CN112237936B - Liquid phase dehydrogenation catalyst - Google Patents
Liquid phase dehydrogenation catalyst Download PDFInfo
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- CN112237936B CN112237936B CN201910638290.5A CN201910638290A CN112237936B CN 112237936 B CN112237936 B CN 112237936B CN 201910638290 A CN201910638290 A CN 201910638290A CN 112237936 B CN112237936 B CN 112237936B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 208
- 238000006356 dehydrogenation reaction Methods 0.000 title claims abstract description 35
- 239000007791 liquid phase Substances 0.000 title claims abstract description 16
- 239000000243 solution Substances 0.000 claims abstract description 112
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 84
- 239000001257 hydrogen Substances 0.000 claims abstract description 80
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 77
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 76
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 75
- 238000002360 preparation method Methods 0.000 claims abstract description 42
- 239000000203 mixture Substances 0.000 claims abstract description 41
- 238000000034 method Methods 0.000 claims abstract description 25
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 20
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 18
- 150000001875 compounds Chemical class 0.000 claims abstract description 17
- 229910052751 metal Inorganic materials 0.000 claims abstract description 15
- 239000002184 metal Substances 0.000 claims abstract description 15
- 150000003839 salts Chemical class 0.000 claims abstract description 12
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 11
- 229910052796 boron Inorganic materials 0.000 claims abstract description 10
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 10
- 230000004048 modification Effects 0.000 claims abstract description 7
- 238000012986 modification Methods 0.000 claims abstract description 7
- 238000005470 impregnation Methods 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 239000012266 salt solution Substances 0.000 claims abstract description 6
- 230000000737 periodic effect Effects 0.000 claims abstract description 4
- 239000007789 gas Substances 0.000 claims description 42
- 239000002356 single layer Substances 0.000 claims description 36
- 239000012298 atmosphere Substances 0.000 claims description 31
- 238000006243 chemical reaction Methods 0.000 claims description 30
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 29
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 22
- 239000007788 liquid Substances 0.000 claims description 16
- 239000010410 layer Substances 0.000 claims description 9
- 239000011232 storage material Substances 0.000 claims description 9
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 claims description 8
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 8
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 6
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 claims description 6
- 238000005984 hydrogenation reaction Methods 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 claims description 4
- 239000003208 petroleum Substances 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
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 claims description 3
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-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
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims 1
- 238000003860 storage Methods 0.000 abstract description 15
- 238000011068 loading method Methods 0.000 abstract description 2
- 229920006395 saturated elastomer Polymers 0.000 abstract description 2
- 238000011156 evaluation Methods 0.000 description 68
- 230000009467 reduction Effects 0.000 description 65
- 238000012360 testing method Methods 0.000 description 33
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 32
- 229910001873 dinitrogen Inorganic materials 0.000 description 28
- 239000002253 acid Substances 0.000 description 27
- 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
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 9
- 239000012528 membrane Substances 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 6
- 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 6
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 5
- 238000001035 drying Methods 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
- 238000003756 stirring Methods 0.000 description 4
- 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
- 239000007858 starting material Substances 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
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 229930195733 hydrocarbon Natural products 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
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 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
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001335 aliphatic alkanes 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
- 230000015556 catabolic process Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000010574 gas phase reaction Methods 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- 238000004519 manufacturing process 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
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000001737 promoting effect 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 Fe with (a) at least one metal selected from noble metal elements of group VIII of the periodic table 2 O 3 Or Co 2 O 3 As active metal, the content is 0.1-6 parts; (b) B, N, S, P modified element and graphene are used as a carrier, and the content is 68-99 parts. The dehydrogenation catalyst is prepared by 1) carrying out B, N, S, P modification element treatment on graphene to obtain a carrier; 2) Mixing a salt solution of a noble metal element in the VIII group with a solution of Fe salt or Co salt, and loading the mixture on a carrier by adopting a saturated impregnation method to prepare the catalyst. The catalyst has higher stability when being applied to the liquid phase dehydrogenation of the hydrogen storage compounds.
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
The hydrogen energy needs to be applied on a large scale, and a plurality of technical problems need to be solved. Among them, safe and efficient transportation of hydrogen is one of the most central problems. Currently, hydrogen storage technologies mainly include physical hydrogen storage, adsorption hydrogen storage, and chemical hydrogen storage. Physical hydrogen storage technology has met the requirements of vehicles, but it is a deviceThe high demands and demanding operating conditions make the contradiction between this technical performance and efficiency increasingly prominent. Adsorption hydrogen storage and chemical hydrogen storage are important points of current researches, and certain research results are obtained, but a certain gap is left from the technical requirements of vehicle-mounted hydrogen storage. The technology for storing hydrogen energy by organic liquid in chemical hydrogen storage (mainly including methylcyclohexane, cyclohexane, tetrahydronaphthalene, decalin, perhydroazoethylcarbazole, perhydrocarbazole and the like) realizes the storage of hydrogen energy by catalytic addition and dehydrogenation reversible reaction, the reaction is reversible, reactant products can be recycled, and the hydrogen storage amount is relatively high (about 60-75kg H) 2 /m 3 The mass fraction is 6-8%), meets the index stipulated by the International energy agency and the United states department of energy (DOE), carries out long-distance transportation in an organic liquid form or can solve the problem of uneven regional distribution of the energy, truly meets the requirements of green chemistry, and has stronger application prospect.
In the organic liquid hydrogen storage technology, hydrogenation and dehydrogenation processes coexist, the hydrogenation process is relatively simple, the technology is mature, the dehydrogenation process is a reaction with strong heat absorption and increased volume, so that the dehydrogenation reaction is carried out at high temperature in terms 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 or even deactivated. 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 conversion rate of the reaction, or a membrane reactor is adopted to promote the reaction balance, which results in high operation cost, large equipment investment and difficult maintenance, and brings difficulty to large-scale application. If the reaction is carried out in the liquid phase, the hydrogen produced by the reaction overflows in the form of gas, so that the problem of reaction balance does not exist, the reaction temperature can be greatly reduced, a membrane reactor is not needed, and the method has a plurality of advantages compared with the gas phase reaction.
CN108067172a discloses a microchannel reactor and a dehydrogenation method suitable for dehydrogenation reaction of a liquid hydrogen source material, a liquid distributor is connected above the microchannel reactor body, a deflector is arranged inside the liquid distributor, a high-temperature flange is arranged between the liquid distributor and an inlet of the hydrogen source material, a hydrogen storage carrier and an outlet of hydrogen are arranged below the microchannel reactor body, and a high-temperature flange is arranged between the microchannel reactor body and the outlet; the inlet side of the micro-channel reactor body is connected with a heat carrier distributor, a guide plate is arranged in 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 at the other side of the micro-channel reactor body, and a high-temperature flange is arranged between the micro-channel reactor body and the heat carrier outlet; the interior of the microchannel reactor body is provided with a plurality of transverse and longitudinal orthogonal microchannels.
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 and degradation of the performance of a dehydrogenation catalyst is suppressed when hydrogen is produced by a combined dehydrogenation reaction. Organic hydrides having hydrogen separation membranes, and the like. A flow-through reactor for the dehydrogenation of organic compounds comprises a hydrogen separation membrane that is selectively permeable to hydrogen; and a dehydrogenation catalyst for promoting a dehydrogenation reaction of the 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 permeation side region separated therefrom, through the hydrogen separation membrane and the hydrogen that has passed through the hydrogen separation membrane can flow.
The two methods described above achieve liquid phase dehydrogenation of organic liquid compounds in an attempt to improve the reaction efficiency by breaking the limitations of the reaction equilibrium. The key problem to be solved by liquid phase reactions is to find a catalyst that can activate hydrogen-containing compounds at lower temperatures and has a higher stability. The noble metal and the graphene substrate partially substituted by the modifying element have very strong interaction, so that the catalyst has very good hydrocarbon bond activation performance, more importantly, the interaction enables the noble metal to be anchored on the surface of the graphene, migration and aggregation of the noble metal are prevented, and the catalyst has a relatively strong effect on improving the stability of the catalyst. According to the idea, the 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 deactivation, high operation cost caused by using 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) At least one metal selected from noble metal elements of group VIII of the periodic Table of elements is doped with Fe 2 O 3 Or Co 2 O 3 As active metal, the content is 0.2-8 parts;
(b) The compound formed by the modifying element and the graphene is used as a carrier, and the content of the compound is 68-99 parts.
In the above technical scheme, preferably, the component (a) comprises platinum and/or palladium, the content of which is 0.1 to 7 parts by weight, preferably the content of which is 0.1 to 6 parts by weight, and Fe 2 O 3 Or Co 2 O 3 The content is 0.01 to 1 part by weight, preferably 0.01 to 0.8 part by weight.
In the above technical solution, the modifying element in the component (B) is at least one selected from B, N, S, P, and after forming a compound with graphene, the carrier content is 70-95 parts by weight, preferably, the modifying element is N and S, preferably, the modifying element is N and P, and still preferably, the modifying element is N and B.
In the above technical solution, the graphene is at least one selected from single-layer graphene and double-layer graphene, preferably the graphene is selected from single-layer graphene co-modified by N and S, double-layer graphene co-modified by N and P, and a mixture of single-layer graphene and double-layer graphene co-modified by N and B.
In the above technical scheme, more preferably, the content of graphene is 50-90 parts, the content of the modifying element is 5-20 parts, most preferably, the content of graphene is 55-80 parts, and the content of the modifying element is 8-20 parts.
In the 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 a salt solution of a noble metal element in the VIII group with a 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 scheme, preferably, the catalyst comprises the following components in parts by weight: (a) At least one metal selected from noble metal elements of group VIII of the periodic Table of elements is doped with Fe 2 O 3 Or Co 2 O 3 As active metal, the content is 0.2-8 parts; (b) At least one compound formed by modifying elements selected from B, N, S, P and graphene is used as a carrier, and the content of the compound is 68-99 parts. In the above technical solution, preferably, the method for performing modification element treatment on graphene includes: introducing the gas containing the modifying element into a reactor filled with graphene, and treating for 4-15h at the temperature of 300-500 ℃ and the gas flow rate of 100-500 mL/min.
In the above technical scheme, preferably, the modifying element is selected from BH 3 ，NH 3 ，H 2 S，PH 3 At least one of the gases of (1), preferably, the modifying element is selected from the group consisting of NH 3 And H 2 S, or NH 3 And pH (potential of Hydrogen) 3 Or NH 3 And BH 3 。
In the above technical solution, preferably, the saturation impregnation 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 graphene treated by a modifying element, standing for 1-4 h, roasting for 2-6 h in an anaerobic atmosphere at 300-500 ℃, and cooling to room temperature.
In the above technical solution, more preferably, the oxygen-free atmosphere is: and (3) nitrogen atmosphere.
In the above technical scheme, preferably, a method for liquid phase dehydrogenation of an organic liquid hydrogen storage material is provided, and the reaction conditions are as follows: the reaction pressure is 0-10 MPa, the temperature is 100-280 ℃ and the mass airspeed is 0.1-10 h -1 The method comprises the steps of carrying out a first treatment on the surface of the The organic liquid hydrogen storage material reacts with the catalyst in a contact way to generate hydrogen and corresponding products.
In the technical scheme, the optimized method for preparing the low-carbon olefin by dehydrogenating the low-carbon alkane adopts isobutane and/or butene as raw materials, and the reaction pressure is 0-10 MPa and the alkane mass airspeed is 0.1-8.0 h at the reaction temperature of 100-380 DEG C -1 The raw materials are contacted and reacted with the catalyst to generate isobutene and/or butadiene.
In the above technical scheme, preferably, the hydrogen storage material comprises at least one of cyclohexane, methylcyclohexane, tetrahydronaphthalene, decalin, perhydroazoethylcarbazole, perhydro phenanthrene, perhydro anthracene, perhydro carbazole or at least one of derivatives thereof, and at least one of a component for cutting a section from petroleum or distillate oil of petroleum or a material after hydrogenation of the cut component.
The interaction between the noble metal and the graphene substrate partially substituted by the modifying element prepares a catalyst in which the noble metal is dispersed on the surface of the metal carbide nano particle in an atomic level, and a high-density atomic scale catalytic active center is constructed, wherein the active center has very good hydrocarbon bond activation performance, and the strong interaction between the noble metal and the graphene substrate can fix the noble metal, prevent migration and aggregation of the noble metal, and has higher catalytic stability.
The present invention is further illustrated by the following examples, but the present invention is not limited to the following examples.
Detailed Description
[ example 1 ]
2g of single-layer graphene is placed in a tubular reactor, and 10 percent NH is introduced 3 The nitrogen gas of (2) was treated at a gas flow rate of 300mL/min at a treatment temperature of 450℃for 10 hours, and cooled to give a catalyst support.
1.244mL of a 1.614g (Pt)/L chloroplatinic acid solution was mixed with 0.378mL of a 3.71g (Fe)/L ferric nitrate solution, 2g of a carrier was added to the solution, and the mixture was stirred, left at room temperature for 2 hours, then dried at 120℃for 4 hours, and finally put into N 2 Roasting in a muffle furnace in atmosphere at 450 ℃ for 4h to obtain the catalyst. The catalyst composition is shown in the table1.
The catalyst obtained was tabletted, ground to a particle size of 12-20 mesh, and 1g was evaluated in an isothermal fixed bed reactor, and was reduced with hydrogen gas before the evaluation under the following conditions: the pressure is normal pressure, the temperature is 450 ℃, the hydrogen flow is 200mL/min, the reduction time is 4h, and then the temperature is reduced and evaluated under the following conditions: the reaction pressure is normal pressure, the temperature is 320 ℃, and the space velocity is 2h -1 Methylcyclohexane is used as a representative raw material for hydrogen storage in organic liquids. TOF represents the catalyst activity, TOF is the conversion rate of the reactant under the active metal in g -1 ·h -1 . (tof=conversion/(active metal mass 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 percent NH is introduced 3 The nitrogen gas of (2) was treated at a gas flow rate of 300mL/min at a treatment temperature of 450℃for 10 hours, and cooled to give a catalyst support.
1.244mL of a chloroplatinic acid solution having a concentration of 16.14g (Pt)/L was mixed with 0.378mL of an iron nitrate solution having a concentration of 3.71g (Fe)/L, 2g of the above carrier was added to the solution, stirred, left at room temperature for 2 hours, then dried at 120℃for 4 hours, and finally put into N 2 Roasting in a muffle furnace in atmosphere at 450 ℃ for 4h to obtain the catalyst. The catalyst composition is shown in table 1.
1g of the catalyst was evaluated in an isothermal fixed bed reactor, and was reduced with hydrogen before the evaluation under the same conditions as in example 1. The preparation method and the test result of the catalyst are shown in Table 2.
[ example 3 ]
2g of single-layer graphene is placed in a tubular reactor, and 10 percent NH is introduced 3 The nitrogen gas of (2) was treated at a gas flow rate of 300mL/min at a treatment temperature of 450℃for 10 hours, and cooled to give a catalyst support.
1.244mL of a chloroplatinic acid solution having a concentration of 8.07g (Pt)/L was mixed with 0.378mL of an iron nitrate solution having a concentration of 3.71g (Fe)/L, 2g of the above carrier was added to the solution, and the mixture was stirred at room temperatureStanding for 2 hr, drying at 120deg.C for 4 hr, and adding into N 2 Roasting in a muffle furnace in atmosphere at 450 ℃ for 4h to obtain the catalyst. The catalyst composition is shown in table 1.
1g of the catalyst was evaluated in an isothermal fixed bed reactor, and hydrogen was used for reduction before the evaluation, and the reduction conditions and the evaluation conditions were the same as those of example 1, and the preparation method and the 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 percent NH is introduced 3 The nitrogen gas of (2) was treated at a gas flow rate of 300mL/min at a treatment temperature of 450℃for 10 hours, and cooled to give a catalyst support.
1.244mL of a 1.614g (Pt)/L chloroplatinic acid solution was mixed with 0.378mL of a 3.71g (Fe)/L ferric nitrate solution, 2g of the above carrier was added to the solution, stirred, left at room temperature for 2 hours, then dried at 120℃for 4 hours, and finally put into N 2 Roasting in a muffle furnace in atmosphere at 450 ℃ for 4h to obtain the catalyst. The catalyst composition is shown in table 1.
1g of the catalyst was evaluated in an isothermal fixed bed reactor, and hydrogen was used for reduction before the evaluation, and the reduction conditions and the evaluation conditions were the same as those of example 1, and the preparation method and the 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 percent NH is introduced 3 The nitrogen gas of (2) was treated at a gas flow rate of 300mL/min at a treatment temperature of 450℃for 10 hours, and cooled to give a catalyst support.
1.244mL of a chloroplatinic acid solution having a concentration of 11.298g (Pt)/L was mixed with 0.378mL of an iron nitrate solution having a concentration of 3.71g (Fe)/L, 2g of the above carrier was added to the solution, stirred, left at room temperature for 2 hours, then dried at 120℃for 4 hours, and finally put into N 2 Roasting in a muffle furnace in atmosphere at 450 ℃ for 4h to obtain the catalyst. The catalyst composition is shown in table 1.
1g of the catalyst was evaluated in an isothermal fixed bed reactor, and hydrogen was used for reduction before the evaluation, and the reduction conditions and the evaluation conditions were the same as those of example 1, and the preparation method and the 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 introduced 3 The nitrogen gas of (2) was treated at a gas flow rate of 300mL/min at a treatment temperature of 450℃for 10 hours, and cooled to give a catalyst support.
1.244mL of a chloroplatinic acid solution having a concentration of 16.14g (Pt)/L was mixed with 0.378mL of an iron nitrate solution having a concentration of 3.71g (Fe)/L, 2g of the above carrier was added to the solution, stirred, left at room temperature for 2 hours, then dried at 120℃for 4 hours, and finally put into N 2 Roasting in a muffle furnace in atmosphere at 450 ℃ for 4h to obtain the catalyst. The catalyst composition is shown in table 1.
1g of the catalyst was evaluated in an isothermal fixed bed reactor, and hydrogen was used for reduction before the evaluation, and the reduction conditions and the evaluation conditions were the same as those of example 1, and the preparation method and the test results of the catalyst are shown in Table 2.
[ example 7 ]
2g of monolayer graphene was placed in a tubular reactor and 10% H was introduced 2 S, treating with nitrogen at a gas flow rate of 300mL/min at a treatment temperature of 450 ℃ for 10 hours, and cooling to obtain the catalyst carrier.
1.244mL of a chloroplatinic acid solution having a concentration of 16.14g (Pt)/L was mixed with 0.378mL of an iron nitrate solution having a concentration of 3.71g (Fe)/L, 2g of the above carrier was added to the solution, stirred, left at room temperature for 2 hours, then dried at 120℃for 4 hours, and finally put into N 2 Roasting in a muffle furnace in atmosphere at 450 ℃ for 4h to obtain the catalyst. The catalyst composition is shown in table 1.
1g of the catalyst was evaluated in an isothermal fixed bed reactor, and hydrogen was used for reduction before the evaluation, and the reduction conditions and the evaluation conditions were the same as those of example 1, and the preparation method and the test results of the catalyst are shown in Table 2.
[ example 8 ]
2g of monolayer graphene was placed in a tubular reactor and introduced at 10% pH 3 The nitrogen gas of (2) is treated, the gas flow rate is 300mL/min, the treatment temperature is 450 ℃, the treatment time is 10h,and cooling to obtain the catalyst carrier.
1.244mL of a chloroplatinic acid solution having a concentration of 16.14g (Pt)/L was mixed with 0.378mL of an iron nitrate solution having a concentration of 3.71g (Fe)/L, 2g of the above carrier was added to the solution, stirred, left at room temperature for 2 hours, then dried at 120℃for 4 hours, and finally put into N 2 Roasting in a muffle furnace in atmosphere at 450 ℃ for 4h to obtain the catalyst. The catalyst composition is shown in table 1.
1g of the catalyst was evaluated in an isothermal fixed bed reactor, and hydrogen was used for reduction before the evaluation, and the reduction conditions and the evaluation conditions were the same as those of example 1, and the preparation method and the 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 percent NH is introduced 3 The nitrogen gas of (2) was treated at a gas flow rate of 500mL/min at a treatment temperature of 450℃for 10 hours, and cooled to give a catalyst support.
1.244mL of a chloroplatinic acid solution having a concentration of 16.14g (Pt)/L was mixed with 0.378mL of an iron nitrate solution having a concentration of 0.371g (Fe)/L, 2g of the above carrier was added to the solution, stirred, left at room temperature for 2 hours, then dried at 120℃for 4 hours, and finally put into N 2 Roasting in a muffle furnace in atmosphere at 450 ℃ for 4h to obtain the catalyst. The catalyst composition is shown in table 1.
1g of the catalyst was evaluated in an isothermal fixed bed reactor, and hydrogen was used for reduction before the evaluation, and the reduction conditions and the evaluation conditions were the same as those of example 1, and the preparation method and the 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 percent NH is introduced 3 The nitrogen gas of (2) was treated at a gas flow rate of 400mL/min at a treatment temperature of 450℃for 10 hours, and cooled to give a catalyst support.
1.244mL of a chloroplatinic acid solution having a concentration of 16.14g (Pt)/L was mixed with 0.378mL of an iron nitrate solution having a concentration of 37.1g (Fe)/L, 2g of the above carrier was added to the solution, stirred, left at room temperature for 2 hours, then dried at 120℃for 4 hours, and finally put into N 2 Atmosphere muffle furnaceRoasting for 4 hours at 450 ℃ to obtain the catalyst. The catalyst composition is shown in table 1.
1g of the catalyst was evaluated in an isothermal fixed bed reactor, and hydrogen was used for reduction before the evaluation, and the reduction conditions and the evaluation conditions were the same as those of example 1, and the preparation method and the 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 percent NH is introduced 3 The nitrogen gas of (2) was treated at a gas flow rate of 300mL/min at a treatment temperature of 450℃for 10 hours, and cooled to give a catalyst support.
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, stirred, left at room temperature for 2 hours, then dried at 120℃for 4 hours, and finally put into N 2 Roasting in a muffle furnace in atmosphere at 450 ℃ for 4h to obtain the catalyst. The catalyst composition is shown in table 1.
1g of the catalyst was evaluated in an isothermal fixed bed reactor, and hydrogen was used for reduction before the evaluation, and the reduction conditions and the evaluation conditions were the same as those of example 1, and the preparation method and the 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 percent NH is introduced 3 The nitrogen gas of (2) was treated at a gas flow rate of 200mL/min at a treatment temperature of 450℃for 10 hours, and cooled to give a catalyst support.
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 83.3g (Co)/L, 2g of the above carrier was added to the solution, stirred, left at room temperature for 2 hours, then dried at 120℃for 4 hours, and finally put into N 2 Roasting in a muffle furnace in atmosphere at 450 ℃ for 4h to obtain the catalyst. The catalyst composition is shown in table 1.
1g of the catalyst was evaluated in an isothermal fixed bed reactor, and hydrogen was used for reduction before the evaluation, and the reduction conditions and the evaluation conditions were the same as those of example 1, and the preparation method and the 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 percent NH is introduced 3 The nitrogen gas of (2) was treated at a gas flow rate of 350mL/min at a treatment temperature of 450℃for 6 hours, and cooled to give a catalyst support.
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, stirred, left at room temperature for 2 hours, then dried at 120℃for 4 hours, and finally put into N 2 Roasting in a muffle furnace in atmosphere at 450 ℃ for 4h to obtain the catalyst. The catalyst composition is shown in table 1.
1g of the catalyst was evaluated in an isothermal fixed bed reactor, and hydrogen was used for reduction before the evaluation, and the reduction conditions and the evaluation conditions were the same as those of example 1, and the preparation method and the 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 percent NH is introduced 3 The nitrogen gas of (2) was treated at a gas flow rate of 400mL/min at a treatment temperature of 450℃for 8 hours, and cooled to give a catalyst support.
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, stirred, left at room temperature for 2 hours, then dried at 120℃for 4 hours, and finally put into N 2 Roasting in a muffle furnace in atmosphere at 450 ℃ for 4h to obtain the catalyst. The catalyst composition is shown in table 1.
1g of the catalyst was evaluated in an isothermal fixed bed reactor, and hydrogen was used for reduction before the evaluation, and the reduction conditions and the evaluation conditions were the same as those of example 1, and the preparation method and the 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 percent NH is introduced 3 The nitrogen gas of (2) was treated at a gas flow rate of 430mL/min at a treatment temperature of 450℃for 10 hours, and cooled to give a catalyst support.
1.244mL of the concentration was takenA solution of chloroplatinic acid of 16.14g (Pt)/L was mixed with 0.378mL of a solution of cobalt nitrate of 8.33g (Co)/L, 2g of the above carrier was added to the solution, stirred, left at room temperature for 2 hours, then dried at 120℃for 4 hours, and finally put into N 2 Roasting in a muffle furnace in atmosphere at 450 ℃ for 4h to obtain the catalyst. The catalyst composition is shown in table 1.
1g of the catalyst was evaluated in an isothermal fixed bed reactor, and hydrogen was used for reduction before the evaluation, and the reduction conditions and the evaluation conditions were the same as those of example 1, and the preparation method and the 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 percent NH is introduced 3 The nitrogen gas of (2) is treated at a gas flow rate of 480mL/min, a treatment temperature of 450 ℃ and a treatment time of 10h, and the catalyst carrier is obtained 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, stirred, left at room temperature for 2 hours, then dried at 120℃for 4 hours, and finally put into N 2 Roasting in a muffle furnace in atmosphere at 450 ℃ for 4h to obtain the catalyst. The catalyst composition is shown in table 1.
1g of the catalyst was evaluated in an isothermal fixed bed reactor, and hydrogen was used for reduction before the evaluation, and the reduction conditions and the evaluation conditions were the same as those of example 1, and the preparation method and the 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 percent NH is introduced 3 The nitrogen gas of (2) was treated at a gas flow rate of 300mL/min at a treatment temperature of 450℃for 10 hours, and cooled to give a catalyst support.
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, stirred, left at room temperature for 2 hours, then dried at 120℃for 4 hours, and finally put into N 2 Roasting in a muffle furnace in atmosphere at 450 ℃ for 4h to obtain the catalyst. The catalyst composition is shown in table 1.
1g of the catalyst was evaluated in an isothermal fixed bed reactor, and hydrogen was used for reduction before the evaluation, and the reduction conditions and the evaluation conditions were the same as those of example 1, and the preparation method and the 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 percent NH is introduced 3 +5％BH 3 The nitrogen gas of (2) was treated at a gas flow rate of 300mL/min at a treatment temperature of 450℃for 10 hours, and cooled to give a catalyst support.
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, stirred, left at room temperature for 2 hours, then dried at 120℃for 4 hours, and finally put into N 2 Roasting in a muffle furnace in atmosphere at 450 ℃ for 4h to obtain the catalyst. The catalyst composition is shown in table 1.
1g of the catalyst was evaluated in an isothermal fixed bed reactor, and hydrogen was used for reduction before the evaluation, and the reduction conditions and the evaluation conditions were the same as those of example 1, and the preparation method and the 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 percent NH is introduced 3 +5％H 2 S, treating with nitrogen at a gas flow rate of 300mL/min at a treatment temperature of 450 ℃ for 10 hours, and cooling to obtain the catalyst carrier.
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, stirred, left at room temperature for 2 hours, then dried at 120℃for 4 hours, and finally put into N 2 Roasting in a muffle furnace in atmosphere at 450 ℃ for 4h to obtain the catalyst. The catalyst composition is shown in table 1.
1g of the catalyst was evaluated in an isothermal fixed bed reactor, and hydrogen was used for reduction before the evaluation, and the reduction conditions and the evaluation conditions were the same as those of example 1, and the preparation method and the 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 percent NH is introduced 3 +5％PH 3 The nitrogen gas of (2) was treated at a gas flow rate of 300mL/min at a treatment temperature of 450℃for 10 hours, and cooled to give a catalyst support.
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, stirred, left at room temperature for 2 hours, then dried at 120℃for 4 hours, and finally put into N 2 Roasting in a muffle furnace in atmosphere at 450 ℃ for 4h to obtain the catalyst. The catalyst composition is shown in table 1.
1g of the catalyst was evaluated in an isothermal fixed bed reactor, and hydrogen was used for reduction before the evaluation, and the reduction conditions and the evaluation conditions were the same as those of example 1, and the preparation method and the 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 percent NH is introduced 3 The nitrogen gas of (2) was treated at a gas flow rate of 300mL/min at a treatment temperature of 450℃for 10 hours, and cooled to give a catalyst support.
1.244mL of a palladium chloride solution having a concentration of 16.14g (Pd)/L was mixed with 0.378mL of a cobalt nitrate solution having a concentration of 8.33g (Co)/L, 2g of the above-mentioned carrier was added to the solution, stirred, left at room temperature for 2 hours, then dried at 120℃for 4 hours, and finally put into N 2 Roasting in a muffle furnace in atmosphere at 450 ℃ for 4h to obtain the catalyst. The catalyst composition is shown in table 1.
1g of the catalyst was evaluated in an isothermal fixed bed reactor, and hydrogen was used for reduction before the evaluation, and the reduction conditions and the evaluation conditions were the same as those of example 1, and the preparation method and the 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 percent NH is introduced 3 The nitrogen gas of (2) was treated at a gas flow rate of 300mL/min at a treatment temperature of 450℃for 10 hours, and cooled to give a catalyst support.
1.244mL of palladium chloride having a concentration of 48.42g (Pd)/L was takenMixing the 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 2 hr, drying at 120deg.C for 4 hr, and adding into N 2 Roasting in a muffle furnace in atmosphere at 450 ℃ for 4h to obtain the catalyst. The catalyst composition is shown in table 1.
1g of the catalyst was evaluated in an isothermal fixed bed reactor, and hydrogen was used for reduction before the evaluation, and the reduction conditions and the evaluation conditions were the same as those of example 1, and the preparation method and the test results of the catalyst are shown in Table 2.
Example 23
2g of monolayer graphene was placed in a tubular reactor and 15% H was introduced 2 S+5％BH 3 The nitrogen gas of (2) was treated at a gas flow rate of 300mL/min at a treatment temperature of 450℃for 10 hours, and cooled to give a catalyst support.
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-mentioned carrier was added to the solution, stirred, left at room temperature for 2 hours, dried at 120℃for 4 hours, and finally put into a muffle furnace having an N2 atmosphere and calcined at 450℃for 4 hours to obtain a catalyst. The catalyst composition is shown in table 1.
1g of the catalyst was evaluated in an isothermal fixed bed reactor, and hydrogen was used for reduction before the evaluation, and the reduction conditions and the evaluation conditions were the same as those of example 1, and the preparation method and the test results of the catalyst are shown in Table 2.
[ example 24 ]
2g of monolayer graphene was placed in a tubular reactor and 15% H was introduced 2 S+5％PH 3 The nitrogen gas of (2) was treated at a gas flow rate of 300mL/min at a treatment temperature of 450℃for 10 hours, and cooled to give a catalyst support.
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, stirred, left at room temperature for 2 hours, then dried at 120℃for 4 hours, and finally put into N 2 Roasting in a muffle furnace in atmosphere at 450 ℃ for 4h to obtain the catalyst. The catalyst composition is shown in table 1.
1g of the catalyst was evaluated in an isothermal fixed bed reactor, and hydrogen was used for reduction before the evaluation, and the reduction conditions and the evaluation conditions were the same as those of example 1, and the preparation method and the 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 introduced 3 +5％PH 3 The nitrogen gas of (2) was treated at a gas flow rate of 300mL/min at a treatment temperature of 450℃for 10 hours, and cooled to give a catalyst support.
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, stirred, left at room temperature for 2 hours, then dried at 120℃for 4 hours, and finally put into N 2 Roasting in a muffle furnace in atmosphere at 450 ℃ for 4h to obtain the catalyst. The catalyst composition is shown in table 1.
1g of the catalyst was evaluated in an isothermal fixed bed reactor, and hydrogen was used for reduction before the evaluation, and the reduction conditions and the evaluation conditions were the same as those of example 1, and the preparation method and the 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 percent NH is introduced 3 The nitrogen gas of (2) was treated at a gas flow rate of 300mL/min at a treatment temperature of 450℃for 10 hours, and cooled to give a catalyst support.
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, stirred, left at room temperature for 2 hours, then dried at 120℃for 4 hours, and finally put into N 2 Roasting in a muffle furnace in atmosphere at 450 ℃ for 4h to obtain the catalyst. The catalyst composition is shown in table 1.
1g of the catalyst was evaluated in an isothermal fixed bed reactor, and hydrogen was used for reduction before the evaluation, and the reduction conditions and the evaluation conditions were the same as those of example 1, and the preparation method and the 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 percent NH is introduced 3 The nitrogen gas of (2) was treated at a gas flow rate of 300mL/min at a treatment temperature of 450℃for 10 hours, and cooled to give a catalyst support.
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, stirred, left at room temperature for 2 hours, then dried at 120℃for 4 hours, and finally put into N 2 Roasting in a muffle furnace in atmosphere at 450 ℃ for 4h to obtain the catalyst. The catalyst composition is shown in table 1.
1g of the catalyst was evaluated in an isothermal fixed bed reactor, and hydrogen was used for reduction before the evaluation, and the reduction conditions and the evaluation conditions were the same as those of example 1, and the preparation method and the 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 percent NH is introduced 3 +5％BH 3 The nitrogen gas of (2) was treated at a gas flow rate of 300mL/min at a treatment temperature of 450℃for 10 hours, and cooled to give a catalyst support.
1.244mL of a palladium chloride solution having a concentration of 16.14g (Pd)/L was mixed with 0.378mL of a cobalt nitrate solution having a concentration of 8.33g (Co)/L, 2g of the above-mentioned carrier was added to the solution, stirred, left at room temperature for 2 hours, then dried at 120℃for 4 hours, and finally put into N 2 Roasting in a muffle furnace in atmosphere at 450 ℃ for 4h to obtain the catalyst. The catalyst composition is shown in table 1.
1g of the catalyst was evaluated in an isothermal fixed bed reactor, and hydrogen was used for reduction before the evaluation, and the reduction conditions and the evaluation conditions were the same as those of example 1, and the preparation method and the 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 percent NH is introduced 3 +5％PH 3 The nitrogen gas of (2) was treated at a gas flow rate of 300mL/min at a treatment temperature of 450℃for 10 hours, and cooled to give a catalyst support.
Mixing 0.622mL of palladium chloride solution with the concentration of 16.14mL/L and 0.378mL of ferric nitrate solution with the concentration of 3.71g (Fe)/L, adding 0.378mL of water to prepare a solution, adding 2g of the carrier into the solution, stirring, standing at room temperature for 2h, drying at 120 ℃ for 4h, and finally placing the mixture into a muffle furnace with the N2 atmosphere and roasting at 450 ℃ for 4h to obtain the catalyst. The catalyst composition is shown in table 1.
1g of the catalyst was evaluated in an isothermal fixed bed reactor, and hydrogen was used for reduction before the evaluation, and the reduction conditions and the evaluation conditions were the same as those of example 1, and the preparation method and the test results of the catalyst are shown in Table 2.
[ example 30 ]
2g of a mixture of multi-wall and single-layer graphene was placed in a tubular reactor and 15% NH was introduced 3 +5％BH 3 The nitrogen gas of (2) was treated at a gas flow rate of 300mL/min at a treatment temperature of 450℃for 10 hours, and cooled to give a catalyst support.
0.622mL of a palladium chloride solution with a concentration of 16.14mL/L was mixed with 0.378mL of an iron nitrate solution with a concentration of 3.71g (Fe)/L, 2g of the above carrier was added to the solution, stirred, left at room temperature for 2 hours, then dried at 120℃for 4 hours, and finally put into a muffle furnace with an N2 atmosphere for calcination at 450℃for 4 hours, to obtain a catalyst. The catalyst composition is shown in table 1.
1g of the catalyst was evaluated in an isothermal fixed bed reactor, and hydrogen was used for reduction before the evaluation, and the reduction conditions and the evaluation conditions were the same as those of example 1, and the preparation method and the test results of the catalyst are shown in Table 2.
Comparative example 1
0.622mL of chloroplatinic acid solution with the concentration of 16.14mL/L is taken, 1.378mL of water is added to prepare a solution, 2g monolayer graphene is added into the solution, the solution is stirred, the solution is placed at room temperature for 2 hours, then the solution is placed in a vacuum drying oven, dried for 4 hours under the pressure of 0MPa at 100 ℃, and then the sample is placed in a muffle furnace to be roasted for 4 hours under the nitrogen atmosphere at 450 ℃ to obtain the required catalyst.
1g of the catalyst was evaluated in an isothermal fixed bed reactor, and hydrogen was used for reduction before the evaluation, and the reduction conditions and the evaluation conditions were the same as those of example 1, and the preparation method and the 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 bilayer graphene into the solution, stirring, standing at room temperature for 2h, then placing into a vacuum drying oven, drying for 4h at 100 ℃ and the pressure of 0MPa, and then placing a sample into a muffle furnace to bake for 4h under the nitrogen atmosphere at 450 ℃ to obtain the required catalyst.
1g of the catalyst was evaluated in an isothermal fixed bed reactor, and hydrogen was used for reduction before the evaluation, and the reduction conditions and the evaluation conditions were the same as those of example 1, and the preparation method and the test results of the catalyst are shown in Table 2.
[ comparative example 3 ]
2g of the mixture of multi-wall and single-layer graphene is placed in a tubular reactor, nitrogen containing 15% H2S+5% of BH3 is introduced for treatment, the gas flow rate is 300mL/min, the treatment temperature is 450 ℃, the treatment time is 12h, and the cooled mixture is used as a catalyst carrier.
Taking 0.622mL of palladium chloride solution with the concentration of 16.14mL/L, adding 2g of the carrier into the solution, stirring, standing at room temperature for 2h, drying at 120 ℃ for 4h, and finally placing the carrier into N 2 Roasting in a muffle furnace in atmosphere at 450 ℃ for 4h to obtain the catalyst. The catalyst composition is shown in table 1.
1g of the catalyst was evaluated in an isothermal fixed bed reactor, and hydrogen was used for reduction before the evaluation, and the reduction conditions and the evaluation conditions were the same as those of example 1, and the preparation method and the test results of the catalyst are shown in Table 2.
1g of the catalyst was evaluated in an isothermal fixed bed reactor, and hydrogen was used for reduction before the evaluation, and the reduction conditions and the evaluation conditions were the same as those of example 1, and the preparation method and the test results of the catalyst are shown in Table 2.
TABLE 1
TABLE 2
Note that: x10 is the conversion of the starting material at 10h of operation.
Examples 31 to 35
The catalyst prepared in example 30 was used for evaluating the performance of low-carbon olefins by dehydrogenation of low-carbon alkanes, and the results are shown in Table 3.
TABLE 3 Table 3
Note that: x10 is the conversion of the starting material at 10h of operation.
Examples 36 to 42
The catalyst prepared in example 30 was used for performance evaluation of dehydrogenation reaction of organic liquid hydrogen storage material, and the results are shown in table 4.
TABLE 4 Table 4
Note that: x10 is the conversion of the starting material at 10h of operation.
Claims (18)
1. The liquid phase dehydrogenation catalyst comprises the following components in parts by weight:
(a) At least one metal selected from noble metal elements of group VIII of the periodic Table of elements is doped with Fe 2 O 3 Or Co 2 O 3 As active metal, the content is 0.2-8 parts;
(b) At least one compound formed by B, N, S, P modified elements and graphene is used as a carrier, and the content of the compound is 68-99 parts;
wherein the component (a) is selected from platinum and/or palladium, and the content of the component (a) is 0.1-7 parts by weight; fe (Fe) 2 O 3 Or Co 2 O 3 0.01-1 parts of a weight fraction;
the preparation method of the 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) The method comprises the steps of (1) contacting a salt solution of a group VIII noble metal element with a solution of Fe salt or Co salt to prepare active metal;
(3) The active metal and the carrier are subjected to a saturation impregnation procedure to prepare a catalyst;
the treatment in the step (1) is to contact the gas containing the modification element with graphene for 4-15 hours at the temperature of 300-500 ℃ at the gas flow rate of 100-500 mL/min.
2. The catalyst according to claim 1, wherein the carrier after forming the compound with graphene is at least one kind of the B, N, S, P modified element in the component (b) in an amount of 70 to 95 parts by weight.
3. The catalyst of claim 1 wherein the modifying elements in component (b) are N and S.
4. The catalyst of claim 1 wherein the modifying elements in component (b) are N and P.
5. The catalyst of claim 1 wherein the modifying elements in component (B) are N and B.
6. The catalyst according to claim 1, wherein the graphene is at least one selected from the group consisting of single-layer graphene and double-layer graphene.
7. The catalyst of claim 1, wherein the graphene is selected from nitrogen-modified single-layer graphene.
8. The catalyst of claim 1, wherein the graphene is selected from the group consisting of N and S co-modified single-layer graphene, N and P co-modified double-layer graphene, and a mixture of N and B co-modified single-layer graphene and double-layer graphene.
9. The catalyst according to claim 1, wherein the content of graphene is 50 to 90 parts and the content of the modifying element is 5 to 20 parts.
10. The catalyst according to claim 1, wherein the graphene content is 55 to 80 parts and the modifying element content is 8 to 20 parts.
11. A process for the preparation of a catalyst as claimed in any one of claims 1 to 10, 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) The method comprises the steps of (1) contacting a salt solution of a group VIII noble metal element with a solution of Fe salt or Co salt to prepare active metal;
(3) The active metal and the carrier are subjected to a saturation impregnation procedure to prepare the catalyst.
12. The preparation method of claim 11, wherein the treatment in the step (1) is to contact the gas containing the modification element with graphene at a temperature of 300-500 ℃ at a gas flow rate of 100-500mL/min for 4-15h.
13. The method according to claim 11, wherein the modifying element in step (1) is selected from BH 3 、NH 3 、H 2 S、PH 3 At least one of the gases of (a) is provided.
14. The method according to claim 11, wherein the modifying element in step (1) is selected from the group consisting of NH 3 And H 2 S is alternatively selected from NH 3 And pH (potential of Hydrogen) 3 Or is selected from NH 3 And BH 3 。
15. The method according to claim 11, wherein the saturation impregnation procedure of step (3) is: mixing a mixed solution of a salt solution of a group VIII noble metal element and a Fe salt or 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 300-500 ℃, and cooling to room temperature.
16. The method of claim 15, wherein the oxygen-free atmosphere is a nitrogen atmosphere.
17. A method for liquid phase dehydrogenation of an 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 airspeed is 0.1-10 h -1 The method comprises the steps of carrying out a first treatment on the surface of the The contact reaction of an organic liquid hydrogen storage material with the catalyst of any one of claims 1-10 to produce hydrogen and corresponding products.
18. The method of liquid phase dehydrogenation of an organic liquid hydrogen storage material according to claim 17, wherein the hydrogen storage material comprises at least one of cyclohexane, methylcyclohexane, tetrahydronaphthalene, decalin, perhydroazoethylcarbazole, perhydro phenanthrene, perhydro anthracene, perhydro carbazole, or at least one of its derivatives, and at least one of a component that cuts a section from petroleum or a distillate of petroleum or a material after hydrogenation of the cut component.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105810956A (en) * | 2014-12-31 | 2016-07-27 | 北京有色金属研究总院 | Method for preparing doped graphene or graphene-like compound |
| CN105964274A (en) * | 2016-06-07 | 2016-09-28 | 东南大学 | Precious metal platinum nanometer catalyst and preparation method and application thereof |
| CN106513013A (en) * | 2016-11-14 | 2017-03-22 | 江汉大学 | Preparation method of Pt/graphene oxide/ferric oxide catalyst used for enhancing room temperature catalytic oxidation activity of formaldehyde |
| CN108273504A (en) * | 2018-01-17 | 2018-07-13 | 浙江大学 | A kind of nitrogen-doped graphene load ferrum-based catalyst and its preparation method and application |
| CN109701520A (en) * | 2017-10-26 | 2019-05-03 | 中国石油化工股份有限公司 | High dispersive dehydrogenation, Preparation method and use method |
| CN109701529A (en) * | 2017-10-26 | 2019-05-03 | 中国石油化工股份有限公司 | High dispersive dehydrogenation, preparation method and application method |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016189553A1 (en) * | 2015-05-26 | 2016-12-01 | Council Of Scientific & Industrial Research | Magnetically separable iron-based heterogeneous catalysts for dehydrogenation of alcohols and amines |
-
2019
- 2019-07-16 CN CN201910638290.5A patent/CN112237936B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105810956A (en) * | 2014-12-31 | 2016-07-27 | 北京有色金属研究总院 | Method for preparing doped graphene or graphene-like compound |
| CN105964274A (en) * | 2016-06-07 | 2016-09-28 | 东南大学 | Precious metal platinum nanometer catalyst and preparation method and application thereof |
| CN106513013A (en) * | 2016-11-14 | 2017-03-22 | 江汉大学 | Preparation method of Pt/graphene oxide/ferric oxide catalyst used for enhancing room temperature catalytic oxidation activity of formaldehyde |
| CN109701520A (en) * | 2017-10-26 | 2019-05-03 | 中国石油化工股份有限公司 | High dispersive dehydrogenation, Preparation method and use method |
| CN109701529A (en) * | 2017-10-26 | 2019-05-03 | 中国石油化工股份有限公司 | High dispersive dehydrogenation, preparation method and application method |
| CN108273504A (en) * | 2018-01-17 | 2018-07-13 | 浙江大学 | A kind of nitrogen-doped graphene load ferrum-based catalyst and its preparation method and application |
Non-Patent Citations (1)
| Title |
|---|
| "Fabrication of PteCo NPs supported on nanoporous graphene as high-efficient catalyst for hydrolytic dehydrogenation of ammonia borane";Dandan Ke等;《i n t e r n a t i o n a l journal o f hydrogen energy》;20171231;第42卷;全文 * |
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