CN112705240B - Catalyst carrier, dehydrogenation catalyst and liquid phase dehydrogenation method - Google Patents

Catalyst carrier, dehydrogenation catalyst and liquid phase dehydrogenation method Download PDF

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CN112705240B
CN112705240B CN201911025137.1A CN201911025137A CN112705240B CN 112705240 B CN112705240 B CN 112705240B CN 201911025137 A CN201911025137 A CN 201911025137A CN 112705240 B CN112705240 B CN 112705240B
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catalyst
dehydrogenation
graphite alkyne
solution
dehydrogenation catalyst
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CN112705240A (en
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童凤丫
孙清
王昊
缪长喜
张磊
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/0005—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes
    • C01B3/001—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes characterised by the uptaking medium; Treatment thereof
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    • 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
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Abstract

The present invention provides a catalyst carrier comprising: graphite alkyne and metal oxide auxiliary agent. According to the invention, graphite alkyne and a metal oxide auxiliary agent are used as a catalyst carrier, so that the electronic structure of noble metal loaded on the surface of the catalyst carrier can be obviously improved, and the energy band energy of the noble metal is reduced, so that the noble metal has higher C-H bond breaking activity, and the consumption of the noble metal can be greatly reduced.

Description

Catalyst carrier, dehydrogenation catalyst and liquid phase dehydrogenation method
Technical Field
The invention relates to the field of petrochemical industry, in particular to a catalyst carrier, a dehydrogenation catalyst and a liquid phase dehydrogenation method.
Background
In recent years, the high-speed consumption of fossil resources threatens the energy safety of human society and also causes irreversible harm to the environment, and the human beings are forced to establish a new sustainable new energy system for solving the problems of fossil energy. Among the new energy sources, hydrogen energy is clean, efficient, and high in energy density, and is considered as an ultimate goal for replacing fossil energy sources. Hydrogen energy must be established from development to application to complete hydrogen storage and transportation methods, however, hydrogen has not been commercially applied as a novel energy source with wide prospects so far, and the root cause is that the storage and transportation methods are not solved.
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 its high demands on equipment 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.
TW094147739 provides a method for dehydrogenating liquid fuels in a microchannel catalytic reactor by introducing an organic liquid compound into the microchannel reactor coated with a dehydrogenation catalyst, dehydrogenating the liquid compound under liquid phase conditions to produce dehydrogenated organic liquid and gaseous hydrogen, and separating the two. The dehydrogenation catalysts of the microchannel reactor are prepared by dispersing zirconium, tantalum, rhodium, palladium and platinum, or oxide precursors thereof and mixtures thereof, in finely divided form, in very finely divided form, in nanoparticle form or as framework structures such as platinum black or Raney nickel, or on carbon, alumina, silica, zirconia or other media or high surface area supports.
CN201611061654.0 provides a device for dehydrogenating liquid organic hydride, the device comprises a shell, a liquid distributor, a reaction tube, electromagnetic coils, fluid inlet and outlet connection tubes, etc., the reaction tubes are uniformly arranged in the device, the heat medium flowing in the tubes provides heat for the reaction, the electromagnetic coils are energized coils wound at two ends of each reaction tube in a certain direction, after being energized, the reaction tubes can be magnetized, the catalyst is adsorbed outside the tubes and an organic hydride thin liquid film is formed to perform dehydrogenation reaction, the technology has the advantages that: the electromagnetic coil is powered on and powered off, so that the catalyst is very convenient to fill and replace, and the requirement of continuous production can be met.
The two methods realize liquid phase dehydrogenation of the organic liquid compound, break the limit of reaction balance and improve the reaction efficiency. However, the microchannel reactor used for TW094147739 has the problems of high cost, complex operation, easy blockage, quick catalyst deactivation and the like, and thus, the large-scale industrial application is difficult. The method provided by CN201611061654.0 needs to control the reaction to be switched between a liquid phase and a gas phase, and has the problems of complex design and difficult control.
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 graphite alkyne substrate partially substituted by the modification 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 graphite alkyne, 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 catalyst carrier, a dehydrogenation catalyst, a preparation method thereof and a liquid phase dehydrogenation method. When the catalyst is used for dehydrogenation reaction of the organic liquid hydrogen storage material, carbon-hydrogen bonds can be activated under the liquid phase condition, migration and aggregation of noble metals can be prevented, and the stability of the catalyst can be greatly improved.
In one aspect, the present invention provides a catalyst support comprising: graphite alkyne and metal oxide auxiliary agent.
According to the present invention, the metal oxide auxiliary agent is selected from at least one of group IVB metal oxides and lanthanide series metal oxides.
According to the invention, the metal oxide auxiliary is selected from TiO 2 、ZrO 2 、CeO 2 At least one of them.
According to the invention, the metal oxide auxiliary agentSelected from TiO 2 、ZrO 2 、CeO 2 At least two of them.
According to the invention, the metal oxide auxiliary agent is TiO 2 And ZrO(s) 2 Or TiO 2 And CeO 2 Or TiO 2 、ZrO 2 And CeO 2 Is a mixture of (a) and (b).
The inventor of the application finds that graphite alkyne and a metal oxide auxiliary agent are used as a catalyst carrier, the electronic structure of noble metal loaded on the surface of the catalyst carrier can be obviously improved, and the energy band energy of the noble metal is reduced, so that the noble metal has higher C-H bond breaking activity, and the consumption of the noble metal can be greatly reduced.
In a preferred embodiment of the invention, the graphite alkyne is selected from pure graphite alkynes and/or heteroatom-doped graphite alkynes, the heteroatom being selected from at least one of nitrogen, boron, sulfur and phosphorus.
According to the invention, the pure graphene alkyne is selected from at least one of single-layer graphene, double-layer graphene and multi-wall graphene.
According to the invention, the heteroatom doped graphite alkyne is prepared by treating pure graphite alkyne for 2 to 6 hours in a gas atmosphere containing 5 to 25 percent of heteroatom at a temperature of between 200 and 350 ℃.
According to the invention, by NH 3 Realizing nitrogen doping by BH 3 Realizing boron doping by H 2 S realizes sulfur doping by PH 3 And realizing phosphorus doping.
According to the invention, the heteroatom content in the heteroatom-doped graphite alkyne is 1 to 20 parts by weight based on 100 parts by weight of the total weight of the catalyst.
In a preferred embodiment of the invention, the mass ratio of the graphite alkyne to the metal oxide auxiliary agent is 10:1-1:3.
In a preferred embodiment of the invention, the mass ratio of the graphite alkyne to the metal oxide auxiliary agent is 5:1-1:3.
According to the invention, the mass ratio of the graphite alkyne to the metal oxide auxiliary agent is 4:1-1:2.
In a preferred embodiment of the present invention, the method for preparing a catalyst carrier comprises: and mixing the graphite alkyne and the metal oxide to prepare the catalyst carrier.
According to the invention, the mixing may take place in a manner known to the person skilled in the art, for example mechanical mixing. After the graphite alkyne and the metal oxide are mixed, the electronic structure of the noble metal loaded on the surface of the catalyst carrier can be obviously improved, and the energy band energy of the noble metal is reduced, so that the noble metal has higher C-H bond breaking activity, and the consumption of the noble metal can be greatly reduced.
In another aspect, the present invention provides a dehydrogenation catalyst comprising:
component A: the above-mentioned catalyst carrier; and
component B: at least one group VIII metal.
According to the invention, component B is selected from at least one of the platinum group metals.
According to the invention, component B is selected from Pd and/or Pt.
In a preferred embodiment of the present invention, the content of the component A is 65 to 99 parts by weight; the content of the component B is 0.01-6.5 parts.
According to the invention, the content of the component A is 65-90 parts by weight; the content of the component B is 0.01-3.0 parts.
In another aspect, the present invention provides a method for preparing the above catalyst, comprising:
and (3) carrying out impregnation treatment on the component A by adopting the salt solution of the component B to obtain the catalyst.
According to the invention, the concentration of the salt solution of component B is 16.14-500 mg/L. Preferably, the salt solution of component B is a saturated solution.
In a preferred embodiment of the present invention, the step of impregnating treatment comprises: placing the component A into the salt solution of the component B, standing for 1-4 h at 25-100 ℃, roasting for 2-6 h in an oxygen-free atmosphere, preferably a nitrogen atmosphere at 400-600 ℃, and finally cooling to room temperature.
According to the invention, room temperature is 25℃to 40℃unless otherwise specified.
In yet another aspect, the present invention provides a liquid phase dehydrogenation process comprising contacting an organic liquid hydrogen storage material with the catalyst described above or a catalyst prepared according to the preparation process described above.
According to the invention, the contact is carried out at a reaction pressure of 0MPa to 10MPa, a reaction temperature of 120 ℃ to 300 ℃ and for 0.1h -1 ～10h -1 Occurs at a mass space velocity of (2).
According to the invention, the contact is carried out at a reaction pressure of 2MPa to 8MPa, a reaction temperature of 180 ℃ to 250 ℃ and for 2.0h -1 ～8.0h -1 Occurs at a mass space velocity of (2).
In a preferred embodiment of the present invention, the organic liquid hydrogen storage material is selected from at least one of cyclohexane, methylcyclohexane, tetrahydronaphthalene, decalin, perhydroazoethylcarbazole, perhydro phenanthrene, perhydro anthracene, perhydro carbazole and derivatives thereof, a component which cuts a segment from petroleum or a fraction of petroleum, and a component which cuts a segment from petroleum or a fraction of petroleum after hydrogenation.
According to the present invention, the organic liquid hydrogen storage material is at least one selected from cyclohexane and its derivatives, methylcyclohexane and its derivatives, tetrahydronaphthalene and its derivatives, decalin and its derivatives, perhydroethylcarbazole and its derivatives, perhydro phenanthrene and its derivatives, perhydro anthracene and its derivatives, perhydro carbazole and its derivatives, a component obtained by cutting a segment from petroleum or a fraction of petroleum, and a component obtained by cutting a segment from petroleum or a fraction of petroleum after hydrogenation.
In yet another aspect, the present invention provides a process for the dehydrogenation of light alkanes to light olefins, comprising contacting light alkanes with the above catalyst or a catalyst prepared according to the above process to produce light olefins.
According to the present invention, the lower alkane comprises isobutane and/or butane. The low-carbon olefin comprises isobutene and/or butene.
According to the invention, the contact is carried out at a reaction pressure of 0MPa to 10MPa, 12The reaction temperature is between 0 and 400 ℃ and 0.1h -1 ～8.0h -1 Occurs at a mass space velocity of (2).
According to the invention, isobutene is produced by contacting isobutane with the above-described catalyst or with a catalyst prepared according to the above-described preparation method. Butane is contacted with the catalyst described above or a catalyst prepared according to the above preparation method to produce butene.
The catalyst provided by the invention can obtain higher conversion rate under the condition of extremely small noble metal dosage. Has wide application prospect in the field of preparing low-carbon olefin by liquid phase dehydrogenation of organic liquid hydrogen storage materials and dehydrogenation of low-carbon alkane.
Detailed Description
The present invention will be described in detail with reference to examples, but the scope of the present invention is not limited to the following description.
In the examples described below, the catalysts obtained were tableted, ground to a particle size of 12-20 mesh and 1 gram was evaluated in an isothermal fixed bed reactor.
In the examples below, the catalyst was reduced with hydrogen prior to evaluation, the reduction conditions being as follows: the pressure is normal pressure, the temperature is 450 ℃, the hydrogen flow is 200mL/min, and the reduction time is 4h.
In the following examples, the conditions for evaluating the catalyst were as follows: the reaction pressure is normal pressure, the temperature is 300 ℃ and the airspeed is 2h -1 Methylcyclohexane is used as a representative raw material for the organic liquid hydrogen storage material. Wherein X10 represents the conversion of the starting material at 10h of operation.
Example 1
2g of graphite alkyne are placed in a tubular reactor and introduced with 10% NH 3 The nitrogen gas of (2) is treated at a gas flow rate of 300mL/min, a treatment temperature of 450 ℃ and a treatment time of 12h, and the cooled nitrogen-doped graphite alkyne is obtained.
80 parts of nitrogen-doped graphite alkyne and 10 parts of TiO 2 Mechanically mixed to serve as a catalyst carrier.
Taking 0.1244mL of chloroplatinic acid solution with the concentration of 16.14mg/L, adding 0.378mL of water to prepare a solution, adding 2g of the carrier into the solution, stirring, and standing at room temperature2h, then drying at 120deg.C for 4h, and finally placing it into N 2 Roasting in a muffle furnace in atmosphere at 500 ℃ for 4h to obtain the catalyst.
The catalyst composition is shown in table 1. The preparation conditions and evaluation results of the catalyst are shown in Table 2.
Example 2
2g of graphite alkyne are placed in a tubular reactor and introduced with 10% NH 3 The nitrogen gas of (2) is treated at a gas flow rate of 300mL/min, a treatment temperature of 450 ℃ and a treatment time of 12h, and the cooled nitrogen-doped graphite alkyne is obtained.
80 parts of nitrogen-doped graphite alkyne and 10 parts of TiO 2 Mechanically mixed to serve as a catalyst carrier.
Taking 0.622mL of chloroplatinic acid solution with the concentration of 16.14mg/L, adding 0.378mL of water to prepare a solution, adding 2g of the carrier into the solution, stirring, standing for 2h at room temperature, drying for 4h at 120 ℃, and finally placing the solution into N 2 Roasting in a muffle furnace in atmosphere at 500 ℃ for 4h to obtain the catalyst.
The catalyst composition is shown in table 1. The preparation conditions and test results of the catalyst are shown in Table 2.
Example 3
2g of graphite alkyne are placed in a tubular reactor and introduced with 10% NH 3 The nitrogen gas of (2) is treated at a gas flow rate of 300mL/min, a treatment temperature of 450 ℃ and a treatment time of 12h, and the cooled nitrogen-doped graphite alkyne is obtained.
Taking 80 parts of the nitrogen-doped graphite alkyne and 10 parts of TiO 2 Mechanically mixed to serve as a catalyst carrier.
Taking 0.622mL of chloroplatinic acid solution with the concentration of 32.28mg/L, adding 0.378mL of water to prepare a solution, adding 2g of the carrier into the solution, stirring, standing for 2h at room temperature, drying for 4h at 120 ℃, and finally placing the solution into N 2 Roasting in a muffle furnace in atmosphere at 500 ℃ for 4h to obtain the catalyst.
The catalyst composition is shown in table 1. The preparation conditions and test results of the catalyst are shown in Table 2.
Example 4
2g of graphite alkyne are placed in a tubular reactor and introduced with 10% NH 3 The nitrogen gas of (2) is treated at a gas flow rate of 300mL/min, a treatment temperature of 450 ℃ and a treatment time of 12h, and the cooled nitrogen-doped graphite alkyne is obtained.
Taking 80 parts of the nitrogen-doped graphite alkyne and 10 parts of TiO 2 Mechanically mixed to serve as a catalyst carrier.
Taking 0.622mL of chloroplatinic acid solution with concentration of 161.4mg/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 solution into N 2 Roasting in a muffle furnace in atmosphere at 500 ℃ for 4h to obtain the catalyst.
The catalyst composition is shown in table 1. The preparation conditions and test results of the catalyst are shown in Table 2.
Example 5
2g of graphite alkyne are placed in a tubular reactor and introduced with 10% NH 3 The nitrogen gas of (2) is treated at a gas flow rate of 300mL/min, a treatment temperature of 450 ℃ and a treatment time of 12h, and the cooled nitrogen-doped graphite alkyne is obtained.
Taking 80 parts of the nitrogen-doped graphite alkyne and 10 parts of TiO 2 Mechanically mixed to serve as a catalyst carrier.
Taking 0.622mL of chloroplatinic acid solution with the concentration of 258.24mg/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 adding the carrier into N 2 Roasting in a muffle furnace in atmosphere at 500 ℃ for 4h to obtain the catalyst.
The catalyst composition is shown in table 1. The preparation conditions and test results of the catalyst are shown in Table 2.
Example 6
2g of graphite alkyne are placed in a tubular reactor and introduced with a BH content of 10% 3 The nitrogen gas of (2) is treated, the gas flow rate is 300mL/min, the treatment temperature is 450 ℃, the treatment time is 12h, and the boron-doped graphene is obtained after cooling.
Taking 80 parts of boron doped graphite alkyne and 10 parts of TiO 2 Mechanically mixed to serve as a catalyst carrier.
0.622mL of chloroplatinic acid solution with the concentration of 16.14mg/L is taken, 0.378mL of water is added to prepare a solution,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 500 ℃ for 4h to obtain the catalyst.
The catalyst composition is shown in table 1. The preparation conditions and test results of the catalyst are shown in Table 2.
Example 7
2g of graphite alkyne are placed in a tubular reactor and introduced into a reactor containing 10% H 2 S, treating with nitrogen at a gas flow rate of 300mL/min at a treatment temperature of 450 ℃ for 12 hours, and cooling to obtain the sulfur-doped graphene.
Taking 80 parts of sulfur-doped graphite alkyne and 10 parts of TiO 2 Mechanically mixed to serve as a catalyst carrier.
Taking 0.622mL of chloroplatinic acid solution with the concentration of 16.14mg/L, adding 0.378mL of water to prepare a solution, adding 2g of the carrier into the solution, stirring, standing for 2h at room temperature, drying for 4h at 120 ℃, and finally placing the solution into N 2 Roasting in a muffle furnace in atmosphere at 500 ℃ for 4h to obtain the catalyst.
The catalyst composition is shown in table 1. The preparation conditions and test results of the catalyst are shown in Table 2.
Example 8
2g of graphite alkyne are placed in a tubular reactor and introduced into a reactor containing 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 12h, and the graphene is taken as the phosphorus doped graphene after cooling.
Taking 80 parts of the phosphorus doped graphite alkyne and 10 parts of TiO 2 Mechanically mixed to serve as a catalyst carrier.
Taking 0.622mL of chloroplatinic acid solution with the concentration of 16.14mg/L, adding 0.378mL of water to prepare a solution, adding 2g of the carrier into the solution, stirring, standing for 2h at room temperature, drying for 4h at 120 ℃, and finally placing the solution into N 2 Roasting in a muffle furnace in atmosphere at 500 ℃ for 4h to obtain the catalyst.
The catalyst composition is shown in table 1. The preparation conditions and test results of the catalyst are shown in Table 2.
Example 9
Will 2gGraphite alkyne is placed in a tubular reactor and introduced with 10 percent NH 3 The nitrogen gas of (2) is treated at a gas flow rate of 500mL/min, a treatment temperature of 450 ℃ and a treatment time of 12h, and the cooled nitrogen-doped graphite alkyne is obtained.
Taking 80 parts of the phosphorus doped graphite alkyne and 10 parts of TiO 2 Mechanically mixed to serve as a catalyst carrier.
Taking 0.622mL of chloroplatinic acid solution with the concentration of 16.14mg/L, adding 0.378mL of water to prepare a solution, adding 2g of the carrier into the solution, stirring, standing for 2h at room temperature, drying for 4h at 120 ℃, and finally placing the solution into N 2 Roasting in a muffle furnace in atmosphere at 500 ℃ for 4h to obtain the catalyst.
The catalyst composition is shown in table 1. The preparation conditions and test results of the catalyst are shown in Table 2.
Example 10
2g of graphite alkyne are placed in a tubular reactor and introduced with 10% NH 3 The nitrogen gas of (2) is treated at a gas flow rate of 400mL/min and a treatment temperature of 450 ℃ for 12 hours, and the cooled nitrogen-doped graphite alkyne is obtained.
Taking 80 parts of the nitrogen-doped graphite alkyne and 10 parts of TiO 2 Mechanically mixed to serve as a catalyst carrier.
Taking 0.622mL of chloroplatinic acid solution with the concentration of 16.14mg/L, adding 0.378mL of water to prepare a solution, adding 2g of the carrier into the solution, stirring, standing for 2h at room temperature, drying for 4h at 120 ℃, and finally placing the solution into N 2 Roasting in a muffle furnace in atmosphere at 500 ℃ for 4h to obtain the catalyst.
The catalyst composition is shown in table 1. The preparation conditions and test results of the catalyst are shown in Table 2.
Example 11
2g of graphite alkyne are placed in a tubular reactor and introduced with 10% NH 3 The nitrogen gas of (2) is treated at a gas flow rate of 300mL/min, a treatment temperature of 450 ℃ and a treatment time of 12h, and the cooled nitrogen-doped graphite alkyne is obtained.
Taking 80 parts of the nitrogen-doped graphite alkyne and 10 parts of TiO 2 Mechanically mixed to serve as a catalyst carrier.
The concentration of 0.622mL was taken to be 16.14mg/L chloroplatinic acid solution, 0.378mL of water is added to prepare a solution, 2g of the carrier is added to the solution, the solution is stirred and left at room temperature for 2 hours, then dried at 120 ℃ for 4 hours, and finally the solution is 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. The preparation conditions and test results of the catalyst are shown in Table 2.
Example 12
2g of graphite alkyne are placed in a tubular reactor and introduced with 10% NH 3 The nitrogen gas of (2) is treated at a gas flow rate of 200mL/min, a treatment temperature of 450 ℃ and a treatment time of 12h, and the cooled nitrogen-doped graphite alkyne is obtained.
Taking 80 parts of the nitrogen-doped graphite alkyne and 10 parts of TiO 2 Mechanically mixed to serve as a catalyst carrier.
Taking 0.622mL of chloroplatinic acid solution with the concentration of 16.14mg/L, adding 0.378mL of water to prepare a solution, adding 2g of the carrier into the solution, stirring, standing for 2h at room temperature, drying for 4h at 120 ℃, and finally placing the solution into N 2 Roasting in a muffle furnace in atmosphere at 500 ℃ for 4h to obtain the catalyst.
The catalyst composition is shown in table 1. The preparation conditions and test results of the catalyst are shown in Table 2.
Example 13
2g of graphite alkyne are placed in a tubular reactor and introduced with 10% NH 3 The nitrogen gas of (2) is treated at a gas flow rate of 350mL/min and a treatment temperature of 450 ℃ for 6 hours, and the cooled nitrogen-doped graphite alkyne is obtained.
Taking 70 parts of the nitrogen-doped graphite alkyne and 10 parts of TiO 2 Mechanically mixed to serve as a catalyst carrier.
Taking 0.622mL of chloroplatinic acid solution with the concentration of 16.14mg/L, adding 0.378mL of water to prepare a solution, adding 2g of the carrier into the solution, stirring, standing for 2h at room temperature, drying for 4h at 120 ℃, and finally placing the solution into N 2 Roasting in a muffle furnace in atmosphere at 500 ℃ for 4h to obtain the catalyst.
The catalyst composition is shown in table 1. The preparation conditions and test results of the catalyst are shown in Table 2.
Example 14
2g of graphite alkyne are placed in a tubular reactor and introduced with 10% NH 3 The nitrogen gas of (2) is treated at a gas flow rate of 400mL/min and a treatment temperature of 450 ℃ for 8 hours, and the cooled nitrogen-doped graphite alkyne is obtained.
Taking 80 parts of the nitrogen-doped graphite alkyne and 10 parts of TiO 2 And CeO 2 (TiO) 2 ：CeO 2 Is 1: 1) Mechanically mixed to serve as a catalyst carrier.
Taking 0.622mL of chloroplatinic acid solution with the concentration of 16.14mg/L, adding 0.378mL of water to prepare a solution, adding 2g of the carrier into the solution, stirring, standing for 2h at room temperature, drying for 4h at 120 ℃, and finally placing the solution into N 2 Roasting in a muffle furnace in atmosphere at 500 ℃ for 4h to obtain the catalyst.
The catalyst composition is shown in table 1. The preparation conditions and test results of the catalyst are shown in Table 2.
Example 15
2g of graphite alkyne are placed in a tubular reactor and introduced with 10% NH 3 The nitrogen gas of (2) is treated at a gas flow rate of 430mL/min, a treatment temperature of 450 ℃ and a treatment time of 12h, and the cooled nitrogen-doped graphite alkyne is obtained.
Taking 80 parts of the nitrogen-doped graphite alkyne and 10 parts of TiO 2 And ZrO(s) 2 (TiO) 2 ：ZrO 2 Is 1: 1) Mechanically mixed to serve as a catalyst carrier.
Taking 0.622mL of chloroplatinic acid solution with the concentration of 16.14mg/L, adding 0.378mL of water to prepare a solution, adding 2g of the carrier into the solution, stirring, standing for 2h at room temperature, drying for 4h at 120 ℃, and finally placing the solution into N 2 Roasting in a muffle furnace in atmosphere at 500 ℃ for 4h to obtain the catalyst.
The catalyst composition is shown in table 1. The preparation conditions and test results of the catalyst are shown in Table 2.
Example 16
2g of graphite alkyne are placed in a tubular reactor and introduced with 10% NH 3 Is treated by nitrogen with the gas flow rate of 480mL/min, the treatment temperature of 450 ℃ and the treatment time of 12h, and is taken as nitrogen after coolingDoped with graphite alkyne.
Taking 80 parts of the nitrogen-doped graphite alkyne and 10 parts of TiO 2 And CeO 2 (TiO) 2 ：CeO 2 Is 1: 1) Mechanically mixed to serve as a catalyst carrier.
Taking 0.622mL of chloroplatinic acid solution with the concentration of 16.14mg/L, adding 0.378mL of water to prepare a solution, adding 2g of the carrier into the solution, stirring, standing for 2h at room temperature, drying for 4h at 120 ℃, and finally placing the solution into N 2 Roasting in a muffle furnace in atmosphere at 500 ℃ for 4h to obtain the catalyst.
The catalyst composition is shown in table 1. The preparation conditions and test results of the catalyst are shown in Table 2.
Example 17
2g of double-layer graphite alkyne are placed in a tubular reactor and introduced with 10% NH 3 The nitrogen gas of (2) is treated at a gas flow rate of 300mL/min, a treatment temperature of 450 ℃ and a treatment time of 12h, and the cooled nitrogen-doped graphite alkyne is obtained.
Taking 80 parts of the nitrogen-doped graphite alkyne and 10 parts of TiO 2 And CeO 2 (TiO) 2 ：CeO 2 Is 2: 1) Mechanically mixed to serve as a catalyst carrier.
Taking 0.622mL of chloroplatinic acid solution with the concentration of 16.14mg/L, adding 0.378mL of water to prepare a solution, adding 2g of the carrier into the solution, stirring, standing for 2h at room temperature, drying for 4h at 120 ℃, and finally placing the solution into N 2 Roasting in a muffle furnace in atmosphere at 500 ℃ for 4h to obtain the catalyst.
The catalyst composition is shown in table 1. The preparation conditions and test results of the catalyst are shown in Table 2.
Example 18
2g of graphite alkyne are placed in a tubular reactor and introduced with 15% NH 3 +5％BH 3 The nitrogen gas of (2) is treated at a gas flow rate of 300mL/min, a treatment temperature of 450 ℃ and a treatment time of 12h, and the cooled nitrogen-doped graphite alkyne is obtained.
Taking 80 parts of the nitrogen-doped graphite alkyne and 10 parts of TiO 2 Mechanically mixed to serve as a catalyst carrier.
0.622mL of 16.14mg/L was takenAdding 0.378mL of water into chloroplatinic acid solution 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 adding the carrier into N 2 Roasting in a muffle furnace in atmosphere at 500 ℃ for 4h to obtain the catalyst.
The catalyst composition is shown in table 1. The preparation conditions and test results of the catalyst are shown in Table 2.
Example 19
2g of graphite alkyne are placed in a tubular reactor and introduced with 15% NH 3 +5％H 2 S, treating with nitrogen at a gas flow rate of 300mL/min at a treatment temperature of 450 ℃ for 12 hours, and cooling to obtain the nitrogen-doped graphite alkyne.
Taking 80 parts of the nitrogen-doped graphite alkyne and 10 parts of TiO 2 Mechanically mixed to serve as a catalyst carrier.
Taking 0.622mL of chloroplatinic acid solution with the concentration of 16.14mg/L, adding 0.378mL of water to prepare a solution, adding 2g of the carrier into the solution, stirring, standing for 2h at room temperature, drying for 4h at 120 ℃, and finally placing the solution into N 2 Roasting in a muffle furnace in atmosphere at 500 ℃ for 4h to obtain the catalyst.
The catalyst composition is shown in table 1. The preparation conditions and test results of the catalyst are shown in Table 2.
Example 20
2g of graphite alkyne are placed in a tubular reactor and introduced with 15% NH 3 +5％PH 3 The nitrogen gas of (2) is treated at a gas flow rate of 300mL/min, a treatment temperature of 450 ℃ and a treatment time of 12h, and the cooled nitrogen-doped graphite alkyne is obtained.
Taking 80 parts of the nitrogen-doped graphite alkyne and 10 parts of TiO 2 Mechanically mixed to serve as a catalyst carrier.
Taking 0.622mL of chloroplatinic acid solution with the concentration of 16.14mg/L, adding 0.378mL of water to prepare a solution, adding 2g of the carrier into the solution, stirring, standing for 2h at room temperature, drying for 4h at 120 ℃, and finally placing the solution into N 2 Roasting in a muffle furnace in atmosphere at 500 ℃ for 4h to obtain the catalyst.
The catalyst composition is shown in table 1. The preparation conditions and test results of the catalyst are shown in Table 2.
Example 21
2g of graphite alkyne are placed in a tubular reactor and introduced with 10% NH 3 The nitrogen gas of (2) is treated at a gas flow rate of 300mL/min, a treatment temperature of 450 ℃ and a treatment time of 12h, and the cooled nitrogen-doped graphite alkyne is obtained.
Taking 80 parts of the nitrogen-doped graphite alkyne and 10 parts of TiO 2 Mechanically mixed to serve as a catalyst carrier.
Taking 0.622mL of palladium chloride solution with the concentration of 16.14mg/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 adding the carrier into N 2 Roasting in a muffle furnace in atmosphere at 500 ℃ for 4h to obtain the catalyst.
The catalyst composition is shown in table 1. The preparation conditions and test results of the catalyst are shown in Table 2.
Example 22
2g of graphite alkyne are placed in a tubular reactor and introduced with 10% NH 3 The nitrogen gas of (2) is treated at a gas flow rate of 300mL/min, a treatment temperature of 450 ℃ and a treatment time of 12h, and the cooled nitrogen-doped graphite alkyne is obtained.
Taking 80 parts of the nitrogen-doped graphite alkyne and 10 parts of TiO 2 Mechanically mixed to serve as a catalyst carrier.
Taking 0.622mL of palladium chloride solution with the concentration of 96.84mg/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 adding the carrier into N 2 Roasting in a muffle furnace in atmosphere at 500 ℃ for 4h to obtain the catalyst.
The catalyst composition is shown in table 1. The preparation conditions and test results of the catalyst are shown in Table 2.
Example 23
2g of nitrogen-doped graphite alkyne are placed in a tubular reactor and introduced into a reactor containing 15% H 2 S+5％BH 3 The nitrogen gas of (2) is treated, the gas flow rate is 300mL/min, the treatment temperature is 450 ℃, the treatment time is 12h, and the sulfur-boron doped graphite alkyne is obtained after cooling.
Taking 80 parts of the sulfur-boron doped stoneInk alkyne and 10 parts of TiO 2 Mechanically mixed to serve as a catalyst carrier.
Taking 0.622mL of chloroplatinic acid solution with the concentration of 16.14mg/L, adding 0.378mL of water to prepare a solution, adding 2g of the carrier into the solution, stirring, standing for 2h at room temperature, drying for 4h at 120 ℃, and finally placing the solution into N 2 Roasting in a muffle furnace in atmosphere at 500 ℃ for 4h to obtain the catalyst.
The catalyst composition is shown in table 1. The preparation conditions and test results of the catalyst are shown in Table 2.
Example 24
2g of graphite alkyne are placed in a tubular reactor and introduced into a reactor containing 15% H 2 S+5％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 12h, and the cooled sulfur-phosphorus doped graphite alkyne is obtained.
Taking 80 parts of the sulfur-phosphorus doped graphite alkyne and 10 parts of TiO 2 Mechanically mixed to serve as a catalyst carrier.
Taking 0.622mL of chloroplatinic acid solution with the concentration of 16.14mg/L, adding 0.378mL of water to prepare a solution, adding 2g of the carrier into the solution, stirring, standing for 2h at room temperature, drying for 4h at 120 ℃, and finally placing the solution into N 2 Roasting in a muffle furnace in atmosphere at 500 ℃ for 4h to obtain the catalyst.
The catalyst composition is shown in table 1. The preparation conditions and test results of the catalyst are shown in Table 2.
Example 25
2g of graphite alkyne are placed in a tubular reactor and introduced with a BH content of 15% 3 +5％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 12h, and the boron-phosphorus doped graphite alkyne is obtained after cooling.
Taking 80 parts of boron-phosphorus doped graphite alkyne and 10 parts of TiO 2 Mechanically mixed to serve as a catalyst carrier.
Taking 0.622mL of chloroplatinic acid solution with the concentration of 16.14mg/L, adding 0.378mL of water to prepare a solution, adding 2g of the carrier into the solution, stirring, standing for 2h at room temperature, drying for 4h at 120 ℃, and finally placing the solution into N 2 In a muffle furnace of atmosphereRoasting for 4 hours at 500 ℃ to obtain the catalyst.
The catalyst composition is shown in table 1. The preparation conditions and test results of the catalyst are shown in Table 2.
Example 26
2g of graphite alkyne are placed in a tubular reactor and introduced with 10% NH 3 The nitrogen gas of (2) is treated at a gas flow rate of 300mL/min, a treatment temperature of 450 ℃ and a treatment time of 12h, and the cooled nitrogen-doped graphite alkyne is obtained.
Taking 80 parts of the nitrogen-doped graphite alkyne and 10 parts of TiO 2 Mechanically mixed to serve as a catalyst carrier.
Taking 0.622mL of chloroplatinic acid solution with the concentration of 16.14mg/L, adding 0.378mL of water to prepare a solution, adding 2g of the carrier into the solution, stirring, standing for 2h at room temperature, drying for 4h at 120 ℃, and finally placing the solution into N 2 Roasting in a muffle furnace in atmosphere at 500 ℃ for 4h to obtain the catalyst.
The catalyst composition is shown in table 1. The preparation conditions and test results of the catalyst are shown in Table 2.
Example 27
2g of graphite alkyne are placed in a tubular reactor and introduced with 10% NH 3 The nitrogen gas of (2) is treated at a gas flow rate of 300mL/min, a treatment temperature of 450 ℃ and a treatment time of 12h, and the cooled nitrogen-doped graphite alkyne is obtained.
Taking 80 parts of the nitrogen-doped graphite alkyne and 10 parts of TiO 2 Mechanically mixed to serve as a catalyst carrier.
Taking 0.622mL of chloroplatinic acid solution with the concentration of 16.14mg/L, adding 0.378mL of water to prepare a solution, adding 2g of the carrier into the solution, stirring, standing for 2h at room temperature, drying for 4h at 120 ℃, and finally placing the solution into N 2 Roasting in a muffle furnace in atmosphere at 500 ℃ for 4h to obtain the catalyst.
The catalyst composition is shown in table 1. The preparation conditions and test results of the catalyst are shown in Table 2.
Example 28
2g of double-layer graphite alkyne are placed in a tubular reactor and introduced with 15% H 2 S+5％BH 3 Is treated by nitrogen with the gas flow rate of 300mL/minThe temperature is 450 ℃, the treatment time is 12 hours, and the product is taken as the sulfur-boron doped graphite alkyne after cooling.
Taking 80 parts of the sulfur-boron doped graphite alkyne and 10 parts of TiO 2 Mechanically mixed to serve as a catalyst carrier.
Taking 0.622mL of chloroplatinic acid solution with the concentration of 16.14mg/L, adding 0.378mL of water to prepare a solution, adding 2g of the carrier into the solution, stirring, standing for 2h at room temperature, drying for 4h at 120 ℃, and finally placing the solution into N 2 Roasting in a muffle furnace in atmosphere at 500 ℃ for 4h to obtain the catalyst.
The catalyst composition is shown in table 1. The preparation conditions and test results of the catalyst are shown in Table 2.
Example 29
2g of double-layer graphite alkyne are placed in a tubular reactor and introduced with 15% H 2 S+5％BH 3 The nitrogen gas of (2) is treated, the gas flow rate is 300mL/min, the treatment temperature is 450 ℃, the treatment time is 12h, and the sulfur-boron doped graphite alkyne is obtained after cooling.
Taking 80 parts of the sulfur-boron doped graphite alkyne and 10 parts of TiO 2 Mechanically mixed to serve as a catalyst carrier.
0.4976mL of a chloroplatinic acid solution with the concentration of 16.14mg/L and 0.1244mL of a palladium chloride solution with the concentration of 16.14mg/L are taken, 0.378mL of water is added to prepare a solution, 2g of the carrier is added to the solution, stirring and standing at room temperature for 2h, then drying is carried out at 120 ℃ for 4h, and finally the solution is put into N 2 Roasting in a muffle furnace in atmosphere at 500 ℃ for 4h to obtain the catalyst.
The catalyst composition is shown in table 1. The preparation conditions and test results of the catalyst are shown in Table 2.
Example 30
2g of a multi-wall graphite alkyne mixture are placed in a tubular reactor and introduced with 15% H 2 S+5％BH 3 The nitrogen gas of (2) is treated, the gas flow rate is 300mL/min, the treatment temperature is 450 ℃, the treatment time is 12h, and the sulfur-boron doped graphite alkyne is obtained after cooling.
Taking 80 parts of the sulfur-boron doped graphite alkyne and 10 parts of TiO 2 Mechanically mixed to serve as a catalyst carrier.
Taking the concentration of 0.1244mL as16.14mg/L of chloroplatinic acid solution and 0.4976mL of palladium chloride solution with the concentration of 16.14mg/L are added with 0.378mL of water to prepare a solution, 2g of the carrier is added into the solution, the mixture is stirred and left at room temperature for 2h, then the mixture is dried for 4h at 120 ℃, and finally the mixture is put into N 2 Roasting in a muffle furnace in atmosphere at 500 ℃ for 4h to obtain the catalyst.
The catalyst composition is shown in table 1. The preparation conditions and test results of the catalyst are shown in Table 2.
Comparative example 1
0.622mL of chloroplatinic acid solution with the concentration of 16.14mg/L is taken, 1.378mL of water is added to prepare a solution, 2g of nitrogen doped graphite alkyne is added into the solution, the solution is stirred, the solution is placed at room temperature for 2 hours, then the solution is placed into a vacuum drying oven, dried for 4 hours under the pressure of 0MPa at 100 ℃, and then the sample is placed into a muffle furnace to be roasted for 4 hours under the nitrogen atmosphere at 550 ℃ to obtain the required catalyst.
The catalyst composition is shown in table 1. The preparation conditions and test results of the catalyst are shown in Table 2.
Comparative example 2
0.622mL of chloroplatinic acid solution with the concentration of 16.14mg/L is taken, 1.378mL of water is added to prepare a solution, 2g double-layer graphite alkyne is added into the solution, the solution is stirred, the solution is placed at room temperature for 2 hours, then the solution is placed into a vacuum drying oven, dried for 4 hours under the pressure of 0MPa at 100 ℃, and then the sample is placed into a muffle furnace to be roasted for 4 hours under the nitrogen atmosphere at 550 ℃ to obtain the required catalyst.
The catalyst composition is shown in table 1. The preparation conditions and test results of the catalyst are shown in Table 2.
Comparative example 3
0.4976mL of a chloroplatinic acid solution with the concentration of 16.14mg/L and 0.1244mL of a palladium chloride solution with the concentration of 16.14mg/L are taken, 0.378mL of water is added to prepare a solution, 2g of nitrogen-doped graphite alkyne is added to the solution, the solution is stirred and placed at room temperature for 2 hours, then the solution is placed in a vacuum drying oven, dried for 4 hours at the temperature of 100 ℃ and the pressure of 0MPa, and then the sample is placed in a muffle furnace and baked for 4 hours in a nitrogen atmosphere at the temperature of 550 ℃ to obtain the required catalyst.
The catalyst composition is shown in table 1. The preparation conditions and test results of the catalyst are shown in Table 2.
Comparative example 4
0.622mL of chloroplatinic acid solution with the concentration of 16.14mg/L is taken, 1.378mL of water is added to prepare a solution, and 2g of TiO is added 2 Adding the catalyst into the solution, stirring, standing at room temperature for 2 hours, then placing into a vacuum drying oven, drying for 4 hours at 100 ℃ and 0MPa, and placing the sample into a muffle furnace for roasting for 4 hours under the nitrogen atmosphere at 550 ℃ to obtain the required catalyst.
The catalyst composition is shown in table 1. The preparation conditions and test results of the catalyst are shown in Table 2.
TABLE 1
Figure BDA0002248403490000171
Table 1 continuous table
Figure BDA0002248403490000181
Note that: the parts of graphite alkyne in table 1 refer to parts of pure graphite alkyne.
TABLE 2
Figure BDA0002248403490000191
Table 2 continuous table
Figure BDA0002248403490000201
Note that: x10 is the conversion of the starting material at 10h of operation.
The roasting atmosphere is nitrogen.
From the data in Table 2, it can be seen that the present invention can achieve higher conversion.
Examples 31 to 35
The catalyst prepared in example 30 was used for performance evaluation of low-carbon olefin production by low-carbon hydrocarbon dehydrogenation, and the results are shown in Table 3.
Wherein the major product of example 31 is isobutylene. The main product of example 32 is butene. The main product of example 33 is butene. The main product of example 34 is butene. The main product of example 35 is butene.
TABLE 3 Table 3
Figure BDA0002248403490000211
Note that: x10 is the conversion of the starting material at 10h of operation
From the data in table 3, the catalyst of the present invention shows higher conversion when used in the dehydrogenation of light alkanes to light olefins.
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
Figure BDA0002248403490000221
Note that: x1 is the conversion of the starting material in 1h of operation
From the data in table 4, the catalysts of the present invention exhibit higher conversions when used in the dehydrogenation of organic liquid hydrogen storage materials.
It should be noted that the above-described embodiments are only for explaining the present invention and do not constitute any limitation of the present invention. The invention has been described with reference to exemplary embodiments, but it is understood that the words which have been used are words of description and illustration, rather than words of limitation. Modifications may be made to the invention as defined in the appended claims, and the invention may be modified without departing from the scope and spirit of the invention. Although the invention is described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, as the invention extends to all other means and applications which perform the same function.

Claims (20)

1. A dehydrogenation catalyst comprising:
component A: a catalyst carrier; and
component B: at least one group VIII metal; the catalyst carrier comprises: graphite alkyne and a metal oxide auxiliary agent, wherein the metal oxide auxiliary agent is selected from at least one of IVB metal oxide and lanthanide metal oxide; the graphite alkyne is selected from heteroatom doped graphite alkynes, and the heteroatom is selected from at least one of nitrogen, boron, sulfur and phosphorus.
2. The dehydrogenation catalyst of claim 1, wherein the metal oxide promoter is selected from the group consisting of TiO 2 、ZrO 2 、CeO 2 At least one of them.
3. The dehydrogenation catalyst of claim 2, wherein the metal oxide promoter is selected from the group consisting of TiO 2 、ZrO 2 、CeO 2 At least two of them.
4. A dehydrogenation catalyst according to any of claims 1-3, characterized in that the heteroatom doped graphite alkyne is prepared by treating a pure graphite alkyne in a 5% -25% heteroatom containing gas atmosphere at a temperature of 200 ℃ -350 ℃ for 2h-6 h.
5. A dehydrogenation catalyst according to any of claims 1-3, characterized in that the mass ratio of the graphite alkyne to the metal oxide promoter is 10:1-1:3.
6. The dehydrogenation catalyst of claim 5, wherein the mass ratio of the graphite alkyne to the metal oxide promoter is from 5:1 to 1:3.
7. The dehydrogenation catalyst of claim 6, wherein the mass ratio of the graphite alkyne to the metal oxide promoter is from 4:1 to 1:2.
8. A dehydrogenation catalyst according to any one of claims 1-3, prepared by a process comprising: and mixing the graphite alkyne and the metal oxide to prepare the catalyst carrier.
9. A dehydrogenation catalyst according to any of claims 1-3, characterized in that component B is Pd and/or Pt.
10. The dehydrogenation catalyst according to claim 9, characterized in that the catalyst comprises, in parts by weight,
the content of the component A is 65-99 parts;
the content of the component B is 0.01-6.5 parts.
11. The dehydrogenation catalyst of claim 10, wherein the catalyst comprises, in parts by weight,
the content of the component A is 65-90 parts;
the content of the component B is 0.01-3.0 parts.
12. A method of preparing the dehydrogenation catalyst of any of claims 1-11, comprising:
and (3) carrying out impregnation treatment on the component A by adopting the salt solution of the component B to prepare the dehydrogenation catalyst.
13. The method for producing a dehydrogenation catalyst according to claim 12, characterized in that the step of impregnating comprises: placing the component A into the salt solution of the component B, standing for 1-4 h at 25-100 ℃, roasting for 2-6 h in an oxygen-free atmosphere at 400-600 ℃, and finally cooling to room temperature.
14. The method for producing a dehydrogenation catalyst according to claim 13, wherein the oxygen-free atmosphere is a nitrogen atmosphere.
15. A liquid phase dehydrogenation process comprising contacting an organic liquid hydrogen storage material with the dehydrogenation catalyst of any one of claims 1-11 or the dehydrogenation catalyst prepared according to the preparation process of any one of claims 12-14.
16. The liquid phase dehydrogenation process according to claim 15, wherein the contacting is at a reaction pressure of 0MPa to 10MPa, a reaction temperature of 120 ℃ to 300 ℃ and for 0.1h -1 -10h -1 Occurs at a mass space velocity of (2).
17. The liquid phase dehydrogenation process according to claim 15, wherein the organic liquid hydrogen storage material is at least one selected from cyclohexane, methylcyclohexane, tetrahydronaphthalene, decalin, perhydroazoethylcarbazole, perhydro phenanthrene, perhydro anthracene, perhydro carbazole and derivatives thereof, a component obtained by cutting a section from petroleum or a fraction of petroleum, and a component obtained by hydrogenating a component obtained by cutting a section from petroleum or a fraction of petroleum.
18. A process for the dehydrogenation of a lower alkane to produce a lower alkene comprising contacting a lower alkane with the dehydrogenation catalyst of any one of claims 1 to 11 or the dehydrogenation catalyst produced according to the production process of any one of claims 12 to 14 to produce a lower alkene.
19. The method for preparing low-carbon olefin by dehydrogenation of low-carbon alkane according to claim 18, wherein the low-carbon alkane comprises isobutane and/or butane, and the low-carbon olefin comprises isobutene and/or butene.
20. The process for preparing a lower olefin by dehydrogenating a lower alkane according to claim 18, wherein the contacting is carried out at a reaction pressure of 0MPa to 10MPa, a reaction temperature of 120 ℃ to 400 ℃ and for 0.1h -1 -8.0h -1 Occurs at a mass space velocity of (2).
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