation catalyst, a preparation method and application thereof, in particular to a liquid-phase dehydrogenation catalyst for an organic liquid hydrogen storage material and a preparation method thereof.
Background
Hydrogen energy is applied in large scale, and a plurality of technical problems need to be solved. Among them, the safe and efficient storage and transportation of hydrogen is one of the most central problems. At present, the hydrogen storage technology mainly comprises physical hydrogen storage, adsorption hydrogen storage and chemical hydrogen storage. Physical hydrogen storage technology has met the requirements of vehicles, but its high requirements on equipment and harsh operating conditions have made the contradiction between performance and efficiency of this technology increasingly prominent. Adsorption hydrogen storage and chemical hydrogen storage are the key points of the current research, and certain research results are obtained, but certain differences exist between the technical requirements of vehicle-mounted hydrogen storage. The organic liquid hydrogen storage technology (organic liquid mainly includes methyl cyclohexane, tetrahydronaphthalene, decahydronaphthalene, perhydro nitrogen ethyl carbazole, perhydro carbazole, etc.) in chemical hydrogen storage realizes hydrogen energy storage by catalytic addition and dehydrogenation reversible reaction, the reaction in the process is reversible, reactant products can be recycled, and the hydrogen storage amount is relatively high (about 60-75kg H)2/m3The mass fraction is 6-8 percent), meets the indexes specified by the International energy agency and the United states department of energy (DOE), is transported for a long distance in the form of organic liquid or can solve the problem of uneven distribution of energy in areas, really meets the requirement of green chemistry and has stronger application prospect.
The hydrogenation process and the dehydrogenation process exist simultaneously in the organic liquid hydrogen storage technology, the hydrogenation process is relatively simple, the technology is mature, and the dehydrogenation process is a reaction with strong heat absorption and volume increase, so that the dehydrogenation reaction is facilitated at high temperature from the aspects of dynamics and thermodynamics, but side reactions such as cracking, carbon deposition and the like are easy to occur at high temperature, and the activity of the catalyst is reduced and even inactivated. The conventional dehydrogenation reaction is carried out under a gas phase condition, and is generally carried out at a high temperature in order to improve the reaction conversion rate, or a membrane reactor is adopted to promote the reaction balance, which causes high operation cost, large equipment investment, difficult maintenance and difficulty in large-scale application. If the reaction is carried out in a liquid phase, hydrogen generated by the reaction overflows in a gas form, the reaction balance problem does not exist, the reaction temperature can be greatly reduced, a membrane reactor is not required, and the method has many advantages compared with a gas phase reaction.
CN108067172A discloses a microchannel reactor and a dehydrogenation method suitable for dehydrogenation reaction of liquid hydrogen source materials, wherein a liquid distributor is connected above a microchannel reactor body, a guide plate is arranged inside the liquid distributor, a high-temperature flange is arranged between the liquid distributor and a hydrogen source material inlet, a hydrogen storage carrier and a hydrogen outlet are arranged below the microchannel reactor body, and a high-temperature flange is arranged between the microchannel reactor body and the outlet; a heat carrier distributor is connected to the inlet side of the microchannel reactor body, a guide plate is arranged inside the heat carrier distributor, a high-temperature flange is arranged between the heat carrier distributor and the heat carrier inlet, a heat carrier outlet is arranged on the other side of the microchannel reactor body, and a high-temperature flange is arranged between the microchannel reactor body and the heat carrier outlet; a plurality of transverse and longitudinal orthogonal microchannels are arranged in the microchannel reactor body.
US20130022536a1 discloses a hydrogen production method and a reactor for dehydrogenation in which hydrogen can be easily and simply mixed with a raw material for dehydrogenation reaction and the performance of a dehydrogenation reaction catalyst is suppressed from being lowered when hydrogen is generated by combining dehydrogenation reactions. Organic hydrides having hydrogen separation membranes, and the like. The flow-type reactor for dehydrogenation of organic compounds includes a hydrogen separation membrane selectively permeable to hydrogen; and a dehydrogenation catalyst for promoting a dehydrogenation reaction of an organic compound that can release hydrogen in the dehydrogenation reaction, comprising: the reaction-side region through which the organic compound can flow, and the reaction-side region including the dehydrogenation catalyst and the permeate-side region separated therefrom passing through the hydrogen separation membrane and the hydrogen having passed through the hydrogen separation membrane can flow.
The above two methods achieve liquid phase dehydrogenation of organic liquid compounds, and attempt to improve reaction efficiency by breaking the limitation of reaction equilibrium. The key problem to be solved in the liquid phase reaction is to find a catalyst which can activate the hydrogen-containing compound at a lower temperature and has higher stability. The noble metal and the graphene substrate partially substituted by the modification element have very strong interaction, so that the graphene substrate has very good carbon-hydrogen bond activation performance, and more importantly, the interaction enables the noble metal to be anchored on the surface of the graphene, prevents the noble metal from migrating and aggregating, and has a strong effect of improving the stability of the catalyst. In accordance with this concept, the present patent provides a high stability liquid phase dehydrogenation catalyst.
Disclosure of Invention
The invention aims to solve the technical problems of high reaction temperature, quick catalyst inactivation, high operation cost caused by using a membrane reaction, large equipment investment, difficult maintenance and the like in the traditional gas-phase dehydrogenation technology, and provides a high-stability liquid-phase dehydrogenation catalyst and a preparation method thereof.
The technical scheme adopted by the invention is as follows:
the liquid-phase dehydrogenation catalyst comprises the following components in parts by weight:
(a) fe doped with at least one metal selected from the group VIII noble metals of the periodic Table of the elements2O3Or Co2O30.2-8 parts of active metal;
(b) and a compound formed by the modification element and the graphene is used as a carrier, and the content of the compound is 68-99 parts.
In the above technical solution, preferably, the component (a) comprises platinum and/or palladium in an amount of 0.1 to 7 parts by weight, preferably 0.1 to 6 parts by weight, and Fe2O3Or Co2O3The content is 0.01 to 1 part by weight, preferably 0.01 to 0.8 part by weight.
In the above technical solution, after the compound is formed by at least one modification element selected from B, N, S, P in the component (B) and graphene, the carrier content is 70-95 parts by weight, preferably, the modification element is N and S, or preferably, the modification element is N and P, or further preferably, the modification element is N and B.
In the above technical solution, the graphene is selected from at least one of single-layer graphene and double-layer graphene, and preferably, the graphene is selected from single-layer graphene modified by N and S together, double-layer graphene modified by N and P together, and a mixture of single-layer graphene and double-layer graphene modified by N and B together.
In the technical scheme, the content of the graphene is more preferably 50-90 parts, the content of the modification element is 5-20 parts, and the most preferably, the content of the graphene is 55-80 parts, and the content of the modification element is 8-20 parts.
In the above technical scheme, the preparation method of the dehydrogenation catalyst comprises the following steps:
1) carrying out modification element treatment on graphene to obtain a compound, wherein the compound is used as a carrier;
2) mixing the salt solution of the VIII group noble metal element with the solution of Fe salt or Co salt, and loading the mixture on a carrier by adopting a saturated impregnation method to prepare the catalyst.
In the above technical solution, preferably, the catalyst comprises the following components in parts by weight: (a) fe doped with at least one metal selected from the group VIII noble metals of the periodic Table of the elements2O3Or Co2O30.2-8 parts of active metal; and (b) 68-99 parts of a compound formed by at least one modification element selected from B, N, S, P and graphene as a carrier. In the above technical solution, preferably, the method for processing the modifying element to the graphene comprises: introducing gas containing the modification element into a reactor filled with graphene, and treating for 4-15h at the temperature of 300-500 ℃ and the gas flow rate of 100-.
In the above technical solution, preferably, the modifying element is selected from BH3,NH3,H2S,PH3Preferably, the modifying element is selected from the group consisting of NH3And H2S, or NH3And pH3Or NH3And BH3。
In the above technical solution, preferably, the saturated dipping procedure is: mixing a salt solution of a group VIII noble metal element with a solution of Fe salt or Co salt at the temperature of 25-100 ℃, mixing with the graphene treated by the modification element, standing for 1-4 h, roasting for 2-6 h in an oxygen-free atmosphere at the temperature of 300-500 ℃, and cooling to room temperature.
In the above technical solution, more preferably, the oxygen-free atmosphere is: and (3) a nitrogen atmosphere.
In the above technical solution, preferably, the reaction conditions of the method for liquid-phase dehydrogenation of the organic liquid hydrogen storage material are as follows: the reaction pressure is 0-10 MPa, the temperature is 100-280 ℃, and the mass space velocity is 0.1-10 h-1(ii) a The organic liquid hydrogen storage material is contacted with the catalyst to react to generate hydrogen and corresponding products.
In the above technical scheme, preferably, the method for preparing the low-carbon olefin by the dehydrogenation of the low-carbon alkane adopts isobutane and/or butene as a raw material, and the reaction temperature is 100-380 ℃, the reaction pressure is 0-10 MPa, and the alkane mass airspeed is 0.1-8.0 h-1And the raw material is contacted with the catalyst to react to generate isobutene and/or butadiene.
In the above technical solution, preferably, the hydrogen storage material includes at least one of cyclohexane, methylcyclohexane, tetrahydronaphthalene, decahydronaphthalene, perhydroazeethylcarbazole, perhydrophenanthrene, perhydroanthracene, perhydrocarbazole or at least one of their derivatives, and at least one of a cut fraction from petroleum or a fraction of petroleum or a cut fraction hydrogenated material.
The interaction between the precious metal and the graphene substrate partially substituted by the modification element is used for preparing the catalyst in which the precious metal is dispersed on the surface of the metal carbide nano-particles in an atomic scale, so that a high-density atomic scale catalytic active center is constructed, the active center has very good carbon-hydrogen bond activation performance, the precious metal can be fixed by the strong interaction between the precious metal and the active center, the migration and aggregation of the precious metal are prevented, and the catalytic stability is high.
The invention is further illustrated by the following examples, but is not limited thereto.
Detailed Description
[ example 1 ]
2g of single-layer graphene is placed in a tubular reactor, and 10% NH is introduced3The nitrogen is treated, the gas flow rate is 300mL/min, the treatment temperature is 450 ℃, the treatment time is 10 hours, and the nitrogen is used as a catalyst carrier after cooling.
Mixing 1.244mL of 1.614g (Pt)/L chloroplatinic acid solution and 0.378mL of 3.71g (Fe)/L ferric nitrate solution, adding 2g of carrier into the solution, stirring, standing at room temperature for 2h, drying at 120 deg.C for 4h, and adding N2And roasting the mixture for 4 hours at 450 ℃ in an atmosphere muffle furnace to obtain the catalyst. The catalyst composition is shown in table 1.
The obtained catalyst was tabletted, ground to a particle size of 12-20 mesh, and 1g was evaluated in an isothermal fixed bed reactor, before the evaluation, reduced with hydrogen under the following reduction conditions: the pressure and the normal pressure are controlled, the temperature is 450 ℃, the hydrogen flow is 200mL/min, the reduction time is 4h, and then the temperature is reduced for evaluation, wherein the evaluation conditions are as follows: the reaction pressure is normal pressure, the temperature is 320 ℃, and the space velocity is 2h-1Methylcyclohexane is used as a representative raw material for storing hydrogen in an organic liquid. Catalyst activity is expressed as TOF, which is the conversion of reactant per unit time of active metal in g-1·h-1. (TOF ═ conversion/(active metal mass × reaction time)) catalyst preparation conditions and evaluation results are shown in table 2.
[ example 2 ]
2g of single-layer graphene is placed in a tubular reactor, and 10% NH is introduced3The nitrogen is treated, the gas flow rate is 300mL/min, the treatment temperature is 450 ℃, the treatment time is 10 hours, and the nitrogen is used as a catalyst carrier after cooling.
Mixing 1.244mL of (Pt)/L chloroplatinic acid solution with concentration of 16.14g and 0.378mL ferric nitrate solution with concentration of 3.71g (Fe)/L, adding 2g of the above carrier into the solution, stirring, standing at room temperature for 2h, drying at 120 deg.C for 4h, and adding N2And roasting the mixture for 4 hours at 450 ℃ in an atmosphere muffle furnace to obtain the catalyst. The catalyst composition is shown in table 1.
1g of the catalyst was put into an isothermal fixed bed reactor and reduced with hydrogen before evaluation, and the reduction conditions and evaluation conditions were the same as those in example 1. The preparation method and test results of the catalyst are shown in table 2.
[ example 3 ]
2g of single-layer graphene is placed in a tubular reactor, and 10% NH is introduced3The nitrogen is treated, the gas flow rate is 300mL/min, the treatment temperature is 450 ℃, the treatment time is 10 hours, and the nitrogen is used as a catalyst carrier after cooling.
Mixing 1.244mL of chloroplatinic acid solution with concentration of 8.07g (Pt)/L and 0.378mL of ferric nitrate solution with concentration of 3.71g (Fe)/L, adding 2g of the above carrier into the solution, stirring, standing at room temperature for 2h, drying at 120 deg.C for 4h, and adding N2And roasting the mixture for 4 hours at 450 ℃ in an atmosphere muffle furnace to obtain the catalyst. The catalyst composition is shown in table 1.
1g of the catalyst was put in an isothermal fixed bed reactor and reduced with hydrogen before evaluation under the same conditions as in example 1, and the preparation method and test results of the catalyst are shown in Table 2.
[ example 4 ]
2g of single-layer graphene is placed in a tubular reactor, and 10% NH is introduced3The nitrogen is treated, the gas flow rate is 300mL/min, the treatment temperature is 450 ℃, the treatment time is 10 hours, and the nitrogen is used as a catalyst carrier after cooling.
Mixing 1.244mL of 1.614g (Pt)/L chloroplatinic acid solution and 0.378mL of 3.71g (Fe)/L ferric nitrate solution, adding 2g of the above carrier into the solution, stirring, standing at room temperature for 2h, drying at 120 deg.C for 4h, and adding N2And roasting the mixture for 4 hours at 450 ℃ in an atmosphere muffle furnace to obtain the catalyst. The catalyst composition is shown in table 1.
1g of the catalyst was put in an isothermal fixed bed reactor and reduced with hydrogen before evaluation under the same conditions as in example 1, and the preparation method and test results of the catalyst are shown in Table 2.
[ example 5 ]
2g of single-layer graphene is placed in a tubular reactor, and 10% NH is introduced3The flow rate of the gas is 300mL/min, the treatment temperature is 450 ℃ andthe treatment time is 10h, and the catalyst carrier is obtained after cooling.
Mixing 1.244mL of a chloroplatinic acid solution having a concentration of 11.298g (Pt)/L with 0.378mL of a ferric nitrate solution having a concentration of 3.71g (Fe)/L, adding 2g of the above carrier to the solution, stirring, standing at room temperature for 2h, drying at 120 deg.C for 4h, and adding N2And roasting the mixture for 4 hours at 450 ℃ in an atmosphere muffle furnace to obtain the catalyst. The catalyst composition is shown in table 1.
1g of the catalyst was put in an isothermal fixed bed reactor and reduced with hydrogen before evaluation under the same conditions as in example 1, and the preparation method and test results of the catalyst are shown in Table 2.
[ example 6 ]
2g of single-layer graphene is placed in a tubular reactor, and 10% BH is introduced3The nitrogen is treated, the gas flow rate is 300mL/min, the treatment temperature is 450 ℃, the treatment time is 10 hours, and the nitrogen is used as a catalyst carrier after cooling.
Mixing 1.244mL of (Pt)/L chloroplatinic acid solution with concentration of 16.14g and 0.378mL ferric nitrate solution with concentration of 3.71g (Fe)/L, adding 2g of the above carrier into the solution, stirring, standing at room temperature for 2h, drying at 120 deg.C for 4h, and adding N2And roasting the mixture for 4 hours at 450 ℃ in an atmosphere muffle furnace to obtain the catalyst. The catalyst composition is shown in table 1.
1g of the catalyst was put in an isothermal fixed bed reactor and reduced with hydrogen before evaluation under the same conditions as in example 1, and the preparation method and test results of the catalyst are shown in Table 2.
[ example 7 ]
2g of single-layer graphene is placed in a tubular reactor, and 10% H is introduced2And treating the S with nitrogen, wherein the gas flow rate is 300mL/min, the treatment temperature is 450 ℃, the treatment time is 10h, and the S is used as a catalyst carrier after being cooled.
Mixing 1.244mL of (Pt)/L chloroplatinic acid solution with concentration of 16.14g and 0.378mL ferric nitrate solution with concentration of 3.71g (Fe)/L, adding 2g of the above carrier into the solution, stirring, standing at room temperature for 2h, drying at 120 deg.C for 4h, and adding N2And roasting the mixture for 4 hours at 450 ℃ in an atmosphere muffle furnace to obtain the catalyst. The catalyst composition is shown in table 1.
1g of the catalyst was put in an isothermal fixed bed reactor and reduced with hydrogen before evaluation under the same conditions as in example 1, and the preparation method and test results of the catalyst are shown in Table 2.
[ example 8 ]
2g of single-layer graphene was placed in a tubular reactor, and 10% pH was passed through3The nitrogen is treated, the gas flow rate is 300mL/min, the treatment temperature is 450 ℃, the treatment time is 10 hours, and the nitrogen is used as a catalyst carrier after cooling.
Mixing 1.244mL of (Pt)/L chloroplatinic acid solution with concentration of 16.14g and 0.378mL ferric nitrate solution with concentration of 3.71g (Fe)/L, adding 2g of the above carrier into the solution, stirring, standing at room temperature for 2h, drying at 120 deg.C for 4h, and adding N2And roasting the mixture for 4 hours at 450 ℃ in an atmosphere muffle furnace to obtain the catalyst. The catalyst composition is shown in table 1.
1g of the catalyst was put in an isothermal fixed bed reactor and reduced with hydrogen before evaluation under the same conditions as in example 1, and the preparation method and test results of the catalyst are shown in Table 2.
[ example 9 ]
2g of single-layer graphene is placed in a tubular reactor, and 10% NH is introduced3The nitrogen is treated, the gas flow rate is 500mL/min, the treatment temperature is 450 ℃, the treatment time is 10 hours, and the nitrogen is used as a catalyst carrier after cooling.
Mixing 1.244mL of chloroplatinic acid solution with concentration of 16.14g (Pt)/L and 0.378mL of ferric nitrate solution with concentration of 0.371g (Fe)/L, adding 2g of the above carrier into the solution, stirring, standing at room temperature for 2h, drying at 120 deg.C for 4h, and adding N2And roasting the mixture for 4 hours at 450 ℃ in an atmosphere muffle furnace to obtain the catalyst. The catalyst composition is shown in table 1.
1g of the catalyst was put in an isothermal fixed bed reactor and reduced with hydrogen before evaluation under the same conditions as in example 1, and the preparation method and test results of the catalyst are shown in Table 2.
[ example 10 ]
2g of single-layer graphene is placed in a tubular reactor, and 10% NH is introduced3The nitrogen is treated, the gas flow rate is 400 mL/min, the treatment temperature is 450 ℃, the treatment time is 10 hours, and the nitrogen is used as a catalyst carrier after cooling.
Mixing 1.244mL of (Pt)/L chloroplatinic acid solution with concentration of 16.14g and 0.378mL ferric nitrate solution with concentration of 37.1g (Fe)/L, adding 2g of the above carrier into the solution, stirring, standing at room temperature for 2h, drying at 120 deg.C for 4h, and adding N2And roasting the mixture for 4 hours at 450 ℃ in an atmosphere muffle furnace to obtain the catalyst. The catalyst composition is shown in table 1.
1g of the catalyst was put in an isothermal fixed bed reactor and reduced with hydrogen before evaluation under the same conditions as in example 1, and the preparation method and test results of the catalyst are shown in Table 2.
[ example 11 ]
2g of single-layer graphene is placed in a tubular reactor, and 10% NH is introduced3The nitrogen is treated, the gas flow rate is 300mL/min, the treatment temperature is 450 ℃, the treatment time is 10 hours, and the nitrogen is used as a catalyst carrier after cooling.
Mixing 1.244mL of (Pt)/L chloroplatinic acid solution with concentration of 16.14g and 0.378mL cobalt nitrate solution with concentration of 8.33g (Co)/L, adding 2g of the above carrier into the solution, stirring, standing at room temperature for 2h, drying at 120 deg.C for 4h, and adding N2And roasting the mixture for 4 hours at 450 ℃ in an atmosphere muffle furnace to obtain the catalyst. The catalyst composition is shown in table 1.
1g of the catalyst was put in an isothermal fixed bed reactor and reduced with hydrogen before evaluation under the same conditions as in example 1, and the preparation method and test results of the catalyst are shown in Table 2.
[ example 12 ]
2g of single-layer graphene is placed in a tubular reactor, and 10% NH is introduced3The nitrogen is treated, the gas flow rate is 200mL/min, the treatment temperature is 450 ℃, the treatment time is 10 hours, and the nitrogen is used as a catalyst carrier after cooling.
Mixing 1.244mL of (Pt)/L chloroplatinic acid solution 16.14g with 0.378mL cobalt nitrate solution 83.3g, stirring, standing at room temperature for 2h, drying at 120 deg.C for 4h, and adding N2And roasting the mixture for 4 hours at 450 ℃ in an atmosphere muffle furnace to obtain the catalyst. The catalyst composition is shown in table 1.
1g of the catalyst was put in an isothermal fixed bed reactor and reduced with hydrogen before evaluation under the same conditions as in example 1, and the preparation method and test results of the catalyst are shown in Table 2.
[ example 13 ]
2g of single-layer graphene is placed in a tubular reactor, and 10% NH is introduced3The nitrogen is treated, the gas flow rate is 350 mL/min, the treatment temperature is 450 ℃, the treatment time is 6h, and the nitrogen is used as a catalyst carrier after cooling.
Mixing 1.244mL of (Pt)/L chloroplatinic acid solution with concentration of 16.14g and 0.378mL cobalt nitrate solution with concentration of 8.33g (Co)/L, adding 2g of the above carrier into the solution, stirring, standing at room temperature for 2h, drying at 120 deg.C for 4h, and adding N2And roasting the mixture for 4 hours at 450 ℃ in an atmosphere muffle furnace to obtain the catalyst. The catalyst composition is shown in table 1.
1g of the catalyst was put in an isothermal fixed bed reactor and reduced with hydrogen before evaluation under the same conditions as in example 1, and the preparation method and test results of the catalyst are shown in Table 2.
[ example 14 ]
2g of single-layer graphene is placed in a tubular reactor, and 10% NH is introduced3The nitrogen is treated, the gas flow rate is 400 mL/min, the treatment temperature is 450 ℃, the treatment time is 8h, and the nitrogen is used as a catalyst carrier after cooling.
Mixing 1.244mL of (Pt)/L chloroplatinic acid solution with concentration of 16.14g and 0.378mL cobalt nitrate solution with concentration of 8.33g (Co)/L, adding 2g of the above carrier into the solution, stirring, standing at room temperature for 2h, drying at 120 deg.C for 4h, and adding N2And roasting the mixture for 4 hours at 450 ℃ in an atmosphere muffle furnace to obtain the catalyst. Catalyst and process for preparing sameThe compositions are shown in Table 1.
1g of the catalyst was put in an isothermal fixed bed reactor and reduced with hydrogen before evaluation under the same conditions as in example 1, and the preparation method and test results of the catalyst are shown in Table 2.
[ example 15 ]
2g of single-layer graphene is placed in a tubular reactor, and 10% NH is introduced3The gas flow rate is 430 mL/min, the treatment temperature is 450 ℃, the treatment time is 10h, and the catalyst carrier is obtained after cooling.
Mixing 1.244mL of (Pt)/L chloroplatinic acid solution with concentration of 16.14g and 0.378mL cobalt nitrate solution with concentration of 8.33g (Co)/L, adding 2g of the above carrier into the solution, stirring, standing at room temperature for 2h, drying at 120 deg.C for 4h, and adding N2And roasting the mixture for 4 hours at 450 ℃ in an atmosphere muffle furnace to obtain the catalyst. The catalyst composition is shown in table 1.
1g of the catalyst was put in an isothermal fixed bed reactor and reduced with hydrogen before evaluation under the same conditions as in example 1, and the preparation method and test results of the catalyst are shown in Table 2.
[ example 16 ]
2g of single-layer graphene is placed in a tubular reactor, and 10% NH is introduced3The nitrogen is treated, the gas flow rate is 480 mL/min, the treatment temperature is 450 ℃, the treatment time is 10h, and the nitrogen is used as a catalyst carrier after cooling.
Mixing 1.244mL of (Pt)/L chloroplatinic acid solution with concentration of 16.14g and 0.378mL cobalt nitrate solution with concentration of 8.33g (Co)/L, adding 2g of the above carrier into the solution, stirring, standing at room temperature for 2h, drying at 120 deg.C for 4h, and adding N2And roasting the mixture for 4 hours at 450 ℃ in an atmosphere muffle furnace to obtain the catalyst. The catalyst composition is shown in table 1.
1g of the catalyst was put in an isothermal fixed bed reactor and reduced with hydrogen before evaluation under the same conditions as in example 1, and the preparation method and test results of the catalyst are shown in Table 2.
[ example 17 ]
2g of double-layer graphene is placed in a tubular reactor, and 10% NH is introduced3The nitrogen is treated, the gas flow rate is 300mL/min, the treatment temperature is 450 ℃, the treatment time is 10 hours, and the nitrogen is used as a catalyst carrier after cooling.
Mixing 1.244mL of (Pt)/L chloroplatinic acid solution with concentration of 16.14g and 0.378mL cobalt nitrate solution with concentration of 8.33g (Co)/L, adding 2g of the above carrier into the solution, stirring, standing at room temperature for 2h, drying at 120 deg.C for 4h, and adding N2And roasting the mixture for 4 hours at 450 ℃ in an atmosphere muffle furnace to obtain the catalyst. The catalyst composition is shown in table 1.
1g of the catalyst was put in an isothermal fixed bed reactor and reduced with hydrogen before evaluation under the same conditions as in example 1, and the preparation method and test results of the catalyst are shown in Table 2.
[ example 18 ]
2g of single-layer graphene is placed in a tubular reactor, and 15% NH is introduced3+5%BH3The nitrogen is treated, the gas flow rate is 300mL/min, the treatment temperature is 450 ℃, the treatment time is 10 hours, and the nitrogen is used as a catalyst carrier after cooling.
Mixing 1.244mL of (Pt)/L chloroplatinic acid solution with concentration of 16.14g and 0.378mL cobalt nitrate solution with concentration of 8.33g (Co)/L, adding 2g of the above carrier into the solution, stirring, standing at room temperature for 2h, drying at 120 deg.C for 4h, and adding N2And roasting the mixture for 4 hours at 450 ℃ in an atmosphere muffle furnace to obtain the catalyst. The catalyst composition is shown in table 1.
1g of the catalyst was put in an isothermal fixed bed reactor and reduced with hydrogen before evaluation under the same conditions as in example 1, and the preparation method and test results of the catalyst are shown in Table 2.
[ example 19 ]
2g of single-layer graphene is placed in a tubular reactor, and 15% NH is introduced3+5%H2And treating the S with nitrogen, wherein the gas flow rate is 300mL/min, the treatment temperature is 450 ℃, the treatment time is 10h, and the S is used as a catalyst carrier after being cooled.
Taking 1.244mL as16.14g of (Pt)/L chloroplatinic acid solution were mixed with 0.378mL of 8.33g of (Co)/L cobalt nitrate solution, 2g of the above carrier was added to the solution, stirred, left at room temperature for 2 hours, dried at 120 ℃ for 4 hours, and finally placed in N2And roasting the mixture for 4 hours at 450 ℃ in an atmosphere muffle furnace to obtain the catalyst. The catalyst composition is shown in table 1.
1g of the catalyst was put in an isothermal fixed bed reactor and reduced with hydrogen before evaluation under the same conditions as in example 1, and the preparation method and test results of the catalyst are shown in Table 2.
[ example 20 ]
2g of single-layer graphene is placed in a tubular reactor, and 15% NH is introduced3+5%PH3The nitrogen is treated, the gas flow rate is 300mL/min, the treatment temperature is 450 ℃, the treatment time is 10 hours, and the nitrogen is used as a catalyst carrier after cooling.
Mixing 1.244mL of (Pt)/L chloroplatinic acid solution with concentration of 16.14g and 0.378mL cobalt nitrate solution with concentration of 8.33g (Co)/L, adding 2g of the above carrier into the solution, stirring, standing at room temperature for 2h, drying at 120 deg.C for 4h, and adding N2And roasting the mixture for 4 hours at 450 ℃ in an atmosphere muffle furnace to obtain the catalyst. The catalyst composition is shown in table 1.
1g of the catalyst was put in an isothermal fixed bed reactor and reduced with hydrogen before evaluation under the same conditions as in example 1, and the preparation method and test results of the catalyst are shown in Table 2.
[ example 21 ]
2g of single-layer graphene is placed in a tubular reactor, and 10% NH is introduced3The nitrogen is treated, the gas flow rate is 300mL/min, the treatment temperature is 450 ℃, the treatment time is 10 hours, and the nitrogen is used as a catalyst carrier after cooling.
Mixing 1.244mL of (Pd)/L palladium chloride solution with concentration of 16.14g and 0.378mL of (Co)/L cobalt nitrate solution with concentration of 8.33g, adding 2g of the above carrier into the solution, stirring, standing at room temperature for 2h, drying at 120 deg.C for 4h, and adding N2And roasting the mixture for 4 hours at 450 ℃ in an atmosphere muffle furnace to obtain the catalyst. The catalyst composition is shown in Table 1Shown in the figure.
1g of the catalyst was put in an isothermal fixed bed reactor and reduced with hydrogen before evaluation under the same conditions as in example 1, and the preparation method and test results of the catalyst are shown in Table 2.
[ example 22 ]
2g of single-layer graphene is placed in a tubular reactor, and 10% NH is introduced3The nitrogen is treated, the gas flow rate is 300mL/min, the treatment temperature is 450 ℃, the treatment time is 10 hours, and the nitrogen is used as a catalyst carrier after cooling.
Mixing 1.244mL of 48.42g (Pd)/L palladium chloride solution with 0.378mL of 8.33g (Co)/L cobalt nitrate solution, adding 2g of the above carrier into the solution, stirring, standing at room temperature for 2h, drying at 120 deg.C for 4h, and adding N2And roasting the mixture for 4 hours at 450 ℃ in an atmosphere muffle furnace to obtain the catalyst. The catalyst composition is shown in table 1.
1g of the catalyst was put in an isothermal fixed bed reactor and reduced with hydrogen before evaluation under the same conditions as in example 1, and the preparation method and test results of the catalyst are shown in Table 2.
[ example 23 ]
2g of single-layer graphene is placed in a tubular reactor, and 15% H is introduced2S+5%BH3The nitrogen is treated, the gas flow rate is 300mL/min, the treatment temperature is 450 ℃, the treatment time is 10 hours, and the nitrogen is used as a catalyst carrier after cooling.
1.244mL of a chloroplatinic acid solution having a concentration of 16.14g (Pt)/L was mixed with 0.378mL of a cobalt nitrate solution having a concentration of 8.33g (Co)/L, 2g of the above carrier was added to the solution, followed by stirring, standing at room temperature for 2 hours, drying at 120 ℃ for 4 hours, and finally, placing the mixture in a muffle furnace having an atmosphere of N2 and calcining at 450 ℃ for 4 hours to obtain a catalyst. The catalyst composition is shown in table 1.
1g of the catalyst was put in an isothermal fixed bed reactor and reduced with hydrogen before evaluation under the same conditions as in example 1, and the preparation method and test results of the catalyst are shown in Table 2.
[ example 24 ]
2g of single-layer graphene is placed in a tubular reactor, and 15% H is introduced2S+5%PH3The nitrogen is treated, the gas flow rate is 300mL/min, the treatment temperature is 450 ℃, the treatment time is 10 hours, and the nitrogen is used as a catalyst carrier after cooling.
Mixing 1.244mL of (Pt)/L chloroplatinic acid solution with concentration of 16.14g and 0.378mL cobalt nitrate solution with concentration of 8.33g (Co)/L, adding 2g of the above carrier into the solution, stirring, standing at room temperature for 2h, drying at 120 deg.C for 4h, and adding N2And roasting the mixture for 4 hours at 450 ℃ in an atmosphere muffle furnace to obtain the catalyst. The catalyst composition is shown in table 1.
1g of the catalyst was put in an isothermal fixed bed reactor and reduced with hydrogen before evaluation under the same conditions as in example 1, and the preparation method and test results of the catalyst are shown in Table 2.
[ example 25 ]
2g of single-layer graphene is placed in a tubular reactor, and 15% BH is introduced3+5%PH3The nitrogen is treated, the gas flow rate is 300mL/min, the treatment temperature is 450 ℃, the treatment time is 10 hours, and the nitrogen is used as a catalyst carrier after cooling.
Mixing 1.244mL of (Pt)/L chloroplatinic acid solution with concentration of 16.14g and 0.378mL cobalt nitrate solution with concentration of 8.33g (Co)/L, adding 2g of the above carrier into the solution, stirring, standing at room temperature for 2h, drying at 120 deg.C for 4h, and adding N2And roasting the mixture for 4 hours at 450 ℃ in an atmosphere muffle furnace to obtain the catalyst. The catalyst composition is shown in table 1.
1g of the catalyst was put in an isothermal fixed bed reactor and reduced with hydrogen before evaluation under the same conditions as in example 1, and the preparation method and test results of the catalyst are shown in Table 2.
[ example 26 ]
2g of single-layer graphene is placed in a tubular reactor, and 10% NH is introduced3The nitrogen is treated, the gas flow rate is 300mL/min, the treatment temperature is 450 ℃, the treatment time is 10 hours, and the nitrogen is used as a catalyst carrier after cooling.
1.244mL of 16.14g (Pt) was taken) Mixing the/L chloroplatinic acid solution with 0.378mL cobalt nitrate solution with concentration of 8.33g (Co)/L, adding 2g of the above carrier into the solution, stirring, standing at room temperature for 2h, drying at 120 deg.C for 4h, and adding N2And roasting the mixture for 4 hours at 450 ℃ in an atmosphere muffle furnace to obtain the catalyst. The catalyst composition is shown in table 1.
1g of the catalyst was put in an isothermal fixed bed reactor and reduced with hydrogen before evaluation under the same conditions as in example 1, and the preparation method and test results of the catalyst are shown in Table 2.
[ example 27 ]
2g of single-layer graphene is placed in a tubular reactor, and 10% NH is introduced3The nitrogen is treated, the gas flow rate is 300mL/min, the treatment temperature is 450 ℃, the treatment time is 10 hours, and the nitrogen is used as a catalyst carrier after cooling.
Mixing 1.244mL of (Pt)/L chloroplatinic acid solution with concentration of 16.14g and 0.378mL cobalt nitrate solution with concentration of 8.33g (Co)/L, adding 2g of the above carrier into the solution, stirring, standing at room temperature for 2h, drying at 120 deg.C for 4h, and adding N2And roasting the mixture for 4 hours at 450 ℃ in an atmosphere muffle furnace to obtain the catalyst. The catalyst composition is shown in table 1.
1g of the catalyst was put in an isothermal fixed bed reactor and reduced with hydrogen before evaluation under the same conditions as in example 1, and the preparation method and test results of the catalyst are shown in Table 2.
[ example 28 ]
2g of double-layer graphene is placed in a tubular reactor, and 15% NH is introduced3+5%BH3The nitrogen is treated, the gas flow rate is 300mL/min, the treatment temperature is 450 ℃, the treatment time is 10 hours, and the nitrogen is used as a catalyst carrier after cooling.
Mixing 1.244mL of (Pd)/L palladium chloride solution with concentration of 16.14g and 0.378mL of (Co)/L cobalt nitrate solution with concentration of 8.33g, adding 2g of the above carrier into the solution, stirring, standing at room temperature for 2h, drying at 120 deg.C for 4h, and adding N2And roasting the mixture for 4 hours at 450 ℃ in an atmosphere muffle furnace to obtain the catalyst. The catalyst composition is shown in table 1.
1g of the catalyst was put in an isothermal fixed bed reactor and reduced with hydrogen before evaluation under the same conditions as in example 1, and the preparation method and test results of the catalyst are shown in Table 2.
[ example 29 ]
2g of double-layer graphene is placed in a tubular reactor, and 15% NH is introduced3+5%PH3The nitrogen is treated, the gas flow rate is 300mL/min, the treatment temperature is 450 ℃, the treatment time is 10 hours, and the nitrogen is used as a catalyst carrier after cooling.
0.622mL of a palladium chloride solution having a concentration of 16.14mL/L was mixed with 0.378mL of a ferric nitrate solution having a concentration of 3.71g of (Fe)/L, 0.378mL of water was added to prepare a solution, 2g of the above carrier was added to the solution, stirred, left at room temperature for 2 hours, dried at 120 ℃ for 4 hours, and finally calcined at 450 ℃ in a muffle furnace having an atmosphere of N2 to obtain a catalyst. The catalyst composition is shown in table 1.
1g of the catalyst was put in an isothermal fixed bed reactor and reduced with hydrogen before evaluation under the same conditions as in example 1, and the preparation method and test results of the catalyst are shown in Table 2.
[ example 30 ]
2g of a mixture of multi-walled and single-walled graphene was placed in a tubular reactor and charged with a solution containing 15% NH3+5%BH3The nitrogen is treated, the gas flow rate is 300mL/min, the treatment temperature is 450 ℃, the treatment time is 10 hours, and the nitrogen is used as a catalyst carrier after cooling.
0.622mL of a palladium chloride solution having a concentration of 16.14mL/L was mixed with 0.378mL of a ferric nitrate solution having a concentration of 3.71g of (Fe)/L, 2g of the above carrier was added to the solution, stirred, left at room temperature for 2 hours, dried at 120 ℃ for 4 hours, and finally calcined at 450 ℃ in a muffle furnace having an atmosphere of N2 to obtain a catalyst. The catalyst composition is shown in table 1.
1g of the catalyst was put in an isothermal fixed bed reactor and reduced with hydrogen before evaluation under the same conditions as in example 1, and the preparation method and test results of the catalyst are shown in Table 2.
Comparative example 1
Taking 0.622mL of chloroplatinic acid solution with the concentration of 16.14mL/L, adding 1.378mL of water to prepare a solution, adding 2g of single-layer graphene into the solution, stirring, standing at room temperature for 2h, then placing the solution into a vacuum drying oven, drying at 100 ℃ and the pressure of 0MPa for 4h, and then placing a sample into a muffle furnace to roast for 4h under the nitrogen atmosphere at 450 ℃ to obtain the required catalyst.
1g of the catalyst was put in an isothermal fixed bed reactor and reduced with hydrogen before evaluation under the same conditions as in example 1, and the preparation method and test results of the catalyst are shown in Table 2.
Comparative example 2
Taking 0.622mL of chloroplatinic acid solution with the concentration of 16.14mL/L, adding 1.378mL of water to prepare a solution, adding 2g of double-layer graphene into the solution, stirring, standing at room temperature for 2h, then placing the solution into a vacuum drying oven, drying at 100 ℃ and the pressure of 0MPa for 4h, and then placing a sample into a muffle furnace to roast for 4h under the nitrogen atmosphere at 450 ℃ to obtain the required catalyst.
1g of the catalyst was put in an isothermal fixed bed reactor and reduced with hydrogen before evaluation under the same conditions as in example 1, and the preparation method and test results of the catalyst are shown in Table 2.
Comparative example 3
Placing 2g of a mixture of multi-wall graphene and single-layer graphene in a tubular reactor, introducing nitrogen containing 15% H2S + 5% BH3 for treatment, wherein the gas flow rate is 300mL/min, the treatment temperature is 450 ℃, the treatment time is 12H, and cooling the mixture to be used as a catalyst carrier.
Taking 0.622mL of 16.14mL/L palladium chloride solution, adding 2g of the above carrier into the solution, stirring, standing at room temperature for 2h, drying at 120 deg.C for 4h, and adding N2And roasting the mixture for 4 hours at 450 ℃ in an atmosphere muffle furnace to obtain the catalyst. The catalyst composition is shown in table 1.
1g of the catalyst was put in an isothermal fixed bed reactor and reduced with hydrogen before evaluation under the same conditions as in example 1, and the preparation method and test results of the catalyst are shown in Table 2.
1g of the catalyst was put in an isothermal fixed bed reactor and reduced with hydrogen before evaluation under the same conditions as in example 1, and the preparation method and test results of the catalyst are shown in Table 2.
TABLE 1
TABLE 2
Note: x10 is the conversion of the feed at 10h of run.
[ examples 31 to 35 ]
The performance of the catalyst prepared in example 30 was evaluated for dehydrogenation of light alkane to light olefin, and the results are shown in table 3.
TABLE 3
Note: x10 is the conversion of the feed at 10h of run.
[ examples 36 to 42 ]
The performance of the catalyst prepared in example 30 for dehydrogenation of organic liquid hydrogen storage material was evaluated and the results are shown in table 4.
TABLE 4
Note: x10 is the conversion of the feed at 10h of run.
Claims (12)
1. The liquid-phase dehydrogenation catalyst comprises the following components in parts by weight:
(a) fe doped with at least one metal selected from the group VIII noble metals of the periodic Table of the elements2O3Or Co2O30.2-8 parts of active metal;
(b) 68-99 parts of a compound formed by at least one modification element selected from B, N, S, P and graphene as a carrier.
2. The dehydrogenation catalyst of claim 1 wherein component (a) is selected from the group consisting of platinum and/or palladium in an amount of 0.1 to 7 parts by weight; fe2O3Or Co2O3The content is 0.01-1 part by weight.
3. The dehydrogenation catalyst according to claim 1, wherein the amount of the carrier after the compound of at least one modification element selected from B, N, S, P and graphene in component (B) is 70-95 parts by weight, preferably the modification elements are N and S, or preferably the modification elements are N and P, or further preferably the modification elements are N and B.
4. The dehydrogenation catalyst of claim 1, the graphene being selected from at least one of single-layer graphene, double-layer graphene, preferably the graphene being selected from nitrogen-modified single-layer graphene, more preferably the graphene being selected from N and S co-modified single-layer graphene, N and P co-modified double-layer graphene, a mixture of N and B co-modified single-layer graphene and double-layer graphene.
5. The dehydrogenation catalyst according to claim 1, wherein the graphene is 50-90 parts and the modifying element is 5-20 parts, preferably, the graphene is 55-80 parts and the modifying element is 8-20 parts.
6. A method of preparing a dehydrogenation catalyst comprising the steps of:
1) carrying out modification element treatment on graphene to obtain a compound, wherein the compound is used as a carrier;
2) contacting a salt solution of a VIII group noble metal element with a solution of Fe salt or Co salt to prepare active metal;
3) the catalyst is prepared by the active metal and the carrier through a saturated dipping procedure.
7. The process for producing a liquid-phase dehydrogenation catalyst according to claim 6, wherein the noble metal element is at least one member selected from the group consisting of noble metal elements belonging to group VIII of the periodic Table of the elements, and the noble metal element is doped with Fe2O3Or Co2O3As an active metal; and a compound formed by at least one modification element selected from B, N, S, P and graphene is used as a carrier.
8. The method for preparing a liquid-phase dehydrogenation catalyst according to claim 6, wherein the gas containing the modification element is contacted with the graphene at a temperature of 300-500 ℃ and a gas flow rate of 100-500mL/min for 4-15 h.
9. The method of claim 7, wherein the modifying element is selected from BH3,NH3,H2S,PH3Preferably NH, in a gas of3And H2S, or is selected from NH3And pH3Or is selected from NH3And BH3。
10. The dehydrogenation catalyst preparation process of claim 6, the saturation impregnation procedure being: mixing a mixed solution of a salt solution of a group VIII noble metal element and a Fe salt or a Co salt with a graphene carrier treated by a modifying element at the temperature of 25-100 ℃, standing for 1-4 h, roasting for 2-6 h in an oxygen-free atmosphere at the temperature of 300-500 ℃, and then cooling to room temperature, wherein the oxygen-free atmosphere is preferably a nitrogen atmosphere.
11. A liquid phase dehydrogenation method of organic liquid hydrogen storage material comprises the following reaction conditions: the reaction pressure is 0-10 MPa, the temperature is 100-280 ℃, and the mass space velocity is 0.1-10 h-1(ii) a The organic liquid hydrogen storage material is contacted with the catalyst of any one of claims 1-10 to react to generate hydrogen and a corresponding product.
12. The method of organic liquid hydrogen storage material dehydrogenation according to claim 11, characterized in that the hydrogen storage material comprises at least one of cyclohexane, methylcyclohexane, tetrahydronaphthalene, decahydronaphthalene, perhydroazeethylcarbazole, perhydrophenanthrene, perhydroanthracene, perhydrocarbazole or derivatives thereof, and at least one of components cut into segments from petroleum or distillate of petroleum or cut components hydrogenated material.
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