CN107537587B - Method for treating catalyst - Google Patents
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- CN107537587B CN107537587B CN201610498151.3A CN201610498151A CN107537587B CN 107537587 B CN107537587 B CN 107537587B CN 201610498151 A CN201610498151 A CN 201610498151A CN 107537587 B CN107537587 B CN 107537587B
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Abstract
The invention relates to a method for treating a catalyst, which is characterized in that carbohydrate is adopted for carbon coating treatment, the technical problems to be solved by the invention are that Pt is not uniformly dispersed, the catalyst is easy to coke, and the activity and the stability are poor in the prior art.
Description
Technical Field
The invention discloses a method for treating a catalyst, and particularly relates to a method for treating a dehydrogenation catalyst or a hydrogenation catalyst.
Background
Hydrogen energy has been widely spotlighted as a representative of green sustainable new energy. In the beginning of the 21 st century, hydrogen energy development plans were made in china and the united states, japan, canada, european union, etc., and related studies were pursued. Hydrogen energy applications include hydrogen gas production, storage, transportation, and application links, where hydrogen energy storage is a key and difficult point. Hydrogen fuel vehicles are the main approach for hydrogen energy application, and the development of hydrogen storage technology suitable for hydrogen fuel vehicles is the premise of large-scale application of hydrogen energy.
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. Organic liquid hydrogen storage technology in chemical hydrogen storage (organic liquid mainly comprises methyl cyclohexane)Alkane, cyclohexane, tetrahydronaphthalene, decahydronaphthalene, perhydroazeethylcarbazole, perhydrocarbazole, etc.) is used to store hydrogen energy by catalytic addition and dehydrogenation reversible reactions, the reaction in the process is reversible, the reactant products can be recycled, and the hydrogen storage capacity is relatively high (about 60-75kg H)2/m3The mass fraction is 6-8 percent), meets the indexes specified by the International energy agency and the United states department of energy (DOE), is transported for a long distance in the form of organic liquid or can solve the problem of uneven distribution of energy in areas, really meets the requirement of green chemistry and has stronger application prospect.
The hydrogenation process and the dehydrogenation process exist simultaneously in the organic liquid hydrogen storage technology, the hydrogenation process is relatively simple, the technology is mature, and the dehydrogenation process is a strong endothermic and highly reversible reaction, so that the dehydrogenation reaction is favorably carried out at high temperature from the aspects of dynamics and thermodynamics, but the activity of the catalyst is reduced and even inactivated due to side reactions such as cracking, carbon deposition and the like which are easily generated at high temperature, and the dehydrogenation reaction is not favorably carried out.
Pt/Al is simple and cheap in preparation method2O3The catalyst is widely used as a dehydrogenation catalyst of an organic liquid hydrogen storage material, but the catalyst needs to be calcined at high temperature and reduced by hydrogen in the preparation process, so that the aggregation size of Pt atoms is easily increased, and the activity is finally reduced, and in addition, Al2O3The weak acidity of the surface and the low specific surface area are easy to generate coking in the reaction process, and Pt is not easy to disperse, so that the activity and the stability of the catalyst are poor, and the Pt/Al catalyst is poor2O3Is not an ideal dehydrogenation catalyst for organic liquid hydrogen storage materials, and the research on high-activity and high-stability dehydrogenation catalysts is urgently needed. Since the dehydrogenation effect of Pt is the best among all metals, the focus of research on organic liquid dehydrogenation catalysts is to select a support with a large specific surface area and a weak or non-acidic surface to prepare a catalyst with small Pt size and low tendency to coke.
Al2O3Good mechanical strength, high thermal stability and low price, and is widely applied to petrochemical industry, but Al2O3Acid sites exist on the surface, and in the reaction processThe C-C bond is easy to break, which causes the catalyst to coke and carbon deposit.
The carbon material has good anti-coking performance due to no acidity on the surface, has large specific surface area and is beneficial to dispersing active components, but the carbon material has low mechanical strength and small micropore diameter, and has certain difficulty when being singly used as a carrier.
If the carbon material is mixed with Al2O3Bonded to Al with a carbon material2O3The surface is modified, and the carrier with the advantages of alumina and carbon material is developed, so that the problem of the existing organic liquid hydrogen storage material dehydrogenation catalyst can be solved.
CN1193655A discloses a preparation method of a dehydrogenation catalyst with carbon-coated alumina. The gamma-Al of the patent is 40-80 meshes (0.2-0.45mm)2O3Placing in a reactor, carrying volatile hydrocarbon into the reactor by using N2, and cracking and coating carbon at the temperature of about 600 ℃ to obtain the carrier. The carrier is used for soaking metals such as Pt, Co, Ni and the like for catalyzing cyclohexane dehydrogenation, and the result shows that the activity of the carrier is higher than that of pure gamma-Al2O3The supported catalyst is improved by about 7-8%.
CN101327454A discloses a modified carbon-coated alumina carrier with a core-shell structure and a preparation method thereof. The patent uses industrial Al with the diameter of 1-3mm and the length of 3-8mm2O3For nucleus, transition metal salt containing Ni, Co and Fe and isopropanol or sec-butanol are dissolved in isopropanol or ethanol to prepare colloid, and then the colloid is loaded on industrial Al in a dipping or spraying manner2O3And (3) drying and calcining the core, placing the core in a reaction furnace, introducing argon, reducing the hydrogen mixed gas at the temperature of 550-650 ℃, then introducing a carbon source and hydrogen mixed gas for carbon coating, and cooling to obtain the modified carbon-coated alumina carrier. The carbon source gas used is methane, ethane or carbon monoxide. On a carrier with industrial Al2O3The alumina with deposited carbon as the core and the shell can be used for hydrotreating in petrochemical processing.
CN201010559898.8 discloses a preparation process of a dehydrogenation catalyst based on a nano carbon-coated alumina carrier, which comprises the steps of,Hydrolyzing, precipitating, pre-burning, N2 heat treating and other steps to obtain nanometer level carbon coated gamma-Al2O3And (3) carrying a carrier, then loading an active metal component on the carrier, and activating to obtain the catalyst with good dehydrogenation performance.
The above patents have achieved certain results in improving the activity and stability of organic liquid dehydrogenation catalysts, but the gas coking method is used to coke Al2O3When the carbon coating is carried out, the gas is condensed and coked after being adsorbed on the acid sites on the surface of the alumina, and the gas easily reaches the outer surface and is easy to be coated on Al2O3Coking is carried out near the pore channel, the pore channel is blocked, the specific surface area of the pore channel is greatly reduced, and the utilization rate is reduced, while the method disclosed in the patent CN101327454A covers carbon and loads metal simultaneously in the preparation process, the carbon is likely to cover the metal surface, so that the metal utilization rate is reduced, and the CN201010559898.8 applies the carbon covering process to Al2O3The preparation process of (2) is not suitable for mass production.
Disclosure of Invention
The technical problem to be solved by the invention is that the catalyst active component has poor dispersion degree and activity and stability in the prior art, and the catalyst obtained by the method has the advantages of high dispersion of the active component, no acidity of the carrier, avoidance of coking in the reaction process, high activity and high stability.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a method for treating catalyst features that the carbohydrate is used for carbon coating.
In the technical scheme, the carbon coating treatment by adopting the carbohydrate is to perform carbon coating treatment on the carrier of the catalyst by adopting the carbohydrate.
In the technical scheme, the catalyst comprises an active component and a carrier, wherein the carrier provides at least part of active centers before the carbon coating treatment.
In the above technical scheme, at least part of the active center of the carrier is an acid center.
In the technical scheme, the active center is not provided after the carbon coating treatment of the carrier.
In the technical scheme, the catalyst is at least one of a dehydrogenation catalyst and a hydrogenation catalyst.
In the above technical solution, the preferred catalyst is one of a dehydrogenation catalyst and a hydrogenation catalyst.
In the technical scheme, the carbon element exists in the form of amorphous carbon after the carbon coating treatment.
In the technical scheme, the content of the carbon element accounts for 0.1-10% of the catalyst in percentage by weight after the carbon coating treatment.
In the above technical solution, preferably, the content of carbon element is 5-8% of the catalyst.
In the above technical scheme, the carrier is selected from at least one of alumina, silica, titania, magnesia, calcia, ceria and zirconia.
In the above technical scheme, the carbohydrate is at least one of sucrose, triose, tetrose, pentose, hexose, sugar alcohol, sugar acid, sugar amine, and glycoside.
In the above technical solution, preferably, the carbohydrate is a mixture of sucrose and triose.
In the technical scheme, the preferable mixing ratio of the sucrose to the triose is 1: 2-2: 1.
In the above technical scheme, the catalyst treatment method comprises the following steps:
(1) carrying out carbon coating treatment on the carrier to obtain a carbon coated carrier;
(2) the active ingredient is introduced by impregnation or precipitation.
In the above technical scheme, the carbon-coating treatment of the carrier is to impregnate the carrier with a carbohydrate solution.
In the technical scheme, the processing method comprises the steps of impregnating the carrier with carbohydrate solution, drying and roasting to obtain the carbon-coated carrier.
In the technical scheme, the treatment method is that roasting is carried out under a non-oxygen condition.
According to the unique properties of the carrier and the carbon carrier, firstly, carbohydrate is uniformly loaded on the surface of the carrier by adopting an impregnation/precipitation method, then, the carrier is roasted in a non-oxygen atmosphere to prepare an alumina carrier uniformly coated with carbon, and then, metal is loaded, so that the dehydrogenation catalyst or the hydrogenation catalyst with high activity and good stability is finally obtained, and a good technical effect is obtained.
The invention is further illustrated by the following examples, but is not limited thereto.
Detailed Description
[ example 1 ]
Preparing 3mL of sucrose solution with the concentration of 1%, and weighing 2g of formed Al2O3(the water absorption was determined to be 1.0) was added thereto, left to stand for 4 hours, then drained, dried in an oven at 120 ℃ for 4 hours, and placed in N2And roasting the mixture for 4 hours at 550 ℃ in an atmosphere muffle furnace to obtain the carbon-coated alumina carrier.
0.622mL of chloroplatinic acid solution with the concentration of 16.14mL/L is taken, 1.378mL of water is added to prepare a solution, 2g of carbon-coated alumina carrier is added into the solution, the solution is stirred and placed at room temperature for 2h, then the solution is dried at 120 ℃ for 4h, and finally the dried solution is placed into a muffle furnace with the atmosphere of N2 and roasted at 550 ℃ for 4h to obtain the catalyst.
The obtained catalyst was ground to a particle size of 12-20 mesh, and 1g was evaluated in an isothermal fixed bed reactor, and reduced with hydrogen gas before evaluation under the following conditions: the pressure and the normal pressure are controlled, the temperature is 450 ℃, the hydrogen flow is 200mL/min, the reduction time is 4h, and then the temperature is reduced for evaluation, wherein the evaluation conditions are as follows: the reaction pressure is normal pressure, the temperature is 320 ℃, and the space velocity is 2h-1Methylcyclohexane is used as a representative raw material for storing hydrogen in an organic liquid. The results are shown in Table 1.
To examine the stability of the catalyst, X2 and X100 were defined as the conversion of the feedstock in the reactions 2h and 100h, respectively.
[ example 2 ]
Preparing 3mL of sucrose solution with the concentration of 5%, and weighing 2g of formed Al2O3(the water absorption was determined to be 1.0) was added thereto, left to stand for 4 hours, then filtered off, oven-dried at 120 ℃ for 4 hours, placed in a muffle furnace under N2 atmosphere at 550 DEG CAnd roasting for 4 hours to obtain the carbon-coated alumina carrier.
0.622mL of chloroplatinic acid solution with the concentration of 16.14mL/L is taken, 1.378mL of water is added to prepare a solution, 2g of carbon-coated alumina carrier is added into the solution, stirred and placed at room temperature for 2h, then the solution is placed into a vacuum drying oven to be dried for 4h at 100 ℃ and the pressure of 0MPa, and then the dried solution is placed into a muffle furnace with the atmosphere of N2 to be roasted for 4h at 550 ℃ to obtain the catalyst.
The obtained catalyst was ground to a particle size of 12 to 20 mesh, 1g of the catalyst was evaluated in an isothermal fixed bed reactor, and before the evaluation, the catalyst was reduced with hydrogen under the same conditions as in example 1, and the results are shown in Table 1.
[ example 3 ]
3mL of a 5% sucrose/fructose (sucrose: fructose 3:1) mixed solution was prepared, and 2g of formed Al was weighed2O3(the water absorption was measured to be 1.0) was added thereto, left to stand for 4 hours, then filtered to dryness, baked in an oven at 120 ℃ for 4 hours, and put into a muffle furnace under an N2 atmosphere to be baked at 550 ℃ for 4 hours, to obtain a carbon-coated alumina carrier.
0.622mL of chloroplatinic acid solution with the concentration of 16.14mL/L is taken, 1.378mL of water is added to prepare a solution, 2g of carbon-coated alumina carrier is added into the solution, the solution is stirred and placed at room temperature for 2h, then the solution is dried at 120 ℃ for 4h, and finally the dried solution is placed into a muffle furnace with the atmosphere of N2 and roasted at 550 ℃ for 4h to obtain the catalyst.
The obtained catalyst was ground to a particle size of 12 to 20 mesh, 1g of the catalyst was evaluated in an isothermal fixed bed reactor, and before the evaluation, the catalyst was reduced with hydrogen under the same conditions as in example 1, and the results are shown in Table 1.
[ example 4 ]
3mL of a 5% sucrose-glycoside (sucrose: glycoside: 3:1) mixed solution was prepared, and 2g of formed Al was weighed2O3(the water absorption was measured to be 1.0) was added thereto, left to stand for 4 hours, then filtered to dryness, baked in an oven at 120 ℃ for 4 hours, and put into a muffle furnace under an N2 atmosphere to be baked at 550 ℃ for 4 hours, to obtain a carbon-coated alumina carrier.
0.622mL of chloroplatinic acid solution with the concentration of 16.14mL/L is taken, 1.378mL of water is added to prepare a solution, 2g of carbon-coated alumina carrier is added into the solution, the solution is stirred and placed at room temperature for 2h, then the solution is dried at 120 ℃ for 4h, and finally the dried solution is placed into a muffle furnace with the atmosphere of N2 and roasted at 550 ℃ for 4h to obtain the catalyst.
The obtained catalyst was ground to a particle size of 12 to 20 mesh, 1g of the catalyst was evaluated in an isothermal fixed bed reactor, and before the evaluation, the catalyst was reduced with hydrogen under the same conditions as in example 1, and the results are shown in Table 1.
[ example 5 ]
3mL of a 5% sucrose-triose (sucrose: triose-3: 1) mixed solution was prepared, and 2g of formed Al was weighed2O3(the water absorption was measured to be 1.0) was added thereto, left to stand for 4 hours, then filtered to dryness, baked in an oven at 120 ℃ for 4 hours, and put into a muffle furnace under an N2 atmosphere to be baked at 550 ℃ for 4 hours, to obtain a carbon-coated alumina carrier.
0.622mL of chloroplatinic acid solution with the concentration of 16.14mL/L is taken, 1.378mL of water is added to prepare a solution, 2g of carbon-coated alumina carrier is added into the solution, the solution is stirred and placed at room temperature for 2h, then the solution is dried at 120 ℃ for 4h, and finally the dried solution is placed into a muffle furnace with the atmosphere of N2 and roasted at 550 ℃ for 4h to obtain the catalyst.
The obtained catalyst was ground to a particle size of 12 to 20 mesh, 1g of the catalyst was evaluated in an isothermal fixed bed reactor, and before the evaluation, the catalyst was reduced with hydrogen under the same conditions as in example 1, and the results are shown in Table 1.
[ example 6 ]
3mL of sucrose solution with the concentration of 8 percent is prepared, and 2g of formed Al is weighed2O3(the water absorption was measured to be 1.0) was added thereto, left to stand for 4 hours, then filtered to dryness, baked in an oven at 120 ℃ for 4 hours, and put into a muffle furnace under an N2 atmosphere to be baked at 550 ℃ for 4 hours, to obtain a carbon-coated alumina carrier.
0.622mL of chloroplatinic acid solution with the concentration of 161.4mL/L is taken, 1.378mL of water is added to prepare a solution, 2g of carbon-coated alumina carrier is added into the solution, the solution is stirred and placed at room temperature for 2h, then the solution is dried at 120 ℃ for 4h, and finally the dried solution is placed into a muffle furnace with the atmosphere of N2 and roasted at 550 ℃ for 4h to obtain the catalyst.
The obtained catalyst was ground to a particle size of 12 to 20 mesh, 1g of the catalyst was evaluated in an isothermal fixed bed reactor, and before the evaluation, the catalyst was reduced with hydrogen under the same conditions as in example 1, and the results are shown in Table 1.
[ example 7 ]
3mL of a 8% sucrose/fructose (sucrose: fructose 2:1) mixed solution was prepared, and 2g of formed Al was weighed2O3(the water absorption was measured to be 1.0) was added thereto, left to stand for 4 hours, then filtered to dryness, baked in an oven at 120 ℃ for 4 hours, and put into a muffle furnace under an N2 atmosphere to be baked at 550 ℃ for 4 hours, to obtain a carbon-coated alumina carrier.
0.622mL of chloroplatinic acid solution with the concentration of 16.14mL/L is taken, 1.378mL of water is added to prepare a solution, 2g of carbon-coated alumina carrier is added into the solution, the solution is stirred and placed at room temperature for 2h, then the solution is dried at 120 ℃ for 4h, and finally the dried solution is placed into a muffle furnace with the atmosphere of N2 and roasted at 550 ℃ for 4h to obtain the catalyst.
The obtained catalyst was ground to a particle size of 12 to 20 mesh, 1g of the catalyst was evaluated in an isothermal fixed bed reactor, and before the evaluation, the catalyst was reduced with hydrogen under the same conditions as in example 1, and the results are shown in Table 1.
[ example 8 ]
3mL of 5% triose solution is prepared, and 2g of formed Al is weighed2O3(the water absorption was measured to be 1.0) was added thereto, left to stand for 4 hours, then filtered to dryness, baked in an oven at 120 ℃ for 4 hours, and put into a muffle furnace under an N2 atmosphere to be baked at 580 ℃ for 4 hours, to obtain a carbon-coated alumina carrier.
0.622mL of chloroplatinic acid solution with the concentration of 16.14mL/L is taken, 1.378mL of water is added to prepare a solution, 2g of carbon-coated alumina carrier is added into the solution, the solution is stirred and placed at room temperature for 2h, then the solution is dried at 120 ℃ for 4h, and finally the dried solution is placed into a muffle furnace with the atmosphere of N2 and roasted at 550 ℃ for 4h to obtain the catalyst.
The obtained catalyst was ground to a particle size of 12 to 20 mesh, 1g of the catalyst was evaluated in an isothermal fixed bed reactor, and before the evaluation, the catalyst was reduced with hydrogen under the same conditions as in example 1, and the results are shown in Table 1.
[ example 9 ]
Preparing 3mL of 10% glucoside solution, weighing 2g of formed Al2O3(the water absorption was measured to be 1.0) was added thereto, left to stand for 4 hours, then filtered to dryness, baked in an oven at 120 ℃ for 4 hours, and put into a muffle furnace under an N2 atmosphere to be baked at 550 ℃ for 4 hours, to obtain a carbon-coated alumina carrier.
0.622mL of chloroplatinic acid solution with the concentration of 16.14mL/L is taken, 1.378mL of water is added to prepare a solution, 2g of carbon-coated alumina carrier is added into the solution, the solution is stirred and placed at room temperature for 2h, then the solution is dried at 120 ℃ for 4h, and finally the dried solution is placed into a muffle furnace with the atmosphere of N2 and roasted at 550 ℃ for 4h to obtain the catalyst.
The obtained catalyst was ground to a particle size of 12 to 20 mesh, 1g of the catalyst was evaluated in an isothermal fixed bed reactor, and before the evaluation, the catalyst was reduced with hydrogen under the same conditions as in example 1, and the results are shown in Table 1.
[ example 10 ]
3mL of a 5% sucrose/fructose (sucrose: 2:1) mixed solution was prepared, and 2g of a molded SiO solution was weighed2(the water absorption was determined to be 0.6) was added thereto, left to stand for 4 hours, then filtered to dryness, baked in an oven at 120 ℃ for 4 hours, and put into a muffle furnace under an N2 atmosphere to be baked at 550 ℃ for 4 hours, to obtain a carbon-coated alumina carrier.
0.622mL of chloroplatinic acid solution with the concentration of 16.14mL/L is taken, 0.578mL of water is added to prepare a solution, 2g of carbon-coated silica carrier is added into the solution, the solution is stirred and placed at room temperature for 2 hours, then the solution is dried at 120 ℃ for 4 hours and finally the dried solution is placed into a muffle furnace with the atmosphere of N2 to be roasted at 550 ℃ for 4 hours, and the catalyst is obtained.
The obtained catalyst was ground to a particle size of 12 to 20 mesh, 1g of the catalyst was evaluated in an isothermal fixed bed reactor, and before the evaluation, the catalyst was reduced with hydrogen under the same conditions as in example 1, and the results are shown in Table 1.
[ example 11 ]
3mL of a 5% sucrose-glycoside (sucrose: glycoside: 2:1) mixed solution was prepared, and 2g of a molded SiO solution was weighed2(the water absorption was determined to be 0.6) was added thereto, left to stand for 4 hours, then drained, baked in an oven at 120 ℃ for 4 hours, and put into a muffle furnace in a He atmosphere to be baked at 550 ℃ for 4 hours, to obtain a carbon-coated alumina carrier.
0.622mL of chloroplatinic acid solution with the concentration of 16.14mL/L is taken, 0.578mL of water is added to prepare a solution, 2g of carbon-coated silica carrier is added into the solution, the solution is stirred and placed at room temperature for 2h, then the solution is dried at 120 ℃ for 4h, and finally the solution is placed into a muffle furnace with the He atmosphere and roasted at 550 ℃ for 4h to obtain the catalyst.
The obtained catalyst was ground to a particle size of 12 to 20 mesh, 1g of the catalyst was evaluated in an isothermal fixed bed reactor, and before the evaluation, the catalyst was reduced with hydrogen under the same conditions as in example 1, and the results are shown in Table 1.
[ example 12 ]
3mL of a 5% sucrose-triose (sucrose: triose 2:1) mixed solution was prepared, and 2g of the molded TiO was weighed2(the water absorption was measured to be 0.8) was added thereto, left to stand for 4 hours, then filtered to dryness, baked in an oven at 120 ℃ for 4 hours, and put into a muffle furnace under an N2 atmosphere to be baked at 550 ℃ for 4 hours, to obtain a carbon-coated alumina carrier.
0.622mL of chloroplatinic acid solution with the concentration of 16.14mL/L is taken, 0.978mL of water is added to prepare a solution, 2g of carbon-coated silica carrier is added into the solution, the solution is stirred and placed at room temperature for 2 hours, then the solution is dried at 120 ℃ for 4 hours and finally the dried solution is placed into a muffle furnace with the atmosphere of N2 and roasted at 550 ℃ for 4 hours to obtain the catalyst.
The obtained catalyst was ground to a particle size of 12 to 20 mesh, 1g of the catalyst was evaluated in an isothermal fixed bed reactor, and before the evaluation, the catalyst was reduced with hydrogen under the same conditions as in example 1, and the results are shown in Table 1.
[ example 13 ]
3mL of a 5% sucrose-fructose (sucrose: fructose 2:1) mixed solution was prepared, and 2g of formed Al was weighed2O3(the water absorption was measured to be 1.0) was added thereto, left to stand for 4 hours, then filtered to dryness, baked in an oven at 120 ℃ for 4 hours, and put into a muffle furnace under an N2 atmosphere to be baked at 550 ℃ for 4 hours, to obtain a carbon-coated alumina carrier.
0.622mL of 16.14mL/L palladium chloride solution is taken and added with 1.378mL of water to prepare a solution, 2g of carbon-coated alumina carrier is added into the solution, stirred and placed at room temperature for 2h, and then dried at 120 ℃ for 4h, and finally the dried product is put into a muffle furnace with an N2 atmosphere and roasted at 550 ℃ for 4h to obtain the catalyst.
The obtained catalyst was ground to a particle size of 12 to 20 mesh, 1g of the catalyst was evaluated in an isothermal fixed bed reactor, and before the evaluation, the catalyst was reduced with hydrogen under the same conditions as in example 1, and the results are shown in Table 1.
[ example 14 ]
3mL of a 5% sucrose-glycoside (sucrose: glycoside: 2:1) mixed solution was prepared, and 2g of formed Al was weighed2O3(the water absorption was measured to be 1.0) was added thereto, left to stand for 4 hours, then filtered to dryness, baked in an oven at 120 ℃ for 4 hours, and put into a muffle furnace under an N2 atmosphere to be baked at 550 ℃ for 4 hours, to obtain a carbon-coated alumina carrier.
0.622mL of chloroplatinic acid solution with the concentration of 161.4mL/L and 0.1mL of KNO3 solution with the concentration of 0.1mL/L are taken, 1.378mL of water is added to prepare a solution, 2g of carbon-coated alumina carrier is added to the solution, stirred and placed at room temperature for 2h, then dried at 120 ℃ for 4h, and finally placed in a muffle furnace with the atmosphere of N2 to be roasted at 550 ℃ for 4h to obtain the catalyst.
The obtained catalyst was ground to a particle size of 12 to 20 mesh, 1g of the catalyst was evaluated in an isothermal fixed bed reactor, and before the evaluation, the catalyst was reduced with hydrogen under the same conditions as in example 1, and the results are shown in Table 1.
Comparative example 1
Taking 0.622mL chloroplatinic acid solution with the concentration of 16.14mL/L, adding 1.378mL water to prepare solution, and adding 2g gamma-Al2O3Adding 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 for 4h to obtain the desired catalyst.
The obtained catalyst was ground to a particle size of 12 to 20 mesh, 1g of the catalyst was evaluated in an isothermal fixed bed reactor, and before the evaluation, the catalyst was reduced with hydrogen under the same conditions as in example 1, and the results are shown in Table 1.
Comparative example 2
The catalyst was prepared by following the procedure of example 1 of CN201010559898.8, the obtained catalyst was ground to a particle size of 12 to 20 mesh, 1g of the catalyst was evaluated in an isothermal fixed bed reactor, and before the evaluation, the catalyst was reduced with hydrogen, and the reduction conditions and the evaluation conditions were the same as those of example 1, and the results are shown in Table 1.
Comparative example 3
The catalyst was prepared by following the procedure of example 1 of CN1193655A, the obtained catalyst was ground to a particle size of 12 to 20 mesh, 1g of the catalyst was evaluated in an isothermal fixed bed reactor, and before the evaluation, the catalyst was reduced with hydrogen, and the reduction conditions and the evaluation conditions were the same as those of example 1, and the results are shown in Table 1.
TABLE 1
[ examples 15 to 20 ]
The performance of the catalyst prepared in example 9 was evaluated for dehydrogenation of light alkane to light olefin, and the results are shown in table 2.
TABLE 2
[ examples 21 to 26 ]
The performance of the catalyst prepared in example 9 for dehydrogenation of organic liquid hydrogen storage material was evaluated and the results are shown in table 3.
TABLE 3
[ examples 27 to 30 ]
The performance of the catalyst prepared in example 9 for the hydrogenation of benzene and/or toluene was evaluated and the results are shown in Table 4.
TABLE 4
Claims (16)
1. The method for treating the catalyst is characterized by adopting carbohydrate for carbon coating treatment, wherein the carbohydrate is selected from a mixture of sucrose and triose, and the mixing weight ratio is 1: 2-2: 1.
2. The method according to claim 1, wherein the carrier of the catalyst is subjected to a carbon coating treatment with a carbohydrate.
3. The method of claim 1, wherein the catalyst comprises an active component and a support, the support providing at least a portion of the active sites prior to the carbon coating.
4. Method for the treatment of a catalyst according to claim 3, characterized in that the active centres are at least partially acid centres.
5. The method of claim 1, wherein no active sites are provided after the carbon coating treatment.
6. The method of claim 1, wherein the catalyst is a dehydrogenation catalyst and/or a hydrogenation catalyst.
7. The method according to any one of claims 1 to 6, wherein the carbon element is present in the form of amorphous carbon after the treatment.
8. The method according to any one of claims 1 to 6, wherein the carbon content of the catalyst after the treatment is 0.1 to 10% by weight.
9. The method of claim 8, wherein the carbon content of the catalyst after the treatment is 5-8 wt%.
10. The method according to claim 3, wherein the carrier is at least one selected from the group consisting of alumina, silica, titania, magnesia, calcia, ceria and zirconia.
11. The method of treating a catalyst according to claim 1, characterized in that the treatment comprises the steps of:
(1) carrying out carbon coating treatment on the carrier to obtain a carbon coated carrier;
(2) the active ingredient is introduced by impregnation or precipitation.
12. The method of claim 11, wherein the step of subjecting the support to carbon coating comprises impregnating the support with a carbohydrate solution.
13. The method of claim 12, wherein the carbon-coated support is obtained by impregnating the support with a carbohydrate solution, drying, and calcining.
14. The method of claim 13, wherein the calcination is performed under non-oxygen conditions.
15. A catalyst, characterised in that the catalyst has been treated by a process according to any one of claims 1 to 14.
16. Catalyst according to claim 15, characterized in that the catalyst is a hydrogenation catalyst and/or a dehydrogenation catalyst.
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| US11305263B2 (en) * | 2019-04-30 | 2022-04-19 | Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences | Method for preparing a supported carbon catalyst, supported carbon catalyst and use thereof |
| CN114433222B (en) * | 2020-10-20 | 2023-08-29 | 中国石油化工股份有限公司 | Catalyst for preparing low-carbon olefin by carbon dioxide hydrogenation and preparation and application thereof |
| CN113559859A (en) * | 2021-07-23 | 2021-10-29 | 中国地质大学（武汉） | Supported cobalt-based hydrogenation catalyst and preparation method and application thereof |
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