CN111056531B - Method for liquid phase dehydrogenation of heterocyclic naphthenic hydrogen storage material - Google Patents

Method for liquid phase dehydrogenation of heterocyclic naphthenic hydrogen storage material Download PDF

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CN111056531B
CN111056531B CN201811201848.5A CN201811201848A CN111056531B CN 111056531 B CN111056531 B CN 111056531B CN 201811201848 A CN201811201848 A CN 201811201848A CN 111056531 B CN111056531 B CN 111056531B
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evaluation
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CN111056531A (en
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童凤丫
孙清
邵一凡
缪长喜
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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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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    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
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    • Y02E60/32—Hydrogen storage

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Abstract

The invention discloses a liquid phase dehydrogenation method of heterocyclic cycloalkane hydrogen storage material, which solves the problems of high reaction temperature and poor catalyst stability of the existing gas phase dehydrogenation technology, and adopts a bifunctional catalyst to react with the heterocyclic cycloalkane hydrogen storage material at boiling point temperature in a reactor to generate hydrogen and corresponding products, wherein the reaction conditions are as follows: the reaction pressure is 2-10 MPa, the temperature is 80-250 ℃, and the mass space velocity is 0.1-10 h‑1The product circulation amount is 0-2%, and the catalyst comprises (a) 0.1-5 parts of at least one metal or alloy thereof selected from group VIII elements in the periodic table of elements; (b) 70-90 parts of carrier, and a compound formed by at least one of Fe, Cu and Zn in the periodic table of elements and carbon element, so that the problems are solved, a carbon-hydrogen bond can be activated under a liquid phase condition, and the catalyst has high stability when applied to liquid phase dehydrogenation of a hydrogen storage compound.

Description

Method for liquid phase dehydrogenation of heterocyclic naphthenic hydrogen storage material
Technical Field
The invention discloses a liquid-phase dehydrogenation method of a heterocyclic cycloalkane hydrogen storage material, which is applicable to the field of hydrogen energy storage and transportation.
Background
Hydrogen is considered to be the ultimate source of energy for humans. From development to application, a perfect hydrogen gas storage and transportation method must be established, however, hydrogen is not commercially applied so far, and the hydrogen storage and transportation technology is not broken through.
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 hydrogen energy storageThe reaction in the process is reversible, the reactant products can be recycled, and the hydrogen storage amount is relatively high (about 60-75kg H)2/m3The mass fraction is 6-8 percent), meets the indexes specified by the International energy agency and the United states department of energy (DOE), is transported for a long distance in the form of organic liquid or can solve the problem of uneven distribution of energy in areas, really meets the requirement of green chemistry and has stronger application prospect.
The hydrogenation process and the dehydrogenation process exist in the heterocyclic naphthenic hydrogen storage technology at the same time, 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 the dehydrogenation reaction is favorably carried out 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 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 by the liquid phase reaction is to find a catalytic technology which can activate the hydrogen-containing compound at the boiling temperature and has higher stability. The bifunctional catalyst formed by noble metal and metal carbide has two active centers, 1) an active central body for carbon-hydrogen bond cracking; 2) the skeleton of the anchoring active central body can crack carbon-hydrogen bonds at the boiling point temperature of the heterocyclic compound, and has high catalytic activity, and the skeleton can anchor the active central body and reduce the loss of the number of active intermediates. According to this concept, the present patent provides a method for liquid phase dehydrogenation of heterocyclic cycloalkane hydrogen storage materials.
Disclosure of Invention
The technical problems to be solved by the invention are that the reaction temperature is high, the catalyst is inactivated quickly, the operation cost is high due to the use of membrane reaction, the equipment investment is large, the maintenance is not easy and the like in the traditional gas phase dehydrogenation technology, and the invention provides a method for liquid phase dehydrogenation of heterocyclic cycloalkane hydrogen storage materials.
The technical scheme adopted by the invention is as follows:
a method for liquid phase dehydrogenation of heterocyclic cycloalkane hydrogen storage materials, comprising the following steps: the heterocyclic naphthenic hydrogen storage material reacts with the bifunctional catalyst in a liquid phase condition in the reactor to generate hydrogen and a product.
In the technical scheme, the reaction conditions are as follows: the reaction pressure is 2-10 MPa, the temperature is 80-250 ℃, the mass space velocity is 0.1-10 h < -1 >, and the product circulation amount is 0-2%.
In the technical scheme, the preferable reaction pressure is 4-8 MPa, the temperature is 100-230 ℃, and the mass space velocity is 0.1-6 h-1(ii) a The product circulation amount is 0-1%.
In the above technical solution, preferably, the heterocyclic cycloalkane is at least one selected from the group consisting of perhydroazeethylcarbazole, perhydrotriazine, perhydropyrrole, and perhydrocarbazole.
In the above technical solution, preferably, the reactor is selected from a fixed bed reactor, a trickle bed reactor, a tank reactor, a slurry bed reactor or a moving bed reactor.
In the above technical solution, preferably, the bifunctional catalyst comprises: 1) a carbon-hydrogen bond cleaving active central body; 2) anchoring the backbone of the active centrosome.
In the above technical solution, preferably, the bifunctional catalyst comprises, in parts by weight, 0.1 to 5 parts of an active central body for carbon-hydrogen bond cleavage, at least one metal selected from platinum group metals or an alloy thereof; 70-90 parts of a framework anchoring the active central body, the framework being a metal carbide.
In the above aspect, the metal carbide is preferably selected from compounds of carbon and at least one of Fe, Cu, and Zn.
In the above technical solution, it is more preferable that Fe, Cu, and Zn are selected from Fe and Cu, or from Fe and Zn; the most preferred scheme is the synergistic combination of Fe, Cu and Zn. In the technical scheme, the mass ratio of Fe to Cu or Zn is 5: 1-1: 2.
In the technical scheme, the mass ratio of Fe, Cu, Zn and C elements is (30-6): 1, and the preferable range is (16-4): 1.
In the above technical solution, preferably, the method is as follows: 1) dissolving salts of metal elements such as Fe, Cu, Zn and the like, mixing with a solution of platinum group metal elements, and coprecipitating to obtain a precursor;
2) activating the precursor in an atmosphere furnace, and partially carbonizing Fe, Cu and Zn by hydrocarbon gas in the atmosphere furnace to obtain an active central body cracked by using platinum metals as carbon-hydrogen bonds, and forming a catalyst anchoring the framework of the active central body by Fe, Cu, Zn and C elements.
In the above technical solution, preferably, the preparation method of the catalyst further comprises a coprecipitation step, and the conditions are as follows: the temperature is 40-100 ℃, the pressure is normal, and the pH is 7.1-12; the dissolution temperature of the group VIB element salt is 40-100 ℃.
In the above technical solution, preferably, the atmosphere furnace gas includes: methane, ethane, propane, butane, isobutane, butene, ethylbenzene, styrene.
In the above aspect, it is more preferable that the atmosphere furnace gas includes: at least one of methane, ethane, propane, butane, isobutane. More preferably, the gas of the atmosphere furnace is selected from a mixture of ethane and propane, and the volume ratio of ethane to propane in the mixture is 9: 1-1: 6.
In the above technical solution, preferably, the precursor activation conditions are: the temperature is 400-600 ℃, the time is 1-8 h, the heating rate is 1-20 ℃/min, the pressure is normal, and the gas flow rate is 50-400 mL/min.
In the above technical solution, more preferably, the precursor activation conditions are: the temperature is 400-580 ℃, the time is 1-6 h, the heating rate is 1-10 ℃/min, the pressure is normal, and the gas flow rate is 50-350 mL/min.
In the above technical solution, preferably, the pH regulator is at least one of ammonia water, sodium hydroxide, sodium bicarbonate, potassium carbonate, sodium citrate, potassium citrate, monosodium citrate, and trisodium bicarbonate.
In the above technical solution, more preferably, the PH regulator is at least one of ammonia water, sodium bicarbonate, sodium citrate, potassium citrate, monosodium citrate, and trisodium bicarbonate.
The invention is based on the characteristics of the bifunctional catalyst formed by noble metal and metal carbide, namely the catalyst has two active centers, 1) an active central body for cracking carbon-hydrogen bonds; 2) the skeleton of the anchoring active central body can crack carbon-hydrogen bonds at the boiling point temperature of the heterocyclic compound, and has high catalytic activity, and the skeleton can anchor the active central body and reduce the loss of the number of active intermediates. Under the guidance of the method, the method for liquid-phase dehydrogenation of the heterocyclic naphthenic hydrogen storage material can realize dehydrogenation reaction at the boiling temperature of a heterocyclic compound under the action of a bifunctional catalyst, and greatly solves the problems of the existing gas-phase reaction.
The invention is further illustrated by the following examples, but is not limited thereto.
Detailed Description
[ example 1 ]
Adding 20g of ferric nitrate nonahydrate and 4g of cobalt nitrate hexahydrate into water, completely dissolving at 80 ℃, dropwise adding 10mL of chloroplatinic acid with the concentration of 16.14mL/L, stirring, dropwise adding ammonia water to adjust the pH value of the mixed solution to 8, stirring until a large amount of precipitates are generated in the solution, filtering the solution, and washing a filter cake to obtain a catalyst precursor. Activating the precursor in an atmosphere furnace to obtain the catalyst, wherein the activation temperature is 500 ℃, the activation time is 4h, the heating rate is 5 ℃/min, the pressure is normal, the gas flow rate is 200mL/min, the activation gas is mixed gas of ethane and propane, and the volume ratio of the ethane to the propane is 9: 1. The composition of the catalyst is shown in table 1, and the preparation conditions are shown in table 2.
1 g of the catalyst was taken for evaluation in an isothermal fixed bed reactor and reduced with hydrogen before evaluation under the following reduction conditions: the pressure and the normal pressure are controlled, the temperature is 350 ℃, the hydrogen flow is 200mL/min, the reduction time is 4h, and then the temperature is reduced for evaluation, wherein the evaluation conditions are as follows: the reaction pressure is 8MPa, the temperature is 80 ℃, and the space velocity is 2h-1Perhydroaminoethylcarbazole is used as a representative raw material for storing hydrogen in an organic liquid. The test conditions and test results are shown in Table 3. Wherein X10 represents the conversion of the feedstock over 10h of run.
[ example 2 ]
Adding 20g of ferric nitrate nonahydrate and 4g of cobalt nitrate hexahydrate into water, completely dissolving at 80 ℃, dropwise adding 10mL of chloroplatinic acid with the concentration of 16.14mL/L, stirring, dropwise adding ammonia water to adjust the pH value of the mixed solution to 8, stirring until a large amount of precipitates are generated in the solution, filtering the solution, and washing a filter cake to obtain a catalyst precursor. Activating the precursor in an atmosphere furnace to obtain the catalyst, wherein the activation temperature is 500 ℃, the activation time is 4h, the heating rate is 5 ℃/min, the pressure is normal, the gas flow rate is 200mL/min, the activation gas is mixed gas of ethane and propane, and the volume ratio of the ethane to the propane is 9: 1. The composition of the catalyst is shown in table 1, and the preparation conditions are shown in table 2.
1 g of the catalyst was taken for evaluation in an isothermal fixed bed reactor and reduced with hydrogen before evaluation under the following reduction conditions: the pressure and the normal pressure are controlled, the temperature is 350 ℃, the hydrogen flow is 200mL/min, the reduction time is 4h, and then the temperature is reduced for evaluation, wherein the evaluation conditions are as follows: the reaction pressure is 8MPa, the temperature is 100 ℃, and the space velocity is 2h-1Perhydroaminoethylcarbazole is used as a representative raw material for storing hydrogen in an organic liquid. The test conditions and test results are shown in Table 3. Wherein X10 represents the conversion of the feedstock over 10h of run.
[ example 3 ]
Adding 20g of ferric nitrate nonahydrate and 4g of cobalt nitrate hexahydrate into water, completely dissolving at 80 ℃, dropwise adding 10mL of chloroplatinic acid with the concentration of 16.14mL/L, stirring, dropwise adding ammonia water to adjust the pH value of the mixed solution to 8, stirring until a large amount of precipitates are generated in the solution, filtering the solution, and washing a filter cake to obtain a catalyst precursor. Activating the precursor in an atmosphere furnace to obtain the catalyst, wherein the activation temperature is 500 ℃, the activation time is 4h, the heating rate is 5 ℃/min, the pressure is normal, the gas flow rate is 200mL/min, the activation gas is mixed gas of ethane and propane, and the volume ratio of the ethane to the propane is 9: 1. The composition of the catalyst is shown in table 1.
1 g of the catalyst was taken for evaluation in an isothermal fixed bed reactor and reduced with hydrogen before evaluation under the following reduction conditions: the pressure and the normal pressure are kept at 350 ℃, the hydrogen flow is 200mL/min, the reduction time is 4h, and then the temperature is reduced for evaluation under the following conditions: the reaction pressure is 8MPa, the temperature is 160 ℃, and the space velocity is 2h-1Perhydroaminoethylcarbazole is used as a representative raw material for storing hydrogen in an organic liquid. The test conditions and test results are shown in Table 3. Wherein X10 represents the conversion of the feedstock over 10h of run.
[ example 4 ]
Adding 20g of ferric nitrate nonahydrate and 4g of cobalt nitrate hexahydrate into water, completely dissolving at 80 ℃, dropwise adding 10mL of chloroplatinic acid with the concentration of 16.14mL/L, stirring, dropwise adding ammonia water to adjust the pH value of the mixed solution to 8, stirring until a large amount of precipitates are generated in the solution, filtering the solution, and washing a filter cake to obtain a catalyst precursor. Activating the precursor in an atmosphere furnace to obtain the catalyst, wherein the activation temperature is 500 ℃, the activation time is 4h, the heating rate is 5 ℃/min, the pressure is normal, the gas flow rate is 200mL/min, the activation gas is mixed gas of ethane and propane, and the volume ratio of the ethane to the propane is 9: 1. The composition of the catalyst is shown in table 1.
1 g of the catalyst was taken for evaluation in an isothermal fixed bed reactor and reduced with hydrogen before evaluation under the following reduction conditions: the pressure and the normal pressure are controlled, the temperature is 350 ℃, the hydrogen flow is 200mL/min, the reduction time is 4h, and then the temperature is reduced for evaluation, wherein the evaluation conditions are as follows: the reaction pressure is 8MPa, the temperature is 230 ℃, and the space velocity is 2h-1Perhydroaminoethylcarbazole is used as a representative raw material for storing hydrogen in an organic liquid. The test conditions and test results are shown in Table 3. Wherein X10 represents the conversion of the feedstock over 10h of run.
[ example 5 ]
Adding 20g of ferric nitrate nonahydrate and 4g of cobalt nitrate hexahydrate into water, completely dissolving at 80 ℃, dropwise adding 10mL of chloroplatinic acid with the concentration of 16.14mL/L, stirring, dropwise adding ammonia water to adjust the pH value of the mixed solution to 8, stirring until a large amount of precipitates are generated in the solution, filtering the solution, and washing a filter cake to obtain a catalyst precursor. Activating the precursor in an atmosphere furnace to obtain the catalyst, wherein the activation temperature is 500 ℃, the activation time is 4h, the heating rate is 5 ℃/min, the pressure is normal, the gas flow rate is 200mL/min, the activation gas is mixed gas of ethane and propane, and the volume ratio of the ethane to the propane is 9: 1. The composition of the catalyst is shown in table 1, and the preparation conditions are shown in table 2.
1 g of the catalyst was taken for evaluation in an isothermal fixed bed reactor and reduced with hydrogen before evaluation under the following reduction conditions: the pressure and the normal pressure are controlled, the temperature is 350 ℃, the hydrogen flow is 200mL/min, the reduction time is 4h, and then the temperature is reduced for evaluation, wherein the evaluation conditions are as follows: the reaction pressure is 8MPa, the temperature is 250 ℃, and the space velocity is 2h-1Perhydroaminoethylcarbazole is used as a representative raw material for storing hydrogen in an organic liquid. The test conditions and test results are shown in Table 3. Wherein X10 represents the conversion of the feedstock over 10h of run.
[ example 6 ]
Adding 20g of ferric nitrate nonahydrate and 4g of cobalt nitrate hexahydrate into water, completely dissolving at 80 ℃, dropwise adding 10mL of chloroplatinic acid with the concentration of 16.14mL/L, stirring, dropwise adding ammonia water to adjust the pH value of the mixed solution to 8, stirring until a large amount of precipitates are generated in the solution, filtering the solution, and washing a filter cake to obtain a catalyst precursor. Activating the precursor in an atmosphere furnace to obtain the catalyst, wherein the activation temperature is 500 ℃, the activation time is 4h, the heating rate is 5 ℃/min, the pressure is normal, the gas flow rate is 200mL/min, the activation gas is mixed gas of ethane and propane, and the volume ratio of the ethane to the propane is 9: 1. The composition of the catalyst is shown in table 1, and the preparation conditions are shown in table 2.
1 g of the catalyst was taken for evaluation in an isothermal fixed bed reactor and reduced with hydrogen before evaluation under the following reduction conditions: the pressure and the normal pressure are controlled, the temperature is 350 ℃, the hydrogen flow is 200mL/min, the reduction time is 4h, and then the temperature is reduced for evaluation, wherein the evaluation conditions are as follows: the reaction pressure is 2MPa, the temperature is 160 ℃, and the space velocity is 2h-1Perhydroaminoethylcarbazole is used as a representative raw material for storing hydrogen in an organic liquid. The test conditions and test results are shown in Table 3. Wherein X10 represents the conversion of the feedstock over 10h of run.
[ example 7 ]
Adding 20g of ferric nitrate nonahydrate and 4g of cobalt nitrate hexahydrate into water, completely dissolving at 80 ℃, dropwise adding 10mL of chloroplatinic acid with the concentration of 16.14mL/L, stirring, dropwise adding ammonia water to adjust the pH value of the mixed solution to 8, stirring until a large amount of precipitates are generated in the solution, filtering the solution, and washing a filter cake to obtain a catalyst precursor. Activating the precursor in an atmosphere furnace to obtain the catalyst, wherein the activation temperature is 500 ℃, the activation time is 4h, the heating rate is 5 ℃/min, the pressure is normal, the gas flow rate is 200mL/min, the activation gas is mixed gas of ethane and propane, and the volume ratio of the ethane to the propane is 9: 1. The composition of the catalyst is shown in table 1, and the preparation conditions are shown in table 2.
1 g of the catalyst was taken for evaluation in an isothermal fixed bed reactor and reduced with hydrogen before evaluation under the following reduction conditions: the pressure and the normal pressure are controlled, the temperature is 350 ℃, the hydrogen flow is 200mL/min, the reduction time is 4h, and then the temperature is reduced for evaluation, wherein the evaluation conditions are as follows: the reaction pressure is 4MPa, the temperature is 160 ℃, and the space velocity is 2h-1Perhydroaminoethylcarbazole is used as a representative raw material for storing hydrogen in an organic liquid. The test conditions and test results are shown in Table 3. Wherein X10 represents the conversion of the feedstock over 10h of run.
[ example 8 ]
Adding 20g of ferric nitrate nonahydrate and 4g of cobalt nitrate hexahydrate into water, completely dissolving at 80 ℃, dropwise adding 10mL of chloroplatinic acid with the concentration of 16.14mL/L, stirring, dropwise adding ammonia water to adjust the pH value of the mixed solution to 8, stirring until a large amount of precipitates are generated in the solution, filtering the solution, and washing a filter cake to obtain a catalyst precursor. Activating the precursor in an atmosphere furnace to obtain the catalyst, wherein the activation temperature is 500 ℃, the activation time is 4h, the heating rate is 5 ℃/min, the pressure is normal, the gas flow rate is 200mL/min, the activation gas is mixed gas of ethane and propane, and the volume ratio of the ethane to the propane is 9: 1. The composition of the catalyst is shown in table 1, and the preparation conditions are shown in table 2.
1 g of the catalyst was taken for evaluation in an isothermal fixed bed reactor and reduced with hydrogen before evaluation under the following reduction conditions: the pressure and the normal pressure are controlled, the temperature is 350 ℃, the hydrogen flow is 200mL/min, the reduction time is 4h, and then the temperature is reduced for evaluation, wherein the evaluation conditions are as follows: the reaction pressure is 6MPa, the temperature is 160 ℃, and the space velocity is 2h-1Perhydroaminoethylcarbazole is used as a representative raw material for storing hydrogen in an organic liquid. The test conditions and test results are shown in Table 3. Wherein X10 represents the conversion of the feedstock over 10h of run.
[ example 9 ]
Adding 20g of ferric nitrate nonahydrate and 4g of cobalt nitrate hexahydrate into water, completely dissolving at 80 ℃, dropwise adding 10mL of chloroplatinic acid with the concentration of 16.14mL/L, stirring, dropwise adding ammonia water to adjust the pH value of the mixed solution to 8, stirring until a large amount of precipitates are generated in the solution, filtering the solution, and washing a filter cake to obtain a catalyst precursor. Activating the precursor in an atmosphere furnace to obtain the catalyst, wherein the activation temperature is 500 ℃, the activation time is 4h, the heating rate is 5 ℃/min, the pressure is normal, the gas flow rate is 200mL/min, the activation gas is mixed gas of ethane and propane, and the volume ratio of the ethane to the propane is 9: 1. The composition of the catalyst is shown in table 1, and the preparation conditions are shown in table 2.
1 g of the catalyst was taken for evaluation in an isothermal fixed bed reactor and reduced with hydrogen before evaluation under the following reduction conditions: the pressure and the normal pressure are controlled, the temperature is 350 ℃, the hydrogen flow is 200mL/min, the reduction time is 4h, and then the temperature is reduced for evaluation, wherein the evaluation conditions are as follows: the reaction pressure is 10MPa, the temperature is 160 ℃, and the space velocity is 2h-1Perhydroaminoethylcarbazole is used as a representative raw material for storing hydrogen in an organic liquid. The test conditions and test results are shown in Table 3. Wherein X10 represents the conversion of the feedstock over 10h of run.
[ example 10 ]
Adding 20g of ferric nitrate nonahydrate and 4g of cobalt nitrate hexahydrate into water, completely dissolving at 80 ℃, dropwise adding 10mL of chloroplatinic acid with the concentration of 16.14mL/L, stirring, dropwise adding ammonia water to adjust the pH value of the mixed solution to 8, stirring until a large amount of precipitates are generated in the solution, filtering the solution, and washing a filter cake to obtain a catalyst precursor. Activating the precursor in an atmosphere furnace to obtain the catalyst, wherein the activation temperature is 500 ℃, the activation time is 4h, the heating rate is 5 ℃/min, the pressure is normal, the gas flow rate is 200mL/min, the activation gas is mixed gas of ethane and propane, and the volume ratio of the ethane to the propane is 9: 1. The composition of the catalyst is shown in table 1, and the preparation conditions are shown in table 2.
1 g of the catalyst was taken for evaluation in an isothermal fixed bed reactor and reduced with hydrogen before evaluation under the following reduction conditions: the pressure and the normal pressure are controlled, the temperature is 350 ℃, the hydrogen flow is 200mL/min, the reduction time is 4h, and then the temperature is reduced for evaluation, wherein the evaluation conditions are as follows: the reaction pressure is 6MPa, the temperature is 160 ℃, and the space velocity is 0.1h-1Perhydroaminoethylcarbazole is used as a representative raw material for storing hydrogen in an organic liquid. The test conditions and test results are shown in Table 3. Wherein X10 represents the conversion of the feedstock over 10h of run.
[ example 11 ]
Adding 20g of ferric nitrate nonahydrate and 4g of cobalt nitrate hexahydrate into water, completely dissolving at 80 ℃, dropwise adding 10mL of chloroplatinic acid with the concentration of 16.14mL/L, stirring, dropwise adding ammonia water to adjust the pH value of the mixed solution to 8, stirring until a large amount of precipitates are generated in the solution, filtering the solution, and washing a filter cake to obtain a catalyst precursor. Activating the precursor in an atmosphere furnace to obtain the catalyst, wherein the activation temperature is 500 ℃, the activation time is 4h, the heating rate is 5 ℃/min, the pressure is normal, the gas flow rate is 200mL/min, the activation gas is mixed gas of ethane and propane, and the volume ratio of the ethane to the propane is 9: 1. The composition of the catalyst is shown in table 1, and the preparation conditions are shown in table 2.
1 g of the catalyst was taken for evaluation in an isothermal fixed bed reactor and reduced with hydrogen before evaluation under the following reduction conditions: the pressure and the normal pressure are controlled, the temperature is 350 ℃, the hydrogen flow is 200mL/min, the reduction time is 4h, and then the temperature is reduced for evaluation, wherein the evaluation conditions are as follows: the reaction pressure is 6MPa, the temperature is 160 ℃, and the space velocity is 1h-1Perhydroaminoethylcarbazole is used as a representative raw material for storing hydrogen in an organic liquid. The test conditions and test results are shown in Table 3. Wherein X10 represents the conversion of the feedstock over 10h of run.
[ example 12 ]
Adding 20g of ferric nitrate nonahydrate and 4g of cobalt nitrate hexahydrate into water, completely dissolving at 80 ℃, dropwise adding 10mL of chloroplatinic acid with the concentration of 16.14mL/L, stirring, dropwise adding ammonia water to adjust the pH value of the mixed solution to 8, stirring until a large amount of precipitates are generated in the solution, filtering the solution, and washing a filter cake to obtain a catalyst precursor. Activating the precursor in an atmosphere furnace to obtain the catalyst, wherein the activation temperature is 500 ℃, the activation time is 4h, the heating rate is 5 ℃/min, the pressure is normal, the gas flow rate is 200mL/min, the activation gas is mixed gas of ethane and propane, and the volume ratio of the ethane to the propane is 9: 1. The composition of the catalyst is shown in table 1, and the preparation conditions are shown in table 2.
1 g of the catalyst was taken for evaluation in an isothermal fixed bed reactor and reduced with hydrogen before evaluation under the following reduction conditions: the pressure and the normal pressure are controlled, the temperature is 350 ℃, the hydrogen flow is 200mL/min, the reduction time is 4h, and then the temperature is reduced for evaluation, wherein the evaluation conditions are as follows: the reaction pressure is 6MPa, the temperature is 160 ℃, and the space velocity is 3h-1Perhydroaminoethylcarbazole is used as a representative raw material for storing hydrogen in an organic liquid. The test conditions and test results are shown in Table 3. Wherein X10 represents the conversion of the feedstock over 10h of run.
[ example 13 ]
Adding 20g of ferric nitrate nonahydrate and 4g of cobalt nitrate hexahydrate into water, completely dissolving at 80 ℃, dropwise adding 10mL of chloroplatinic acid with the concentration of 16.14mL/L, stirring, dropwise adding ammonia water to adjust the pH value of the mixed solution to 8, stirring until a large amount of precipitates are generated in the solution, filtering the solution, and washing a filter cake to obtain a catalyst precursor. Activating the precursor in an atmosphere furnace to obtain the catalyst, wherein the activation temperature is 500 ℃, the activation time is 4h, the heating rate is 5 ℃/min, the pressure is normal, the gas flow rate is 200mL/min, the activation gas is mixed gas of ethane and propane, and the volume ratio of the ethane to the propane is 9: 1. The composition of the catalyst is shown in table 1, and the preparation conditions are shown in table 2.
1 g of the catalyst was taken for evaluation in an isothermal fixed bed reactor and reduced with hydrogen before evaluation under the following reduction conditions: the pressure and the normal pressure are controlled, the temperature is 350 ℃, the hydrogen flow is 200mL/min, the reduction time is 4h, and then the temperature is reduced for evaluation, wherein the evaluation conditions are as follows: the reaction pressure is 6MPa, the temperature is 160 ℃, and the space velocity is 6h-1Perhydroaminoethylcarbazole is used as a representative raw material for storing hydrogen in an organic liquid. The test conditions and test results are shown in Table 3. Wherein X10 represents the conversion of the feedstock over 10h of run.
[ example 14 ]
Adding 20g of ferric nitrate nonahydrate and 4g of cobalt nitrate hexahydrate into water, completely dissolving at 80 ℃, dropwise adding 10mL of chloroplatinic acid with the concentration of 16.14mL/L, stirring, dropwise adding ammonia water to adjust the pH value of the mixed solution to 8, stirring until a large amount of precipitates are generated in the solution, filtering the solution, and washing a filter cake to obtain a catalyst precursor. Activating the precursor in an atmosphere furnace to obtain the catalyst, wherein the activation temperature is 500 ℃, the activation time is 4h, the heating rate is 5 ℃/min, the pressure is normal, the gas flow rate is 200mL/min, the activation gas is mixed gas of ethane and propane, and the volume ratio of the ethane to the propane is 9: 1. The composition of the catalyst is shown in table 1, and the preparation conditions are shown in table 2.
1 g of the catalyst was taken for evaluation in an isothermal fixed bed reactor and reduced with hydrogen before evaluation under the following reduction conditions: the pressure and the normal pressure are controlled, the temperature is 350 ℃, the hydrogen flow is 200mL/min, the reduction time is 4h, and then the temperature is reduced for evaluation, wherein the evaluation conditions are as follows: the reaction pressure is 8MPa, the temperature is 160 ℃, and the space velocity is 2h-1Perhydroaminoethylcarbazole was used as a representative raw material for hydrogen storage in the organic liquid, and 0.1% of the amount of the product was recycled to the inlet of the reactor. The test conditions and test results are shown in Table 3. Wherein X10 represents the conversion of the feedstock over 10h of run.
[ example 15 ]
Adding 20g of ferric nitrate nonahydrate and 4g of cobalt nitrate hexahydrate into water, completely dissolving at 80 ℃, dropwise adding 10mL of chloroplatinic acid with the concentration of 16.14mL/L, stirring, dropwise adding ammonia water to adjust the pH value of the mixed solution to 8, stirring until a large amount of precipitates are generated in the solution, filtering the solution, and washing a filter cake to obtain a catalyst precursor. Activating the precursor in an atmosphere furnace to obtain the catalyst, wherein the activation temperature is 500 ℃, the activation time is 4h, the heating rate is 5 ℃/min, the pressure is normal, the gas flow rate is 200mL/min, the activation gas is mixed gas of ethane and propane, and the volume ratio of the ethane to the propane is 9: 1. The composition of the catalyst is shown in table 1, and the preparation conditions are shown in table 2.
1 g of the catalyst was taken for evaluation in an isothermal fixed bed reactor and reduced with hydrogen before evaluation under the following reduction conditions: the pressure and the normal pressure are controlled, the temperature is 350 ℃, the hydrogen flow is 200mL/min, the reduction time is 4h, and then the temperature is reduced for evaluation, wherein the evaluation conditions are as follows: the reaction pressure is 8MPa, the temperature is 160 ℃, and the space velocity is 2h-1Perhydroaminoethylcarbazole was used as a representative raw material for hydrogen storage in the organic liquid, and 0.5% of the product amount was recycled to the inlet of the reactor. The test conditions and test results are shown in Table 3. Wherein X10 represents the conversion of the feedstock over 10h of run.
[ example 16 ]
Adding 20g of ferric nitrate nonahydrate and 4g of cobalt nitrate hexahydrate into water, completely dissolving at 80 ℃, dropwise adding 10mL of chloroplatinic acid with the concentration of 16.14mL/L, stirring, dropwise adding ammonia water to adjust the pH value of the mixed solution to 8, stirring until a large amount of precipitates are generated in the solution, filtering the solution, and washing a filter cake to obtain a catalyst precursor. Activating the precursor in an atmosphere furnace to obtain the catalyst, wherein the activation temperature is 500 ℃, the activation time is 4h, the heating rate is 5 ℃/min, the pressure is normal, the gas flow rate is 200mL/min, the activation gas is mixed gas of ethane and propane, and the volume ratio of the ethane to the propane is 9: 1. The composition of the catalyst is shown in table 1, and the preparation conditions are shown in table 2.
1 g of the catalyst was taken for evaluation in an isothermal fixed bed reactor and reduced with hydrogen before evaluation under the following reduction conditions: the pressure and the normal pressure are controlled, the temperature is 350 ℃, the hydrogen flow is 200mL/min, the reduction time is 4h, and then the temperature is reduced for evaluation, wherein the evaluation conditions are as follows: the reaction pressure is 8MPa, the temperature is 160 ℃, and the space velocity is 2h-1Perhydroaminoethylcarbazole was used as a representative raw material for hydrogen storage in organic liquids, and 1% of the product amount was recycled to the reactor inlet. The test conditions and test results are shown in Table 3. Wherein X10 represents the conversion of the feedstock over 10h of run.
[ example 17 ]
Adding 20g of ferric nitrate nonahydrate and 4g of cobalt nitrate hexahydrate into water, completely dissolving at 80 ℃, dropwise adding 10mL of chloroplatinic acid with the concentration of 16.14mL/L, stirring, dropwise adding ammonia water to adjust the pH value of the mixed solution to 8, stirring until a large amount of precipitates are generated in the solution, filtering the solution, and washing a filter cake to obtain a catalyst precursor. Activating the precursor in an atmosphere furnace to obtain the catalyst, wherein the activation temperature is 500 ℃, the activation time is 4h, the heating rate is 5 ℃/min, the pressure is normal, the gas flow rate is 200mL/min, the activation gas is mixed gas of ethane and propane, and the volume ratio of the ethane to the propane is 9: 1. The composition of the catalyst is shown in table 1, and the preparation conditions are shown in table 2.
1 g of the catalyst was taken for evaluation in an isothermal fixed bed reactor and reduced with hydrogen before evaluation under the following reduction conditions: reducing at 350 deg.C under normal pressure and hydrogen flow of 200mL/minThe time is 4h, and then the temperature is reduced for evaluation, wherein the evaluation conditions are as follows: the reaction pressure is 8MPa, the temperature is 160 ℃, and the space velocity is 2h-1Perhydroaminoethylcarbazole was used as a representative raw material for hydrogen storage in organic liquids, and 2% of the product amount was recycled to the reactor inlet. The test conditions and test results are shown in Table 3. Wherein X10 represents the conversion of the feedstock over 10h of run.
[ example 18 ]
Adding 20g of ferric nitrate nonahydrate and 4g of cobalt nitrate hexahydrate into water, completely dissolving at 80 ℃, dropwise adding 10mL of chloroplatinic acid with the concentration of 16.14mL/L, stirring, dropwise adding ammonia water to adjust the pH value of the mixed solution to 8, stirring until a large amount of precipitates are generated in the solution, filtering the solution, and washing a filter cake to obtain a catalyst precursor. Activating the precursor in an atmosphere furnace to obtain the catalyst, wherein the activation temperature is 500 ℃, the activation time is 4h, the heating rate is 5 ℃/min, the pressure is normal, the gas flow rate is 200mL/min, the activation gas is mixed gas of ethane and propane, and the volume ratio of the ethane to the propane is 9: 1. The composition of the catalyst is shown in table 1, and the preparation conditions are shown in table 2.
1 g of the catalyst was taken for evaluation in an isothermal fixed bed reactor and reduced with hydrogen before evaluation under the following reduction conditions: the pressure and the normal pressure are controlled, the temperature is 350 ℃, the hydrogen flow is 200mL/min, the reduction time is 4h, and then the temperature is reduced for evaluation, wherein the evaluation conditions are as follows: the reaction pressure is 8MPa, the temperature is 160 ℃, and the space velocity is 2h-1Perhydrocarbazole is used as a representative raw material for storing hydrogen in an organic liquid. The test conditions and test results are shown in Table 3. Wherein X10 represents the conversion of the feedstock over 10h of run.
[ example 19 ]
Adding 20g of ferric nitrate nonahydrate and 4g of cobalt nitrate hexahydrate into water, completely dissolving at 80 ℃, dropwise adding 10mL of chloroplatinic acid with the concentration of 16.14mL/L, stirring, dropwise adding ammonia water to adjust the pH value of the mixed solution to 8, stirring until a large amount of precipitates are generated in the solution, filtering the solution, and washing a filter cake to obtain a catalyst precursor. Activating the precursor in an atmosphere furnace to obtain the catalyst, wherein the activation temperature is 500 ℃, the activation time is 4h, the heating rate is 5 ℃/min, the pressure is normal, the gas flow rate is 200mL/min, the activation gas is mixed gas of ethane and propane, and the volume ratio of the ethane to the propane is 9: 1. The composition of the catalyst is shown in table 1, and the preparation conditions are shown in table 2.
1 g of the catalyst was taken for evaluation in an isothermal fixed bed reactor and reduced with hydrogen before evaluation under the following reduction conditions: the pressure and the normal pressure are controlled, the temperature is 350 ℃, the hydrogen flow is 200mL/min, the reduction time is 4h, and then the temperature is reduced for evaluation, wherein the evaluation conditions are as follows: the reaction pressure is 8MPa, the temperature is 160 ℃, and the space velocity is 2h-1Perhydropyridine was used as a representative raw material for organic liquid hydrogen storage. The test conditions and test results are shown in Table 3. Wherein X10 represents the conversion of the feedstock over 10h of run.
[ example 20 ]
Adding 20g of ferric nitrate nonahydrate and 4g of cobalt nitrate hexahydrate into water, completely dissolving at 80 ℃, dropwise adding 10mL of chloroplatinic acid with the concentration of 16.14mL/L, stirring, dropwise adding ammonia water to adjust the pH value of the mixed solution to 8, stirring until a large amount of precipitates are generated in the solution, filtering the solution, and washing a filter cake to obtain a catalyst precursor. Activating the precursor in an atmosphere furnace to obtain the catalyst, wherein the activation temperature is 500 ℃, the activation time is 4h, the heating rate is 5 ℃/min, the pressure is normal, the gas flow rate is 200mL/min, the activation gas is mixed gas of ethane and propane, and the volume ratio of the ethane to the propane is 9: 1. The composition of the catalyst is shown in table 1, and the preparation conditions are shown in table 2.
1 g of the catalyst was taken for evaluation in a slurry bed reactor and reduced with hydrogen before evaluation under the following reduction conditions: the pressure and the normal pressure are controlled, the temperature is 350 ℃, the hydrogen flow is 200mL/min, the reduction time is 4h, and then the temperature is reduced for evaluation, wherein the evaluation conditions are as follows: the reaction pressure is 8MPa, the temperature is 160 ℃, and the space velocity is 2h-1Perhydroaminoethylcarbazole is used as a representative raw material for storing hydrogen in an organic liquid. The test conditions and test results are shown in Table 3. Wherein X10 represents the conversion of the feedstock over 10h of run.
[ example 21 ]
Adding 20g of ferric nitrate nonahydrate and 4g of cobalt nitrate hexahydrate into water, completely dissolving at 80 ℃, dropwise adding 10mL of chloroplatinic acid with the concentration of 16.14mL/L, stirring, dropwise adding ammonia water to adjust the pH value of the mixed solution to 8, stirring until a large amount of precipitates are generated in the solution, filtering the solution, and washing a filter cake to obtain a catalyst precursor. Activating the precursor in an atmosphere furnace to obtain the catalyst, wherein the activation temperature is 500 ℃, the activation time is 4h, the heating rate is 5 ℃/min, the pressure is normal, the gas flow rate is 200mL/min, the activation gas is mixed gas of ethane and propane, and the volume ratio of the ethane to the propane is 9: 1. The composition of the catalyst is shown in table 1, and the preparation conditions are shown in table 2.
1 g of the catalyst was taken for evaluation in a moving bed reactor and reduced with hydrogen before evaluation under the following reduction conditions: the pressure and the normal pressure are controlled, the temperature is 350 ℃, the hydrogen flow is 200mL/min, the reduction time is 4h, and then the temperature is reduced for evaluation, wherein the evaluation conditions are as follows: the reaction pressure is 8MPa, the temperature is 160 ℃, and the space velocity is 2h-1Perhydroaminoethylcarbazole is used as a representative raw material for storing hydrogen in an organic liquid. The test conditions and test results are shown in Table 3. Wherein X10 represents the conversion of the feedstock over 10h of run.
[ example 22 ]
Adding 40g of ferric nitrate nonahydrate into water, completely dissolving at 80 ℃, dropwise adding 10mL of chloroplatinic acid with the concentration of 16.14mL/L, stirring, dropwise adding ammonia water to adjust the pH value of the mixed solution to 8, stirring until a large amount of precipitate is generated in the solution, filtering the solution, and washing a filter cake to obtain a catalyst precursor. Activating the precursor in an atmosphere furnace at the activation temperature of 500 ℃ for 4h, at the heating rate of 5 ℃/min under normal pressure and at the gas flow rate of 200mL/min, wherein the activated gas is methane, and thus obtaining the catalyst. The composition of the catalyst is shown in table 1, and the preparation conditions are shown in table 2.
1 g of the catalyst was taken for evaluation in a moving bed reactor and reduced with hydrogen before evaluation under the following reduction conditions: the pressure and the normal pressure are controlled, the temperature is 350 ℃, the hydrogen flow is 200mL/min, the reduction time is 4h, and then the temperature is reduced for evaluation, wherein the evaluation conditions are as follows: the reaction pressure is 8MPa, the temperature is 160 ℃, and the space velocity is 2h-1Perhydroaminoethylcarbazole is used as a representative raw material for storing hydrogen in an organic liquid. The test conditions and test results are shown in Table 3. Wherein X10 represents the conversion of the feedstock over 10h of run.
[ example 23 ]
Adding 10g of cobalt nitrate hexahydrate into water, completely dissolving the cobalt nitrate hexahydrate at 80 ℃, dropwise adding 10mL of chloroplatinic acid with the concentration of 16.14mL/L into the cobalt nitrate hexahydrate, stirring, dropwise adding ammonia water to adjust the pH value of the mixed solution to 8, stirring until a large amount of precipitates are generated in the solution, filtering the solution, and washing a filter cake to obtain a catalyst precursor. Activating the precursor in an atmosphere furnace to obtain the catalyst, wherein the activation temperature is 500 ℃, the activation time is 4h, the heating rate is 5 ℃/min, the pressure is normal, the gas flow rate is 200mL/min, the activation gas is mixed gas of ethane and propane, and the volume ratio of the ethane to the propane is 9: 1. The composition of the catalyst is shown in table 1, and the preparation conditions are shown in table 2.
1 g of the catalyst was taken for evaluation in a moving bed reactor and reduced with hydrogen before evaluation under the following reduction conditions: the pressure and the normal pressure are controlled, the temperature is 350 ℃, the hydrogen flow is 200mL/min, the reduction time is 4h, and then the temperature is reduced for evaluation, wherein the evaluation conditions are as follows: the reaction pressure is 8MPa, the temperature is 160 ℃, and the space velocity is 2h-1Perhydroaminoethylcarbazole is used as a representative raw material for storing hydrogen in an organic liquid. The test conditions and test results are shown in Table 3. Wherein X10 represents the conversion of the feedstock over 10h of run.
[ example 24 ]
Adding 20g of ferric nitrate nonahydrate and 6g of cupric nitrate trihydrate into water, completely dissolving the ferric nitrate nonahydrate and the cupric nitrate trihydrate at 80 ℃, dropwise adding 60mL of palladium chloride with the concentration of 16.14mL/L into the mixture, stirring, dropwise adding ammonia water to adjust the pH value of the mixed solution to 8, stirring until a large amount of precipitates are generated in the solution, filtering the solution, and washing a filter cake to obtain a catalyst precursor. Activating the precursor in an atmosphere furnace to obtain the catalyst, wherein the activation temperature is 500 ℃, the activation time is 4h, the heating rate is 5 ℃/min, the pressure is normal, the gas flow rate is 200mL/min, the activation gas is mixed gas of ethane and propane, and the volume ratio of the ethane to the propane is 9: 1. The composition of the catalyst is shown in table 1, and the preparation conditions are shown in table 2.
1 g of the catalyst was taken for evaluation in a moving bed reactor and reduced with hydrogen before evaluation under the following reduction conditions: the pressure and the normal pressure are controlled, the temperature is 350 ℃, the hydrogen flow is 200mL/min, the reduction time is 4h, and then the temperature is reduced for evaluation, wherein the evaluation conditions are as follows: the reaction pressure is 8MPa, the temperature is 160 ℃, and the space velocity is 2h-1With perhydroazeethylcarbazole as baseIs a representative raw material for organic liquid hydrogen storage. The test conditions and test results are shown in Table 3. Wherein X10 represents the conversion of the feedstock over 10h of run.
[ example 25 ]
Adding 20g of ferric nitrate nonahydrate and 4g of cobalt nitrate hexahydrate into water, completely dissolving at 80 ℃, dropwise adding 60mL of palladium chloride with the concentration of 16.14mL/L, stirring, dropwise adding sodium citrate to adjust the pH value of the mixed solution to 8, stirring until a large amount of precipitates are generated in the solution, filtering the solution, and washing a filter cake to obtain a catalyst precursor. Activating the precursor in an atmosphere furnace to obtain the catalyst, wherein the activation temperature is 500 ℃, the activation time is 4h, the heating rate is 5 ℃/min, the pressure is normal, the gas flow rate is 200mL/min, the activation gas is mixed gas of ethane and propane, and the volume ratio of the ethane to the propane is 9: 1. The composition of the catalyst is shown in table 1, and the preparation conditions are shown in table 2.
1 g of the catalyst was taken for evaluation in a moving bed reactor and reduced with hydrogen before evaluation under the following reduction conditions: the pressure and the normal pressure are controlled, the temperature is 350 ℃, the hydrogen flow is 200mL/min, the reduction time is 4h, and then the temperature is reduced for evaluation, wherein the evaluation conditions are as follows: the reaction pressure is 8MPa, the temperature is 160 ℃, and the space velocity is 2h-1Perhydroaminoethylcarbazole is used as a representative raw material for storing hydrogen in an organic liquid. The test conditions and test results are shown in Table 3. Wherein X10 represents the conversion of the feedstock over 10h of run.
[ example 26 ]
Adding 20g of ferric nitrate nonahydrate and 4g of cobalt nitrate hexahydrate into water, completely dissolving at 80 ℃, dropwise adding 60mL of palladium chloride with the concentration of 16.14mL/L, stirring, dropwise adding ammonia water to adjust the pH value of the mixed solution to 10, stirring until a large amount of precipitates are generated in the solution, filtering the solution, and washing a filter cake to obtain a catalyst precursor. Activating the precursor in an atmosphere furnace to obtain the catalyst, wherein the activation temperature is 500 ℃, the activation time is 4h, the heating rate is 5 ℃/min, the pressure is normal, the gas flow rate is 200mL/min, the activation gas is mixed gas of ethane and propane, and the volume ratio of the ethane to the propane is 9: 1. The composition of the catalyst is shown in table 1, and the preparation conditions are shown in table 2.
Taking 1 g of catalyst in a moving bed reactorThe evaluation was carried out by reducing with hydrogen before the evaluation under the following reducing conditions: the pressure and the normal pressure are controlled, the temperature is 350 ℃, the hydrogen flow is 200mL/min, the reduction time is 4h, and then the temperature is reduced for evaluation, wherein the evaluation conditions are as follows: the reaction pressure is 8MPa, the temperature is 160 ℃, and the space velocity is 2h-1Perhydroaminoethylcarbazole is used as a representative raw material for storing hydrogen in an organic liquid. The test conditions and test results are shown in Table 3. Wherein X10 represents the conversion of the feedstock over 10h of run.
[ example 27 ]
Adding 20g of ferric nitrate nonahydrate, 5g of cobalt nitrate hexahydrate and 3g of copper nitrate trihydrate into water, completely dissolving the mixture at 80 ℃, dropwise adding 60mL of palladium chloride with the concentration of 16.14mL/L, stirring, dropwise adding ammonia water to adjust the pH value of the mixed solution to 8, stirring until a large amount of precipitates are generated in the solution, filtering the solution, and washing a filter cake to obtain a catalyst precursor. Activating the precursor in an atmosphere furnace to obtain the catalyst, wherein the activation temperature is 500 ℃, the activation time is 4h, the heating rate is 5 ℃/min, the pressure is normal, the gas flow rate is 200mL/min, the activation gas is mixed gas of ethane and propane, and the volume ratio of the ethane to the propane is 9: 1. The composition of the catalyst is shown in table 1, and the preparation conditions are shown in table 2.
1 g of the catalyst was taken for evaluation in a moving bed reactor and reduced with hydrogen before evaluation under the following reduction conditions: the pressure and the normal pressure are controlled, the temperature is 350 ℃, the hydrogen flow is 200mL/min, the reduction time is 4h, and then the temperature is reduced for evaluation, wherein the evaluation conditions are as follows: the reaction pressure is 8MPa, the temperature is 160 ℃, and the space velocity is 2h-1Perhydroaminoethylcarbazole is used as a representative raw material for storing hydrogen in an organic liquid. The test conditions and test results are shown in Table 3. Wherein X10 represents the conversion of the feedstock over 10h of run.
Comparative example 1
Adding 20g of ferric nitrate nonahydrate and 4g of cobalt nitrate hexahydrate into water, completely dissolving at 80 ℃, dropwise adding 10mL of chloroplatinic acid with the concentration of 16.14mL/L, stirring, dropwise adding ammonia water to adjust the pH value of the mixed solution to 8, stirring until a large amount of precipitates are generated in the solution, filtering the solution, and washing a filter cake to obtain a catalyst precursor. Activating the precursor in an atmosphere furnace to obtain the catalyst, wherein the activation temperature is 500 ℃, the activation time is 4h, the heating rate is 5 ℃/min, the pressure is normal, the gas flow rate is 200mL/min, the activation gas is mixed gas of ethane and propane, and the volume ratio of the ethane to the propane is 9: 1. The composition of the catalyst is shown in table 1, and the preparation conditions are shown in table 2.
The agent was evaluated in an isothermal fixed bed reactor, and reduced with hydrogen before evaluation under the following conditions: the pressure and the normal pressure are controlled, the temperature is 350 ℃, the hydrogen flow is 200mL/min, the reduction time is 4h, and then the temperature is reduced for evaluation, wherein the evaluation conditions are as follows: the reaction pressure is 2MPa, the temperature is 320 ℃, and the space velocity is 2h-1Perhydroaminoethylcarbazole is used as a representative raw material for storing hydrogen in an organic liquid. The test conditions and test results are shown in Table 3. Wherein X10 represents the conversion of the feedstock over 10h of run.
Comparative example 2
Adding 20g of ferric nitrate nonahydrate and 4g of cobalt nitrate hexahydrate into water, completely dissolving at 80 ℃, dropwise adding 10mL of chloroplatinic acid with the concentration of 16.14mL/L, stirring, dropwise adding ammonia water to adjust the pH value of the mixed solution to 8, stirring until a large amount of precipitates are generated in the solution, filtering the solution, and washing a filter cake to obtain a catalyst precursor. Activating the precursor in an atmosphere furnace to obtain the catalyst, wherein the activation temperature is 500 ℃, the activation time is 4h, the heating rate is 5 ℃/min, the pressure is normal, the gas flow rate is 200mL/min, the activation gas is mixed gas of ethane and propane, and the volume ratio of the ethane to the propane is 9: 1. The composition of the catalyst is shown in table 1, and the preparation conditions are shown in table 2.
The catalyst was evaluated in an isothermal fixed bed reactor, and reduced with hydrogen before evaluation under the following conditions: the pressure and the normal pressure are controlled, the temperature is 350 ℃, the hydrogen flow is 200mL/min, the reduction time is 4h, and then the temperature is reduced for evaluation, wherein the evaluation conditions are as follows: the reaction pressure is 2MPa, the temperature is 250 ℃, and the space velocity is 2h-1Perhydroaminoethylcarbazole is used as a representative raw material for storing hydrogen in an organic liquid. The test conditions and test results are shown in Table 3. Wherein X10 represents the conversion of the feedstock over 10h of run.
Comparative example 3
Adding 20g of ferric nitrate nonahydrate and 4g of cobalt nitrate hexahydrate into water, completely dissolving at 80 ℃, dropwise adding 10mL of chloroplatinic acid with the concentration of 16.14mL/L, stirring, dropwise adding ammonia water to adjust the pH value of the mixed solution to 8, stirring until a large amount of precipitates are generated in the solution, filtering the solution, and washing a filter cake to obtain a catalyst precursor. Activating the precursor in an atmosphere furnace to obtain the catalyst, wherein the activation temperature is 500 ℃, the activation time is 4h, the heating rate is 5 ℃/min, the pressure is normal, the gas flow rate is 200mL/min, the activation gas is mixed gas of ethane and propane, and the volume ratio of the ethane to the propane is 9: 1. The composition of the catalyst is shown in table 1, and the preparation conditions are shown in table 2.
The catalyst was evaluated in a membrane reactor, before the evaluation, using hydrogen for reduction under the following conditions: the pressure and the normal pressure are controlled, the temperature is 350 ℃, the hydrogen flow is 200mL/min, the reduction time is 4h, and then the temperature is reduced for evaluation, wherein the evaluation conditions are as follows: the reaction pressure is 2MPa, the temperature is 280 ℃, and the space velocity is 2h-1Perhydroaminoethylcarbazole is used as a representative raw material for storing hydrogen in an organic liquid. The test conditions and test results are shown in Table 3. Wherein X10 represents the conversion of the feedstock over 10h of run.
TABLE 1 catalyst composition
Figure BDA0001830197800000171
Figure BDA0001830197800000181
TABLE 2 catalyst preparation conditions
Figure BDA0001830197800000182
Figure BDA0001830197800000191
TABLE 3 evaluation results of heterocyclic cycloalkane Hydrogen storage Compounds
Figure BDA0001830197800000192
Figure BDA0001830197800000201
Figure BDA0001830197800000211

Claims (12)

1. A method for dehydrogenating the hydrogen storage material containing heterocyclic cycloalkane in liquid phase includes such steps as reaction between said hydrogen storage material and bifunctional catalyst in reactor to generate hydrogen and resultant; wherein,
the bifunctional catalyst comprises the following components in percentage by weight: 1) 0.1-5 parts of an active central body for carbon-hydrogen bond cleavage; 2) 70-90 parts of a backbone anchoring the active centrosome; wherein the active central body is at least one metal selected from platinum group metals or an alloy thereof, and the skeleton is a metal carbide;
the metal carbide is selected from a compound formed by at least one of Fe and Cu and carbon element.
2. The liquid phase dehydrogenation process of claim 1, wherein the reaction conditions are as follows: the reaction pressure is 2-10 MPa, the temperature is 80-250 ℃, and the mass space velocity is 0.1-10 h-1And the product circulation amount is 0-2%.
3. The liquid phase dehydrogenation process of claim 2, wherein the reaction conditions are as follows: the reaction pressure is 4-8 MPa, the temperature is 100-230 ℃, and the mass space velocity is 0.1-6 h-1And the product circulation amount is 0-1%.
4. The liquid phase dehydrogenation process of claim 1, wherein the heterocyclic cycloalkane is selected from at least one of the group consisting of perhydroazeethylcarbazole, perhydrotriazine, perhydropyrrole, perhydrocarbazole.
5. The liquid phase dehydrogenation process of claim 1, wherein the reactor is selected from the group consisting of a fixed bed reactor, a trickle bed reactor, a tank reactor, a slurry bed reactor, and a moving bed reactor.
6. The bifunctional catalyst according to claim 1, wherein the mass ratio of Fe, Cu and C is (30-6): 1.
7. The bifunctional catalyst according to claim 6, wherein the mass ratio of Fe, Cu and C is (16-4): 1.
8. Bifunctional catalyst according to claim 6 or 7, characterized in that the preparation process is as follows:
1) dissolving at least one metal element salt of Fe and Cu, and mixing with a platinum group metal element solution to obtain a precursor;
2) activating the precursor in an atmosphere furnace, and partially carbonizing Fe and Cu by hydrocarbon gas to obtain an active central body cracked by taking platinum group metal as a carbon-hydrogen bond, wherein at least one metal element in Fe and Cu and C form a catalyst for anchoring the framework of the active central body.
9. The method for preparing a bifunctional catalyst according to claim 8, characterized in that the method for preparing a catalyst further comprises a step of co-precipitation, with the proviso that: the temperature is 40-100 ℃, the pressure is normal, and the pH is 7.1-12; the dissolution temperature of the salt of the metal element is 40 to 100 ℃.
10. The method of claim 8, wherein the atmosphere furnace gas comprises: methane, ethane, propane, butane, isobutane, butene, ethylbenzene, styrene.
11. The method of claim 8, wherein the precursor activation conditions are: the temperature is 400-600 ℃, the time is 1-8 h, the heating rate is 1-20 ℃/min, the pressure is normal, and the gas flow rate is 50-400 mL/min.
12. The method of claim 9, wherein the pH controlling agent is at least one of ammonia, sodium hydroxide, sodium bicarbonate, potassium carbonate, sodium citrate, potassium citrate, monosodium citrate, trisodium bicarbonate.
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