CN112705240A - 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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CN112705240A
CN112705240A CN201911025137.1A CN201911025137A CN112705240A CN 112705240 A CN112705240 A CN 112705240A CN 201911025137 A CN201911025137 A CN 201911025137A CN 112705240 A CN112705240 A CN 112705240A
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catalyst
parts
nitrogen
solution
component
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CN112705240B (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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    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
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    • 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: graphdine and a metal oxide adjuvant. The method takes the graphite alkyne and the metal oxide auxiliary agent as the catalyst carrier, can obviously improve the electronic structure of the noble metal loaded on the surface of the catalyst carrier, and reduces the energy band energy of the noble metal, so that the noble metal has higher C-H bond fracture activity, and the dosage 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 causes irreversible harm to the environment, which all compels people to establish a new sustainable new energy system for solving the problems of fossil energy. Among many new energy sources, hydrogen energy is clean, efficient, and has high energy density, and is considered as a final target for replacing fossil energy. From development to application of hydrogen energy, a perfect hydrogen storage and transportation method must be established, however, hydrogen has not been commercialized as a novel energy source with a wide prospect so far, and the fundamental reason is that the storage and transportation method is not solved.
At present, the hydrogen storage technology mainly comprises physical hydrogen storage, adsorption hydrogen storage and chemical hydrogen storage. Physical hydrogen storage technology has met the requirements of vehicles, but its high requirements on equipment and harsh operating conditions have made the contradiction between performance and efficiency of this technology increasingly prominent. Adsorption hydrogen storage and chemical hydrogen storage are the key points of the current research, and certain research results are obtained, but certain differences exist between the technical requirements of vehicle-mounted hydrogen storage. The organic liquid hydrogen storage technology (organic liquid mainly includes methyl cyclohexane, tetrahydronaphthalene, decahydronaphthalene, perhydro-azoethylcarbazole, perhydro-carbazole, etc.) in chemical hydrogen storage is characterized by that it utilizes catalytic addition and dehydrogenation reversible reaction to implement storage of hydrogen energy, said process is reversible, and the reactant product isThe product can be recycled, and has relatively high hydrogen storage capacity (about 60-75kg H)2/m3The mass fraction is 6-8 percent), meets the indexes specified by the International energy agency and the United states department of energy (DOE), is transported for a long distance in the form of organic liquid or can solve the problem of uneven distribution of energy in areas, really meets the requirement of green chemistry and has stronger application prospect.
The hydrogenation process and the dehydrogenation process exist simultaneously in the organic liquid hydrogen storage technology, the hydrogenation process is relatively simple, the technology is mature, and the dehydrogenation process is a reaction with strong heat absorption and volume increase, so that the dehydrogenation reaction is facilitated at high temperature from the aspects of dynamics and thermodynamics, but side reactions such as cracking, carbon deposition and the like are easy to occur at high temperature, and the activity of the catalyst is reduced and even inactivated. The conventional dehydrogenation reaction is carried out under a gas phase condition, and is generally carried out at a high temperature in order to improve the reaction conversion rate, or a membrane reactor is adopted to promote the reaction balance, which causes high operation cost, large equipment investment, difficult maintenance and difficulty in large-scale application. If the reaction is carried out in a liquid phase, hydrogen generated by the reaction overflows in a gas form, the reaction balance problem does not exist, the reaction temperature can be greatly reduced, a membrane reactor is not required, and the method has many advantages compared with a gas phase reaction.
TW094147739 provides a method for dehydrogenation of liquid fuel in a microchannel catalytic reactor, introducing an organic liquid compound into a microchannel reactor coated with a dehydrogenation catalyst, performing dehydrogenation under liquid phase conditions to produce dehydrogenated organic liquid and gaseous hydrogen, and then separating the two. The dehydrogenation catalysts for microchannel reactors are prepared from zirconium, tantalum, rhodium, palladium and platinum, or their oxide precursors and mixtures thereof in finely divided form, in the form of very fine powders, in the form of nanoparticles or as a framework structure such as platinum black or Raney nickel, or in a form dispersed on carbon, alumina, silica, zirconia or other media or high surface area supports.
CN201611061654.0 provides a device for dehydrogenating liquid organic hydride, which comprises a casing, a liquid distributor, reaction tubes, electromagnetic coils, and fluid inlet and outlet connection tubes, wherein the reaction tubes are uniformly arranged in the device, heat medium is circulated in the tubes to provide heat for reaction, the electromagnetic coils are electrified coils wound on two ends of each reaction tube in a certain direction, after being electrified, the reaction tubes can be magnetized, and catalyst is adsorbed outside the tubes to form an organic hydride thin liquid film for dehydrogenation reaction, and the device has the advantages that: the catalyst is very convenient to fill and replace by electrifying and cutting off the electromagnetic coil, and the requirement of continuous production can be met.
The two methods realize liquid phase dehydrogenation of the organic liquid compound, break the limitation of reaction balance and improve reaction efficiency. However, the microchannel reactor used in TW094147739 has the problems of high cost, complicated operation, easy blockage, rapid catalyst deactivation, etc., which makes large-scale industrial application difficult. The method provided by CN201611061654.0 needs to control the reaction to switch between liquid phase and gas phase, and has the problems of complicated design and difficult control.
The key problem to be solved in the liquid phase reaction is to find a catalyst which can activate the hydrogen-containing compound at a lower temperature and has higher stability. The noble metal and the graphite alkyne substrate partially substituted by the modification element have very strong interaction, and have very good carbon-hydrogen bond activation performance, and more importantly, the interaction enables the noble metal to be anchored on the surface of the graphite alkyne, prevents the noble metal from migrating and aggregating, and has stronger effect of improving the stability of the catalyst. In accordance with this concept, the present patent provides a high stability liquid phase dehydrogenation catalyst.
Disclosure of Invention
The invention aims to solve the technical problems of high reaction temperature, quick catalyst inactivation, high operation cost caused by 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, the carbon-hydrogen bond can be activated under the liquid phase condition, the migration and aggregation of noble metal can be prevented, and the stability of the catalyst can be greatly improved.
In one aspect, the present invention provides a catalyst carrier comprising: graphdine and a metal oxide adjuvant.
According to the present invention, the metal oxide promoter is selected from at least one of group IVB metal oxides and lanthanide metal oxides.
According to the invention, the metal oxide auxiliary is chosen from TiO2、ZrO2、CeO2At least one of (1).
According to the invention, the metal oxide auxiliary is chosen from TiO2、ZrO2、CeO2At least two of them.
According to the invention, the metal oxide auxiliary agent is TiO2And ZrO2Or TiO mixtures of2And CeO2Or TiO mixtures of2、ZrO2And CeO2A mixture of (a).
The inventor of the application finds that 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 can be reduced by taking the graphite alkyne and the metal oxide auxiliary agent as the catalyst carrier, so that the noble metal has higher C-H bond fracture activity and the dosage of the noble metal can be greatly reduced.
In a preferred embodiment of the invention, the grapliine is selected from pure grapliine and/or heteroatom-doped grapliine, the heteroatom being selected from at least one of nitrogen, boron, sulfur and phosphorus.
According to the invention, the pure graphdiyne is selected from at least one of single-layer graphene, double-layer graphene and multi-wall graphene.
According to the invention, the heteroatom-doped graphdine is prepared by treating pure graphdine for 2 to 6 hours at a temperature of 200 to 350 ℃ in an atmosphere of 5 to 25% of gas containing heteroatoms.
According to the invention, by NH3Effecting nitrogen doping by BH3Effecting boron doping by H2S Sulfur doping by PH3And realizing phosphorus doping.
According to the invention, the content of the heteroatom in the heteroatom-doped graphdine is 1-20 parts by weight based on 100 parts by weight of the total weight of the catalyst.
In a preferred embodiment of the present invention, the mass ratio of the graphyne to the metal oxide auxiliary is 10:1 to 1: 3.
In a preferred embodiment of the present invention, the mass ratio of the graphyne to the metal oxide auxiliary is 5:1 to 1: 3.
According to the invention, the mass ratio of the graphdiyne to the metal oxide auxiliary agent is 4: 1-1: 2.
In a preferred embodiment of the present invention, a method for preparing a catalyst support comprises: mixing the graphdiyne and the metal oxide to prepare the catalyst carrier.
According to the invention, the mixing can be carried out 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 fracture activity, and the using amount of the noble metal can be greatly reduced.
In another aspect, the present invention provides a dehydrogenation catalyst comprising:
and (2) component A: the above-mentioned catalyst carrier; and
and (B) component: 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 invention, the content of the component A is 65-99 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 of the present invention, a method for preparing the catalyst comprises:
and (3) carrying out impregnation treatment on the component A by adopting the salt solution of the component B to prepare the catalyst.
According to the invention, the concentration of the salt solution of the 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 the impregnation treatment comprises: placing the component A in the salt solution of the component B, standing for 1-4 h at 25-100 ℃, then roasting for 2-6 h in an oxygen-free atmosphere at 400-600 ℃, preferably a nitrogen atmosphere, and finally cooling to room temperature.
According to the invention, room temperature means 25 ℃ to 40 ℃ unless otherwise specified.
In a further aspect, the present invention provides a liquid phase dehydrogenation process comprising contacting an organic liquid hydrogen storage material with the above catalyst or a catalyst prepared according to the above preparation process.
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 0.1h-1～10h-1Occurs at a mass space velocity of (c).
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 a reaction time of 2.0h-1～8.0h-1Occurs at a mass space velocity of (c).
In a preferred embodiment of the present invention, the organic liquid hydrogen storage material is selected from at least one of cyclohexane, methylcyclohexane, tetrahydronaphthalene, decahydronaphthalene, perhydroazeethylcarbazole, perhydrophenanthrene, perhydroanthracene, perhydrocarbazole and their derivatives, a component cut from petroleum or a distillate of petroleum after hydrogenation of the component cut from petroleum or a distillate of petroleum.
According to the present invention, the organic liquid hydrogen storage material is selected from at least one of cyclohexane and its derivatives, methylcyclohexane and its derivatives, tetrahydronaphthalene and its derivatives, decahydronaphthalene and its derivatives, perhydroazeethylcarbazole and its derivatives, perhydrophenanthrene and its derivatives, perhydroanthracene and its derivatives, perhydrocarbazole and its derivatives, a component cut from petroleum or a fraction of petroleum, and a component cut from petroleum or a fraction of petroleum after hydrogenation.
In another aspect, the present invention provides a method for preparing light olefins by dehydrogenation of light alkanes, comprising contacting light alkanes with the catalyst or the catalyst prepared by the above preparation method to generate light olefins.
According to the invention, the lower alkane comprises isobutane and/or butane. The lower olefins include isobutene and/or butenes.
According to the invention, the contact is carried out at a reaction pressure of 0MPa to 10MPa, a reaction temperature of 120 ℃ to 400 ℃ and 0.1h-1～8.0h-1Occurs at a mass space velocity of (c).
According to the present invention, isobutane is contacted with the above-mentioned catalyst or the catalyst prepared according to the above-mentioned preparation method to produce isobutene. Butane is contacted with the above catalyst or the 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 consumption of noble metal. Has wide application prospect in the fields of organic liquid hydrogen storage material liquid phase dehydrogenation and low carbon alkane dehydrogenation for preparing low carbon olefin.
Detailed Description
The present invention will be described in detail below with reference to examples, but the scope of the present invention is not limited to the following description.
In the following examples, the obtained catalyst was pelletized, ground into a particle size of 12 to 20 mesh, and 1 g was evaluated in an isothermal fixed bed reactor.
In the following examples, the catalyst was reduced with hydrogen before evaluation, under the following conditions: the pressure and the pressure are normal pressure, the temperature is 450 ℃, the hydrogen flow is 200mL/min, and the reduction time is 4 h.
In the following examples, the conditions under which the catalyst was evaluated were as follows: the reaction pressure is normal pressure, the temperature is 300 ℃, and the space velocity is 2h-1Methylcyclohexane is used as a representative raw material of the organic liquid hydrogen storage material. Wherein X10 represents the conversion of the feedstock over 10h of run.
Example 1
2g of graphdiyne are placed in a tubular reactor and 10% NH is introduced3The nitrogen is treated, the gas flow rate is 300mL/min, the treatment temperature is 450 ℃, the treatment time is 12h, and the nitrogen-doped graphite alkyne is obtained after cooling.
80 parts of nitrogen-doped graphdiyne and 10 parts of TiO2Mechanically mixed to act as a catalyst support.
Adding 0.378mL of water into 0.1244mL of chloroplatinic acid solution with concentration of 16.14mg/L to obtain solution, adding 2g of the above carrier into the solution, stirring, standing at room temperature for 2h, drying at 120 deg.C for 4h, and adding N2And roasting the mixture for 4 hours at 500 ℃ in an atmosphere muffle furnace to obtain the catalyst.
The catalyst composition is shown in table 1. The catalyst preparation conditions and the evaluation results are shown in table 2.
Example 2
2g of graphdiyne are placed in a tubular reactor and 10% NH is introduced3The nitrogen is treated, the gas flow rate is 300mL/min, the treatment temperature is 450 ℃, the treatment time is 12h, and the nitrogen-doped graphite alkyne is obtained after cooling.
80 parts of nitrogen-doped graphdiyne and 10 parts of TiO2Mechanically mixed to act as a catalyst support.
Adding 0.622mL of chloroplatinic acid solution with concentration of 16.14mg/L into 0.378mL of water to obtain solution, adding 2g of the above carrier into the solution, stirring, standing at room temperature for 2h, drying at 120 deg.C for 4h, and adding N2And roasting the mixture for 4 hours at 500 ℃ in an atmosphere muffle furnace to obtain the catalyst.
The catalyst composition is shown in table 1. The catalyst preparation conditions and test results are shown in table 2.
Example 3
2g of graphdiyne are placed in a tubular reactor and 10% NH is introduced3The nitrogen is treated, the gas flow rate is 300mL/min, the treatment temperature is 450 ℃, the treatment time is 12h, and the nitrogen-doped graphite alkyne is obtained after cooling.
Taking 80 parts of nitrogen-doped graphdiyne and 10 parts of TiO2Mechanically mixed to act as a catalyst support.
0.622mL of chloroplatinic acid solution with the concentration of 32.28mg/L is taken and added with 0.378mL of water to prepare solution,adding 2g of the above carrier into the solution, stirring, standing at room temperature for 2h, drying at 120 deg.C for 4h, and adding N2And roasting the mixture for 4 hours at 500 ℃ in an atmosphere muffle furnace to obtain the catalyst.
The catalyst composition is shown in table 1. The catalyst preparation conditions and test results are shown in table 2.
Example 4
2g of graphdiyne are placed in a tubular reactor and 10% NH is introduced3The nitrogen is treated, the gas flow rate is 300mL/min, the treatment temperature is 450 ℃, the treatment time is 12h, and the nitrogen-doped graphite alkyne is obtained after cooling.
Taking 80 parts of nitrogen-doped graphdiyne and 10 parts of TiO2Mechanically mixed to act as a catalyst support.
Adding 0.622mL of 161.4mg/L chloroplatinic acid solution into 0.378mL of water to obtain a solution, adding 2g of the above carrier into the solution, stirring, standing at room temperature for 2h, drying at 120 deg.C for 4h, and adding N2And roasting the mixture for 4 hours at 500 ℃ in an atmosphere muffle furnace to obtain the catalyst.
The catalyst composition is shown in table 1. The catalyst preparation conditions and test results are shown in table 2.
Example 5
2g of graphdiyne are placed in a tubular reactor and 10% NH is introduced3The nitrogen is treated, the gas flow rate is 300mL/min, the treatment temperature is 450 ℃, the treatment time is 12h, and the nitrogen-doped graphite alkyne is obtained after cooling.
Taking 80 parts of nitrogen-doped graphdiyne and 10 parts of TiO2Mechanically mixed to act as a catalyst support.
Adding 0.622mL chloroplatinic acid solution with concentration of 258.24mg/L into 0.378mL water to obtain solution, adding 2g above carrier into the solution, stirring, standing at room temperature for 2 hr, drying at 120 deg.C for 4 hr, and adding N2And roasting the mixture for 4 hours at 500 ℃ in an atmosphere muffle furnace to obtain the catalyst.
The catalyst composition is shown in table 1. The catalyst preparation conditions and test results are shown in table 2.
Example 6
Will 2g of graphdiyne is placed in a tubular reactor and 10% BH is introduced3The nitrogen is treated, the gas flow rate is 300mL/min, the treatment temperature is 450 ℃, the treatment time is 12 hours, and the boron-doped graphene is obtained after cooling.
Mixing 80 parts of boron-doped graphyne and 10 parts of TiO2Mechanically mixed to act as a catalyst support.
Adding 0.622mL of chloroplatinic acid solution with concentration of 16.14mg/L into 0.378mL of water to obtain solution, adding 2g of the above carrier into the solution, stirring, standing at room temperature for 2h, drying at 120 deg.C for 4h, and adding N2And roasting the mixture for 4 hours at 500 ℃ in an atmosphere muffle furnace to obtain the catalyst.
The catalyst composition is shown in table 1. The catalyst preparation conditions and test results are shown in table 2.
Example 7
2g of graphdiyne are placed in a tubular reactor and 10% H are introduced2And (3) treating the S with nitrogen, wherein the gas flow rate is 300mL/min, the treatment temperature is 450 ℃, the treatment time is 12h, and the S is cooled to be used as sulfur-doped graphene.
Mixing 80 parts of sulfur-doped graphdiyne and 10 parts of TiO2Mechanically mixed to act as a catalyst support.
Adding 0.622mL of chloroplatinic acid solution with concentration of 16.14mg/L into 0.378mL of water to obtain solution, adding 2g of the above carrier into the solution, stirring, standing at room temperature for 2h, drying at 120 deg.C for 4h, and adding N2And roasting the mixture for 4 hours at 500 ℃ in an atmosphere muffle furnace to obtain the catalyst.
The catalyst composition is shown in table 1. The catalyst preparation conditions and test results are shown in table 2.
Example 8
2g of graphdiyne are placed in a tubular reactor and 10% pH is passed through3The nitrogen is treated, the gas flow rate is 300mL/min, the treatment temperature is 450 ℃, the treatment time is 12 hours, and the cooled graphene is used as phosphorus-doped graphene.
Taking 80 parts of phosphorus-doped graphdiyne and 10 parts of TiO2Mechanically mixed to act as a catalyst support.
Taking 0.622mL of the solution with the concentration of 16.1Adding 0.378mL of water into 4mg/L chloroplatinic acid solution to obtain solution, adding 2g of the above carrier into the solution, stirring, standing at room temperature for 2h, drying at 120 deg.C for 4h, and adding N2And roasting the mixture for 4 hours at 500 ℃ in an atmosphere muffle furnace to obtain the catalyst.
The catalyst composition is shown in table 1. The catalyst preparation conditions and test results are shown in table 2.
Example 9
2g of graphdiyne are placed in a tubular reactor and 10% NH is introduced3The nitrogen is treated, the gas flow rate is 500mL/min, the treatment temperature is 450 ℃, the treatment time is 12h, and the nitrogen-doped graphite alkyne is obtained after cooling.
Taking 80 parts of phosphorus-doped graphdiyne and 10 parts of TiO2Mechanically mixed to act as a catalyst support.
Adding 0.622mL of chloroplatinic acid solution with concentration of 16.14mg/L into 0.378mL of water to obtain solution, adding 2g of the above carrier into the solution, stirring, standing at room temperature for 2h, drying at 120 deg.C for 4h, and adding N2And roasting the mixture for 4 hours at 500 ℃ in an atmosphere muffle furnace to obtain the catalyst.
The catalyst composition is shown in table 1. The catalyst preparation conditions and test results are shown in table 2.
Example 10
2g of graphdiyne are placed in a tubular reactor and 10% NH is introduced3The nitrogen is treated, the gas flow rate is 400mL/min, the treatment temperature is 450 ℃, the treatment time is 12h, and the nitrogen-doped graphite alkyne is obtained after cooling.
Taking 80 parts of nitrogen-doped graphdiyne and 10 parts of TiO2Mechanically mixed to act as a catalyst support.
Adding 0.622mL of chloroplatinic acid solution with concentration of 16.14mg/L into 0.378mL of water to obtain solution, adding 2g of the above carrier into the solution, stirring, standing at room temperature for 2h, drying at 120 deg.C for 4h, and adding N2And roasting the mixture for 4 hours at 500 ℃ in an atmosphere muffle furnace to obtain the catalyst.
The catalyst composition is shown in table 1. The catalyst preparation conditions and test results are shown in table 2.
Example 11
2g of graphdiyne are placed in a tubular reactor and 10% NH is introduced3The nitrogen is treated, the gas flow rate is 300mL/min, the treatment temperature is 450 ℃, the treatment time is 12h, and the nitrogen-doped graphite alkyne is obtained after cooling.
Taking 80 parts of nitrogen-doped graphdiyne and 10 parts of TiO2Mechanically mixed to act as a catalyst support.
Adding 0.622mL of chloroplatinic acid solution with concentration of 16.14mg/L into 0.378mL of water to obtain solution, adding 2g of the above carrier into the solution, stirring, standing at room temperature for 2h, drying at 120 deg.C for 4h, and adding N2And roasting the mixture for 4 hours at 450 ℃ in an atmosphere muffle furnace to obtain the catalyst.
The catalyst composition is shown in table 1. The catalyst preparation conditions and test results are shown in table 2.
Example 12
2g of graphdiyne are placed in a tubular reactor and 10% NH is introduced3The nitrogen is treated, the gas flow rate is 200mL/min, the treatment temperature is 450 ℃, the treatment time is 12h, and the nitrogen-doped graphite alkyne is obtained after cooling.
Taking 80 parts of nitrogen-doped graphdiyne and 10 parts of TiO2Mechanically mixed to act as a catalyst support.
Adding 0.622mL of chloroplatinic acid solution with concentration of 16.14mg/L into 0.378mL of water to obtain solution, adding 2g of the above carrier into the solution, stirring, standing at room temperature for 2h, drying at 120 deg.C for 4h, and adding N2And roasting the mixture for 4 hours at 500 ℃ in an atmosphere muffle furnace to obtain the catalyst.
The catalyst composition is shown in table 1. The catalyst preparation conditions and test results are shown in table 2.
Example 13
2g of graphdiyne are placed in a tubular reactor and 10% NH is introduced3The nitrogen is treated, the gas flow rate is 350mL/min, the treatment temperature is 450 ℃, the treatment time is 6h, and the nitrogen-doped graphite alkyne is obtained after cooling.
Taking 70 parts of nitrogen-doped graphdiyne and 10 parts of TiO2Mechanical mixing, as catalyst support。
Adding 0.622mL of chloroplatinic acid solution with concentration of 16.14mg/L into 0.378mL of water to obtain solution, adding 2g of the above carrier into the solution, stirring, standing at room temperature for 2h, drying at 120 deg.C for 4h, and adding N2And roasting the mixture for 4 hours at 500 ℃ in an atmosphere muffle furnace to obtain the catalyst.
The catalyst composition is shown in table 1. The catalyst preparation conditions and test results are shown in table 2.
Example 14
2g of graphdiyne are placed in a tubular reactor and 10% NH is introduced3The nitrogen is treated, the gas flow rate is 400mL/min, the treatment temperature is 450 ℃, the treatment time is 8 hours, and the nitrogen-doped graphite alkyne is obtained after cooling.
Taking 80 parts of nitrogen-doped graphdiyne and 10 parts of TiO2And CeO2Mixture of (TiO)2：CeO2Is 1: 1) mechanically mixed to act as a catalyst support.
Adding 0.622mL of chloroplatinic acid solution with concentration of 16.14mg/L into 0.378mL of water to obtain solution, adding 2g of the above carrier into the solution, stirring, standing at room temperature for 2h, drying at 120 deg.C for 4h, and adding N2And roasting the mixture for 4 hours at 500 ℃ in an atmosphere muffle furnace to obtain the catalyst.
The catalyst composition is shown in table 1. The catalyst preparation conditions and test results are shown in table 2.
Example 15
2g of graphdiyne are placed in a tubular reactor and 10% NH is introduced3The nitrogen is treated, the gas flow rate is 430mL/min, the treatment temperature is 450 ℃, the treatment time is 12h, and the nitrogen-doped graphite alkyne is obtained after cooling.
Taking 80 parts of nitrogen-doped graphdiyne and 10 parts of TiO2And ZrO2Mixture of (TiO)2：ZrO2Is 1: 1) mechanically mixed to act as a catalyst support.
Adding 0.622mL of chloroplatinic acid solution with concentration of 16.14mg/L into 0.378mL of water to obtain solution, adding 2g of the above carrier into the solution, stirring, standing at room temperature for 2h, drying at 120 deg.C for 4h, and adding N2And roasting the mixture for 4 hours at 500 ℃ in an atmosphere muffle furnace to obtain the catalyst.
The catalyst composition is shown in table 1. The catalyst preparation conditions and test results are shown in table 2.
Example 16
2g of graphdiyne are placed in a tubular reactor and 10% NH is introduced3The nitrogen is treated, the gas flow rate is 480mL/min, the treatment temperature is 450 ℃, the treatment time is 12 hours, and the nitrogen-doped graphite alkyne is obtained after cooling.
Taking 80 parts of nitrogen-doped graphdiyne and 10 parts of TiO2And CeO2Mixture of (TiO)2：CeO2Is 1: 1) mechanically mixed to act as a catalyst support.
Adding 0.622mL of chloroplatinic acid solution with concentration of 16.14mg/L into 0.378mL of water to obtain solution, adding 2g of the above carrier into the solution, stirring, standing at room temperature for 2h, drying at 120 deg.C for 4h, and adding N2And roasting the mixture for 4 hours at 500 ℃ in an atmosphere muffle furnace to obtain the catalyst.
The catalyst composition is shown in table 1. The catalyst preparation conditions and test results are shown in table 2.
Example 17
2g of double-layer graphdiyne was placed in a tubular reactor and 10% NH was added3The nitrogen is treated, the gas flow rate is 300mL/min, the treatment temperature is 450 ℃, the treatment time is 12h, and the nitrogen-doped graphite alkyne is obtained after cooling.
Taking 80 parts of nitrogen-doped graphdiyne and 10 parts of TiO2And CeO2Mixture of (TiO)2：CeO2Is that 2: 1) mechanically mixed to act as a catalyst support.
Adding 0.622mL of chloroplatinic acid solution with concentration of 16.14mg/L into 0.378mL of water to obtain solution, adding 2g of the above carrier into the solution, stirring, standing at room temperature for 2h, drying at 120 deg.C for 4h, and adding N2And roasting the mixture for 4 hours at 500 ℃ in an atmosphere muffle furnace to obtain the catalyst.
The catalyst composition is shown in table 1. The catalyst preparation conditions and test results are shown in table 2.
Example 18
2g of graphdiyne are placed in a tubular reactor and 15% NH is introduced3+5％BH3The nitrogen is treated, the gas flow rate is 300mL/min, the treatment temperature is 450 ℃, the treatment time is 12h, and the nitrogen-doped graphite alkyne is obtained after cooling.
Taking 80 parts of nitrogen-doped graphdiyne and 10 parts of TiO2Mechanically mixed to act as a catalyst support.
Adding 0.622mL of chloroplatinic acid solution with concentration of 16.14mg/L into 0.378mL of water to obtain solution, adding 2g of the above carrier into the solution, stirring, standing at room temperature for 2h, drying at 120 deg.C for 4h, and adding N2And roasting the mixture for 4 hours at 500 ℃ in an atmosphere muffle furnace to obtain the catalyst.
The catalyst composition is shown in table 1. The catalyst preparation conditions and test results are shown in table 2.
Example 19
2g of graphdiyne are placed in a tubular reactor and 15% NH is introduced3+5％H2And (3) treating the nitrogen of the S at the gas flow rate of 300mL/min and the treatment temperature of 450 ℃ for 12h, and cooling the treated gas to obtain the nitrogen-doped graphdiyne.
Taking 80 parts of nitrogen-doped graphdiyne and 10 parts of TiO2Mechanically mixed to act as a catalyst support.
Adding 0.622mL of chloroplatinic acid solution with concentration of 16.14mg/L into 0.378mL of water to obtain solution, adding 2g of the above carrier into the solution, stirring, standing at room temperature for 2h, drying at 120 deg.C for 4h, and adding N2And roasting the mixture for 4 hours at 500 ℃ in an atmosphere muffle furnace to obtain the catalyst.
The catalyst composition is shown in table 1. The catalyst preparation conditions and test results are shown in table 2.
Example 20
2g of graphdiyne are placed in a tubular reactor and 15% NH is introduced3+5％PH3The nitrogen is treated, the gas flow rate is 300mL/min, the treatment temperature is 450 ℃, the treatment time is 12h, and the nitrogen-doped graphite alkyne is obtained after cooling.
Taking 80 parts of nitrogen-doped graphdiyne and 10 parts of TiO2Mechanically mixed to act as a catalyst support.
Adding 0.622mL of chloroplatinic acid solution with concentration of 16.14mg/L into 0.378mL of water to obtain solution, adding 2g of the above carrier into the solution, stirring, standing at room temperature for 2h, drying at 120 deg.C for 4h, and adding N2And roasting the mixture for 4 hours at 500 ℃ in an atmosphere muffle furnace to obtain the catalyst.
The catalyst composition is shown in table 1. The catalyst preparation conditions and test results are shown in table 2.
Example 21
2g of graphdiyne are placed in a tubular reactor and 10% NH is introduced3The nitrogen is treated, the gas flow rate is 300mL/min, the treatment temperature is 450 ℃, the treatment time is 12h, and the nitrogen-doped graphite alkyne is obtained after cooling.
Taking 80 parts of nitrogen-doped graphdiyne and 10 parts of TiO2Mechanically mixed to act as a catalyst support.
Adding 0.622mL of 16.14mg/L palladium chloride solution into 0.378mL of water to obtain a solution, adding 2g of the above carrier into the solution, stirring, standing at room temperature for 2h, drying at 120 deg.C for 4h, and adding N2And roasting the mixture for 4 hours at 500 ℃ in an atmosphere muffle furnace to obtain the catalyst.
The catalyst composition is shown in table 1. The catalyst preparation conditions and test results are shown in table 2.
Example 22
2g of graphdiyne are placed in a tubular reactor and 10% NH is introduced3The nitrogen is treated, the gas flow rate is 300mL/min, the treatment temperature is 450 ℃, the treatment time is 12h, and the nitrogen-doped graphite alkyne is obtained after cooling.
Taking 80 parts of nitrogen-doped graphdiyne and 10 parts of TiO2Mechanically mixed to act as a catalyst support.
Adding 0.622mL palladium chloride solution with concentration of 96.84mg/L into 0.378mL water to obtain solution, adding 2g above carrier into the solution, stirring, standing at room temperature for 2 hr, drying at 120 deg.C for 4 hr, and adding N2And roasting the mixture for 4 hours at 500 ℃ in an atmosphere muffle furnace to obtain the catalyst.
The catalyst composition is shown in table 1. The catalyst preparation conditions and test results are shown in table 2.
Example 23
2g of nitrogen-doped graphdiyne was placed in a tubular reactor and charged with a solution containing 15% H2S+5％BH3The nitrogen is treated, the gas flow rate is 300mL/min, the treatment temperature is 450 ℃, the treatment time is 12h, and the cooled gas is used as sulfur-boron doped graphite alkyne.
Mixing 80 parts of sulfur-boron doped graphyne and 10 parts of TiO2Mechanically mixed to act as a catalyst support.
Adding 0.622mL of chloroplatinic acid solution with concentration of 16.14mg/L into 0.378mL of water to obtain solution, adding 2g of the above carrier into the solution, stirring, standing at room temperature for 2h, drying at 120 deg.C for 4h, and adding N2And roasting the mixture for 4 hours at 500 ℃ in an atmosphere muffle furnace to obtain the catalyst.
The catalyst composition is shown in table 1. The catalyst preparation conditions and test results are shown in table 2.
Example 24
2g of graphdiyne are placed in a tubular reactor and 15% H are introduced2S+5％PH3The nitrogen is treated, the gas flow rate is 300mL/min, the treatment temperature is 450 ℃, the treatment time is 12h, and the cooled graphite alkyne is used as sulfur-phosphorus doped graphite alkyne.
Mixing 80 parts of sulfur-phosphorus doped grapyne and 10 parts of TiO2Mechanically mixed to act as a catalyst support.
Adding 0.622mL of chloroplatinic acid solution with concentration of 16.14mg/L into 0.378mL of water to obtain solution, adding 2g of the above carrier into the solution, stirring, standing at room temperature for 2h, drying at 120 deg.C for 4h, and adding N2And roasting the mixture for 4 hours at 500 ℃ in an atmosphere muffle furnace to obtain the catalyst.
The catalyst composition is shown in table 1. The catalyst preparation conditions and test results are shown in table 2.
Example 25
2g of graphdine are placed in a tubular reactor and 15% BH is introduced3+5％PH3The flow rate of the gas is 300mL/min, the treatment temperature is 450 ℃, and the treatment is carried out during the treatmentThe time is 12 hours, and the graphite alkyne is used as boron-phosphorus doped graphite alkyne after cooling.
Taking 80 parts of boron-phosphorus doped graphane and 10 parts of TiO2Mechanically mixed to act as a catalyst support.
Adding 0.622mL of chloroplatinic acid solution with concentration of 16.14mg/L into 0.378mL of water to obtain solution, adding 2g of the above carrier into the solution, stirring, standing at room temperature for 2h, drying at 120 deg.C for 4h, and adding N2And roasting the mixture for 4 hours at 500 ℃ in an atmosphere muffle furnace to obtain the catalyst.
The catalyst composition is shown in table 1. The catalyst preparation conditions and test results are shown in table 2.
Example 26
2g of graphdiyne are placed in a tubular reactor and 10% NH is introduced3The nitrogen is treated, the gas flow rate is 300mL/min, the treatment temperature is 450 ℃, the treatment time is 12h, and the nitrogen-doped graphite alkyne is obtained after cooling.
Taking 80 parts of nitrogen-doped graphdiyne and 10 parts of TiO2Mechanically mixed to act as a catalyst support.
Adding 0.622mL of chloroplatinic acid solution with concentration of 16.14mg/L into 0.378mL of water to obtain solution, adding 2g of the above carrier into the solution, stirring, standing at room temperature for 2h, drying at 120 deg.C for 4h, and adding N2And roasting the mixture for 4 hours at 500 ℃ in an atmosphere muffle furnace to obtain the catalyst.
The catalyst composition is shown in table 1. The catalyst preparation conditions and test results are shown in table 2.
Example 27
2g of graphdiyne are placed in a tubular reactor and 10% NH is introduced3The nitrogen is treated, the gas flow rate is 300mL/min, the treatment temperature is 450 ℃, the treatment time is 12h, and the nitrogen-doped graphite alkyne is obtained after cooling.
Taking 80 parts of nitrogen-doped graphdiyne and 10 parts of TiO2Mechanically mixed to act as a catalyst support.
Adding 0.622mL of chloroplatinic acid solution with concentration of 16.14mg/L into 0.378mL of water to obtain solution, adding 2g of the above carrier into the solution, stirring, standing at room temperature for 2h, and standing at 120 deg.CDrying for 4h, and finally adding it into N2And roasting the mixture for 4 hours at 500 ℃ in an atmosphere muffle furnace to obtain the catalyst.
The catalyst composition is shown in table 1. The catalyst preparation conditions and test results are shown in table 2.
Example 28
2g of double-layer graphdiyne are placed in a tubular reactor, and 15% H is introduced2S+5％BH3The nitrogen is treated, the gas flow rate is 300mL/min, the treatment temperature is 450 ℃, the treatment time is 12h, and the cooled gas is used as sulfur-boron doped graphite alkyne.
Mixing 80 parts of sulfur-boron doped graphyne and 10 parts of TiO2Mechanically mixed to act as a catalyst support.
Adding 0.622mL of chloroplatinic acid solution with concentration of 16.14mg/L into 0.378mL of water to obtain solution, adding 2g of the above carrier into the solution, stirring, standing at room temperature for 2h, drying at 120 deg.C for 4h, and adding N2And roasting the mixture for 4 hours at 500 ℃ in an atmosphere muffle furnace to obtain the catalyst.
The catalyst composition is shown in table 1. The catalyst preparation conditions and test results are shown in table 2.
Example 29
2g of double-layer graphdiyne are placed in a tubular reactor, and 15% H is introduced2S+5％BH3The nitrogen is treated, the gas flow rate is 300mL/min, the treatment temperature is 450 ℃, the treatment time is 12h, and the cooled gas is used as sulfur-boron doped graphite alkyne.
Mixing 80 parts of sulfur-boron doped graphyne and 10 parts of TiO2Mechanically mixed to act as a catalyst support.
Adding 0.378mL of water into 0.4976mL of chloroplatinic acid solution with concentration of 16.14mg/L and 0.1244mL of palladium chloride solution with concentration of 16.14mg/L to obtain solution, adding 2g of the above carrier into the solution, stirring, standing at room temperature for 2h, drying at 120 deg.C for 4h, and adding N2And roasting the mixture for 4 hours at 500 ℃ in an atmosphere muffle furnace to obtain the catalyst.
The catalyst composition is shown in table 1. The catalyst preparation conditions and test results are shown in table 2.
Example 30
2g of multiwalled graphdine mixture are placed in a tubular reactor and a 15% H content is introduced2S+5％BH3The nitrogen is treated, the gas flow rate is 300mL/min, the treatment temperature is 450 ℃, the treatment time is 12h, and the cooled gas is used as sulfur-boron doped graphite alkyne.
Mixing 80 parts of sulfur-boron doped graphyne and 10 parts of TiO2Mechanically mixed to act as a catalyst support.
Adding 0.378mL of water into 0.1244mL of chloroplatinic acid solution with concentration of 16.14mg/L and 0.4976mL of palladium chloride solution with concentration of 16.14mg/L to obtain solution, adding 2g of the above carrier into the solution, stirring, standing at room temperature for 2h, drying at 120 deg.C for 4h, and adding N2And roasting the mixture for 4 hours at 500 ℃ in an atmosphere muffle furnace to obtain the catalyst.
The catalyst composition is shown in table 1. The catalyst preparation conditions and test results are shown in table 2.
Comparative example 1
Taking 0.622mL of chloroplatinic acid solution with the concentration of 16.14mg/L, adding 1.378mL of water to prepare solution, adding 2g of nitrogen-doped graphdine into the solution, stirring, standing at room temperature for 2 hours, then placing the solution into a vacuum drying oven, drying at 100 ℃ and the pressure of 0MPa for 4 hours, and then placing a sample into a muffle furnace to roast for 4 hours under the nitrogen atmosphere at 550 ℃ to obtain the required catalyst.
The catalyst composition is shown in table 1. The catalyst preparation conditions and test results are shown in table 2.
Comparative example 2
Taking 0.622mL of chloroplatinic acid solution with the concentration of 16.14mg/L, adding 1.378mL of water to prepare solution, adding 2g of double-layer graphdine into the solution, stirring, standing at room temperature for 2 hours, then placing the solution into a vacuum drying oven, drying at 100 ℃ and the pressure of 0MPa for 4 hours, and then placing a sample into a muffle furnace to roast for 4 hours under the nitrogen atmosphere at 550 ℃ to obtain the required catalyst.
The catalyst composition is shown in table 1. The catalyst preparation conditions and test results are shown in table 2.
Comparative example 3
0.4976mL of chloroplatinic acid solution with the concentration of 16.14mg/L and 0.1244mL of palladium chloride solution with the concentration of 16.14mg/L are taken, 0.378mL of water is added to prepare solution, 2g of nitrogen-doped graphdine is added to the solution, the solution is stirred and placed at room temperature for 2 hours, then the solution is placed into a vacuum drying oven to be dried for 4 hours at the temperature of 100 ℃ and the pressure of 0MPa, and then a sample is placed into a muffle furnace to be roasted for 4 hours at the temperature of 550 ℃ under the nitrogen atmosphere, so that the required catalyst is obtained.
The catalyst composition is shown in table 1. The catalyst preparation conditions and test results are shown in table 2.
Comparative example 4
Taking 0.622mL chloroplatinic acid solution with the concentration of 16.14mg/L, adding 1.378mL water to prepare solution, and adding 2g TiO2Adding into the solution, stirring, standing at room temperature for 2h, then placing into a vacuum drying oven, drying at 100 deg.C under 0MPa for 4h, and then placing the sample into a muffle furnace, and calcining at 550 deg.C under nitrogen atmosphere for 4h to obtain the desired catalyst.
The catalyst composition is shown in table 1. The catalyst preparation conditions and test results are shown in table 2.
TABLE 1
Figure BDA0002248403490000171
TABLE 1 continuation of the table
Figure BDA0002248403490000181
Note: the parts of graphdiyne in table 1 refer to the parts of pure graphdiyne.
TABLE 2
Figure BDA0002248403490000191
TABLE 2 continuation of the table
Figure BDA0002248403490000201
Note: x10 is the conversion of the feed at 10h of run.
The roasting atmosphere is nitrogen.
As can be seen from the data in table 2, the present invention enables higher conversion rates to be achieved.
Examples 31 to 35
The performance of the catalyst prepared in example 30 was evaluated for dehydrogenation of lower hydrocarbons to lower olefins, and the results are shown in table 3.
The major product of example 31 was isobutylene. The major product of example 32 was butene. The major product of example 33 was butene. The major product of example 34 was butene. The major product of example 35 was butene.
TABLE 3
Figure BDA0002248403490000211
Note: x10 is the conversion of the feedstock on 10h run
As can be seen from the data in table 3, the catalyst of the present invention shows higher conversion rate when used for the dehydrogenation of lower alkane to lower alkene.
Examples 36 to 42
The performance of the catalyst prepared in example 30 for dehydrogenation of organic liquid hydrogen storage material was evaluated and the results are shown in table 4.
TABLE 4
Figure BDA0002248403490000221
Note: x1 is the conversion of the feedstock at 1h of run
As can be seen from the data in table 4, the catalyst of the present invention exhibits a higher conversion when used in the dehydrogenation reaction of an organic liquid hydrogen storage material.
It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not constitute any limitation to the present invention. The present invention has been described with reference to exemplary embodiments, but the words which have been used herein are words of description and illustration, rather than words of limitation. The invention can be modified, as prescribed, within the scope of the claims and without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.

Claims (10)

1. A catalyst support comprising: a graphatidine and a metal oxide promoter, preferably, the metal oxide promoter is selected from at least one of a group IVB metal oxide and a lanthanide metal oxide, more preferably, the metal oxide promoter is selected from TiO2、ZrO2、CeO2More preferably, the metal oxide promoter is selected from TiO2、ZrO2、CeO2At least two of them.
2. The catalyst support according to claim 1, wherein the grapliyne is selected from pure grapliyne and/or heteroatom-doped grapliyne, wherein the heteroatom is selected from at least one of nitrogen, boron, sulfur and phosphorus, preferably wherein the heteroatom-doped grapliyne is prepared by treating pure grapliyne in a 5% -25% heteroatom-containing gas atmosphere at a temperature of 200 ℃ to 350 ℃ for 2h to 6 h.
3. The catalyst carrier according to claim 1 or 2, wherein the mass ratio of the graphdiyne to the metal oxide promoter is 10:1 to 1:3, preferably 5:1 to 1:3, and more preferably 4:1 to 1: 2.
4. The catalyst carrier according to any one of claims 1 to 3, which is prepared by a method comprising: mixing the graphdiyne and the metal oxide to prepare the catalyst carrier.
5. A dehydrogenation catalyst comprising:
and (2) component A: the catalyst support of any one of claims 1-4; and
and (B) component: at least one group VIII metal, preferably Pd and/or Pt.
6. The catalyst according to claim 5, characterized in that the catalyst is, in parts by weight,
the content of the component A is 65-99 parts, preferably 65-90 parts;
the content of the component B is 0.01-6.5 parts, preferably 0.01-3.0 parts.
7. A method of preparing the catalyst of claim 5 or 6, comprising:
dipping the component A by using the salt solution of the component B to prepare the catalyst; preferably, the step of impregnating comprises: placing the component A in the salt solution of the component B, standing for 1-4 h at 25-100 ℃, then roasting for 2-6 h in an oxygen-free atmosphere at 400-600 ℃, preferably a nitrogen atmosphere, and finally cooling to room temperature.
8. A liquid phase dehydrogenation process comprising contacting an organic liquid hydrogen storage material with a catalyst according to claim 5 or 6 or a catalyst prepared according to the preparation process of claim 7, preferably at a reaction pressure of 0MPa to 10MPa, a reaction temperature of 120 ℃ to 300 ℃ and 0.1h-1～10h-1Occurs at a mass space velocity of (c).
9. The liquid phase dehydrogenation process of claim 8, wherein the organic liquid hydrogen storage material is selected from at least one of cyclohexane, methylcyclohexane, tetrahydronaphthalene, decahydronaphthalene, perhydroazeethylcarbazole, perhydrophenanthrene, perhydroanthracene, perhydrocarbazole and their derivatives, a component obtained by cutting a segment from petroleum or a distillate of petroleum, and a component obtained by hydrogenating a component obtained by cutting a segment from petroleum or a distillate of petroleum.
10. A process for preparing low-carbon olefin by dehydrogenating low-carbon alkane includes such steps as mixing low-carbon alkane with hydrogenContacting the catalyst of claim 5 or 6 or the catalyst prepared by the preparation method of claim 7 to produce lower olefins; preferably, the low-carbon alkane comprises isobutane and/or butane, the low-carbon olefin comprises isobutene and/or butene, and more preferably, the contact is carried out at the reaction pressure of 0MPa to 10MPa, the reaction temperature of 120 ℃ to 400 ℃ and 0.1h-1～8.0h-1Occurs at a mass space velocity of (c).
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