CN114700084B - Catalyst for hydrogenation and dehydrogenation of organic hydrogen storage liquid, preparation method thereof and hydrogenation and dehydrogenation method of organic hydrogen storage liquid - Google Patents
Catalyst for hydrogenation and dehydrogenation of organic hydrogen storage liquid, preparation method thereof and hydrogenation and dehydrogenation method of organic hydrogen storage liquid Download PDFInfo
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Abstract
The invention relates to the technical field of hydrogen storage catalysts, and discloses a catalyst for hydrogenation and dehydrogenation of organic hydrogen storage liquid, a preparation method of the catalyst and a hydrogenation and dehydrogenation method of the organic hydrogen storage liquid. The catalyst comprises a carrier, a main active component and an auxiliary active component, wherein the carrier is one or two of alumina, silica and titanium oxide; the main active component comprises non-noble metal and noble metal, the non-noble metal is nickel, the noble metal is one or two of ruthenium, rhodium and palladium, and the auxiliary active component is one or two of yttrium, cobalt and molybdenum; based on the total weight of the catalyst, the content of the main active component is 15-75wt%, and the content of the auxiliary active component is 0.3-5wt%. The catalyst has higher hydrogenation and dehydrogenation activities, can reduce the decomposition of the organic hydrogen storage liquid in the hydrogenation and dehydrogenation processes, improves the purity of hydrogen, and greatly reduces the cost.
Description
Technical Field
The invention relates to the technical field of hydrogen storage catalysts, in particular to a catalyst for hydrogenation and dehydrogenation of organic hydrogen storage liquid, a preparation method thereof and a method for hydrogenation and dehydrogenation of organic hydrogen storage liquid.
Background
The organic hydrogen storage liquid has the advantages of higher hydrogen storage capacity, stable performance, high safety, capability of being stored and transported at normal temperature and normal pressure as gasoline in principle and the like, and receives more and more attention. The organic liquid heterocyclic compound is a hydrogen storage material with excellent performance, and can realize cyclic catalytic hydrogenation and dehydrogenation under mild conditions. The hydrogen storage technology of the organic hydrogen storage liquid has the hydrogenation process and the dehydrogenation process at the same time, the hydrogenation process is relatively simple, the technology is mature, the dehydrogenation process is a strong endothermic and highly reversible reaction, and the high temperature is beneficial to the dehydrogenation reaction from the aspects of dynamics and thermodynamics. The liquid organic hydrogen storage is carried out by taking liquid organic matter as hydrogen storage agent and reacting with H 2 The reversible reaction realizes hydrogenation and dehydrogenation, and the method has the advantages of high safety, easy transportation, large hydrogen storage capacity, low hydrogen storage cost and repeated recycling. Among the materials, N-ethyl carbazole has higher mass hydrogen storage density (5.8 wt%), and the dehydrogenation temperature of the N-ethyl carbazole is reduced compared with that of the traditional organic hydride, so that the N-ethyl carbazole has good application prospect in the field of hydrogen storage.
The existing noble metal catalyst has achieved staged achievements in the field of liquid organic hydrogen storage, and in the commonly used dehydrogenation catalyst, a noble metal component plays a dehydrogenation role, but in the dehydrogenation process, the noble metal active component on the catalyst is easy to aggregate and grow in size, so that the activity is reduced, and in addition, the noble metal is expensive, so that the dehydrogenation cost is high. Meanwhile, the existing catalyst for hydrogenation and dehydrogenation of organic hydrogen storage liquid has harsh operating conditions and high operating cost, and the catalytic dehydrogenation process is accompanied by side reaction, so that hydrogen is impure. Therefore, the hydrogenation catalyst needs to be further optimized to obtain better catalytic hydrogenation effect.
Disclosure of Invention
The invention aims to overcome the problems of high price, low hydrogenation and dehydrogenation activity and the like of a conventional noble metal catalyst in the prior art, and provides a catalyst for hydrogenation and dehydrogenation of organic hydrogen storage liquid, a preparation method thereof and a hydrogenation and dehydrogenation method of the organic hydrogen storage liquid.
In order to achieve the above object, the first aspect of the present invention provides a catalyst for hydrogenation and dehydrogenation of an organic hydrogen storage liquid, the catalyst comprising a carrier, a main active component and a co-active component, wherein the carrier is one or two selected from alumina, silica and titania; the main active component comprises non-noble metal and noble metal, the non-noble metal is nickel, the noble metal is one or two of ruthenium, rhodium and palladium, and the auxiliary active component is one or two of yttrium, cobalt and molybdenum;
based on the total weight of the catalyst, the content of the main active component is 15-75wt%, and the content of the auxiliary active component is 0.3-5wt%.
In a second aspect, the present invention provides a method for preparing a catalyst for hydrogenation and dehydrogenation of an organic hydrogen storage liquid, the method comprising the steps of:
adding alkali liquor into the mixed solution of the non-noble metal precursor and the carrier precursor, and precipitating to obtain a precipitate;
sequentially filtering, washing, drying and first roasting the precipitate to obtain a catalyst precursor I;
and mixing the catalyst precursor with a mixed solution of a noble metal precursor and an auxiliary active component precursor, performing rotary evaporation dehydration, and performing second roasting to obtain the catalyst.
In a third aspect, the present invention provides a method for preparing a catalyst for hydrogenation and dehydrogenation of an organic hydrogen storage liquid, the method comprising the steps of:
carrying out first kneading on the non-noble metal precursor and the carrier precursor, adding an acid solution or an alkali solution, carrying out second kneading, and sequentially carrying out extrusion molding, drying and third roasting to obtain a catalyst precursor;
and mixing the catalyst precursor with a mixed solution of a noble metal precursor and a promoter component precursor, dehydrating by rotary evaporation, and roasting for the fourth time to obtain the catalyst.
In a fourth aspect, the present invention provides a method for hydrogenation and dehydrogenation of an organic hydrogen storage liquid, the method comprising: in the presence of the catalyst of the first aspect and the catalyst prepared by the preparation method of the second aspect or the third aspect, the organic hydrogen storage liquid is subjected to hydrogenation reaction and dehydrogenation reaction alternately to realize storage and release of hydrogen.
Through the technical scheme, the beneficial technical effects obtained by the invention are as follows:
the catalyst has higher hydrogenation and dehydrogenation activities, can reduce the decomposition of the organic hydrogen storage liquid in the hydrogenation and dehydrogenation processes, further improve the cycle service life of the organic hydrogen storage liquid, improve the purity of hydrogen products and greatly reduce the cost.
The invention solves the technical problems of high price of the conventional noble metal catalyst, low hydrogenation and dehydrogenation activity of the non-noble metal catalyst and the like.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For numerical ranges, each range between its endpoints and individual point values, and each individual point value can be combined with each other to give one or more new numerical ranges, and such numerical ranges should be construed as specifically disclosed herein.
The invention provides a catalyst for hydrogenation and dehydrogenation of organic hydrogen storage liquid, which comprises a carrier, a main active component and an auxiliary active component, wherein the carrier is one or two of aluminum oxide, silicon oxide and titanium oxide; the main active component comprises non-noble metal and noble metal, the non-noble metal is nickel, the noble metal is one or two of ruthenium, rhodium and palladium, and the auxiliary active component is one or two of yttrium, cobalt and molybdenum;
based on the total weight of the catalyst, the content of the main active component is 15-75wt%, and the content of the auxiliary active component is 0.3-5wt%.
The catalyst has higher hydrogenation and dehydrogenation activities, can reduce the decomposition of the organic hydrogen storage liquid in the hydrogenation and dehydrogenation processes, further improve the cycle service life of the organic hydrogen storage liquid, improve the purity of hydrogen and greatly reduce the cost.
In some embodiments, the primary active component is present in an amount of 20 to 70wt%, preferably 25 to 60wt%, and the co-active component is present in an amount of 0.4 to 4wt%, preferably 1 to 3wt%, based on the total weight of the catalyst.
In some embodiments, the weight ratio of non-noble metal to noble metal in the main active component is greater than 10.
In some embodiments, the weight ratio of the primary and secondary active components is greater than 5.
The invention solves the technical problems of high price of the conventional noble metal catalyst, low hydrogenation and dehydrogenation activity of the non-noble metal catalyst and the like.
In a second aspect, the present invention provides a method for preparing a catalyst for hydrogenation and dehydrogenation of an organic hydrogen storage liquid, the method comprising the steps of:
adding alkali liquor into the mixed solution of the non-noble metal precursor and the carrier precursor, and precipitating to obtain a precipitate;
sequentially filtering, washing, drying and first roasting the precipitate to obtain a catalyst precursor I;
and mixing the catalyst precursor with a mixed solution of a noble metal precursor and an auxiliary active component precursor, performing rotary evaporation dehydration, and performing second roasting to obtain the catalyst.
The catalyst prepared by adopting the precipitation method has high Ni loading amount of non-noble metal active components, high catalyst activity, and more importantly, the catalyst has low decomposition rate of organic liquid (high organic liquid selectivity) in hydrogen adding and dehydrogenation reactions when the high Ni loading amount is adopted.
In some embodiments, the non-noble metal precursor is selected from nickel nitrate, nickel sulfate, nickel chloride, nickel oxalate, or nickel acetate.
In some embodiments, the support precursor comprises one or two of an alumina precursor, a silica precursor and a titania precursor, wherein the alumina precursor is selected from at least one of aluminum nitrate, aluminum sulfate, aluminum chloride, aluminum hydroxide and pseudoboehmite having an alumina content of 60-85wt%, preferably 65-75wt%; the silicon oxide precursor is selected from at least one of silicon oxide, silica sol, tetraethoxysilane and methyl orthosilicate; the titanium oxide precursor is at least one selected from the group consisting of titanium hydroxide, titanium oxide, titanium chloride, titanium oxychloride and metatitanic acid.
In some embodiments, the non-noble metal precursor is selected from one or two of soluble salts of ruthenium, rhodium, and palladium; the soluble salt is preferably a nitrate or chloride salt.
In some embodiments, the co-active component precursor is selected from one or two of soluble salts of yttrium, cobalt and molybdenum; the soluble salt is preferably a nitrate or chloride salt.
In some embodiments, the base solution is ammonia or sodium hydroxide.
In some embodiments, the precipitate has a pH of 6 to 11.
In some embodiments, the first calcination is at a temperature of 300 to 700 ℃, preferably 400 to 500 ℃, for a time of 0.5 to 10 hours, preferably 3 to 5 hours.
In some embodiments, the rotary evaporation dehydration temperature is 80-150 ℃, preferably 100-120 ℃, and the time is 1-24h, preferably 5-10h.
In some embodiments, the second calcination is at a temperature of 250 to 600 ℃, preferably 350 to 500 ℃, for a time of 0.5 to 10 hours, preferably 3 to 5 hours.
In some embodiments, the method of making further comprises: and after the second roasting, carrying out reduction reaction on the roasted sample to obtain the catalyst.
In some preferred embodiments, the reduction is carried out under a hydrogen atmosphere at a temperature of 200 to 450 ℃, preferably 300 to 400 ℃, for a time of 1 to 48 hours, preferably 5 to 20 hours.
In some preferred embodiments, the reduction reaction is carried out with a reducing agent at a temperature of 160 to 350 ℃, preferably 200 to 300 ℃, for a time of 2 to 30 hours, preferably 5 to 20 hours.
In some preferred embodiments, the reducing agent is sodium borohydride.
In a third aspect, the present invention provides a method for preparing a catalyst for hydrogenation and dehydrogenation of an organic hydrogen storage liquid, the method comprising the steps of:
performing first mixing and kneading on the non-noble metal precursor and the carrier precursor, adding an acid solution or an alkali solution, performing second mixing and kneading, and sequentially performing extrusion molding, drying and third roasting to obtain a catalyst precursor;
and mixing the catalyst precursor with a mixed solution of a noble metal precursor and a promoter component precursor, dehydrating by rotary evaporation, and roasting for the fourth time to obtain the catalyst.
The catalyst prepared by the kneading method has high Ni loading amount of non-noble metal active components, high catalyst activity, and more importantly, the catalyst has low decomposition rate of hydrogen addition gas and organic liquid in dehydrogenation reaction (high organic liquid selectivity) when the Ni loading amount is high.
In some embodiments, the non-noble metal precursor is selected from nickel nitrate, nickel hydroxide, nickel hydroxycarbonate, nickel oxalate, or nickel acetate.
In some embodiments, the carrier precursor comprises one or two of an alumina precursor, a silica precursor and a titania precursor, wherein the alumina precursor is selected from at least one of aluminum nitrate, aluminum sulfate, aluminum chloride, aluminum hydroxide and pseudo-boehmite having an alumina content of 60 to 85wt%, preferably 65 to 75wt%; the silicon oxide precursor is selected from at least one of silicon oxide, silica sol, tetraethoxysilane and methyl orthosilicate; the titanium oxide precursor is at least one selected from titanium hydroxide, titanium oxide, titanium chloride, titanium oxychloride and metatitanic acid.
In some embodiments, the co-active component precursor I is selected from one or two of soluble salts of ruthenium, rhodium and palladium; the soluble salt is preferably a nitrate or chloride salt.
In some embodiments, the promoter component precursor iii is selected from one or two of soluble salts of yttrium, cobalt and molybdenum; the soluble salt is preferably a nitrate or chloride salt.
In some embodiments, the acid solution is selected from hydrochloric acid, nitric acid, sulfuric acid, or glacial acetic acid.
In some embodiments, the base solution is selected from aqueous ammonia or ammonium carbonate.
In some embodiments, the first kneading time is 10 to 90min, preferably 20 to 60min.
In some embodiments, the second kneading time is 10 to 90min, preferably 30 to 70min.
In some embodiments, the temperature of the third calcination is 300 to 700 ℃, preferably 400 to 500 ℃, and the time is 0.5 to 10 hours, preferably 3 to 5 hours.
In some embodiments, the fourth calcination is at a temperature of 250 to 600 ℃, preferably 300 to 500 ℃, for a time of 0.5 to 10 hours, preferably 3 to 5 hours.
In some embodiments, the method of making further comprises: and after the second roasting, carrying out reduction reaction on the roasted sample to obtain the catalyst.
In some preferred embodiments, the reduction is carried out under a hydrogen atmosphere at a temperature of 200 to 450 ℃, preferably 300 to 400 ℃, for a time of 1 to 48 hours, preferably 5 to 20 hours.
In some preferred embodiments, the reduction reaction is carried out with a reducing agent at a temperature of 160 to 350 ℃, preferably 200 to 300 ℃, for a time of 2 to 30 hours, preferably 5 to 20 hours.
In some preferred embodiments, the reducing agent is sodium borohydride.
After the catalyst obtained by the preparation method is roasted, the metal active component and the metal auxiliary active component of the catalyst exist in the form of metal oxide. In some catalysts, the catalyst in an oxidized state does not have catalytic activity, and an active component oxide of the catalyst needs to be partially or completely reduced into a metal simple substance through reduction activation, for example, nickel oxide does not have activity, and the nickel oxide needs to be subjected to reduction activation treatment before use to reduce the nickel oxide into active metal nickel. The reduction-oxidation treatment may be performed during the production process or before the use. In view of the possibility of oxidation of the active metal element during storage and transportation, it is preferable to perform the reduction activation treatment before the catalytic reaction, that is, before use. Therefore, before using the catalyst, it is necessary to confirm the state of the active component of the catalyst, and if the active component of the catalyst used is in an oxidized state, the catalyst needs to be subjected to a reduction activation treatment before use.
In a fourth aspect, the present invention provides a method for hydrogenation and dehydrogenation of an organic hydrogen storage liquid, the method comprising: in the presence of the catalyst of the first aspect and the catalyst prepared by the preparation method of the second aspect or the third aspect, the organic hydrogen storage liquid is subjected to hydrogenation reaction and dehydrogenation reaction alternately to realize storage and release of hydrogen.
In some embodiments, the organic hydrogen storage liquid is dibenzyltoluene, cyclohexane, methylcyclohexane, decalin, quinoline, carbazole, N-methylcarbazole, N-ethylcarbazole, or N-propylcarbazole.
In some preferred embodiments, the organic hydrogen storage liquid is N-ethylcarbazole, and the space velocity of N-ethylcarbazole is 0.1-4 mL/(g.h).
In some embodiments, the conditions of the hydrogenation reaction are: the reaction temperature is 140-250 ℃, the preferable temperature is 150-200 ℃, and the hydrogen pressure is 3-10MPa, the preferable pressure is 5-8MPa;
in some embodiments, the dehydrogenation reaction conditions are: the reaction temperature is 140-250 ℃, preferably 150-200 ℃, and the hydrogen pressure is 0.01-1.5MPa, preferably 0.1-1MPa.
In order to further understand the present invention, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Unless otherwise specified, the reagents involved in the examples of the present invention are all commercially available products, and all of them are commercially available. The present invention will be described in detail below by way of examples.
Example 1
(1) Weighing 200g of pseudo-boehmite (the content of alumina is 75%) and placing the pseudo-boehmite in a kneading machine, then adding 187g of nickel oxalate, kneading for 20min, then mixing 5g of concentrated nitric acid with 110g of deionized water, then adding the mixture into the kneading machine, kneading for 30min, then extruding and molding by a strip extruder, dehydrating and drying at 120 ℃, roasting at 400 ℃ to obtain 40Ni/100Al 2 O 3 ；
(2) 100g of the above Ni/Al was weighed 2 O 3 Placing in a rotary evaporation bottle, dissolving 1.54g of ruthenium chloride and 1.48g of cobalt nitrate hexahydrate in 55ml of deionized water to obtain a ruthenium solution, then adding into the rotary evaporation bottle, carrying out rotary evaporation dehydration, dehydrating and drying at 120 ℃ for 4h, and roasting at 350 ℃ for 2h to obtain 0.3Co/0.5Ru/40Ni/100Al 2 O 3 A catalyst.
Example 2
(1) Weighing 200g of pseudo-boehmite (the content of alumina is 75%) and placing the pseudo-boehmite in a kneading machine, then adding 140.2g of nickel oxalate, kneading for 20min, then mixing 5g of concentrated nitric acid with 110g of deionized water, then adding the mixture into the kneading machine, kneading for 30min, then extruding and molding by a strip extruder, dehydrating and drying at 120 ℃, roasting at 400 ℃ to obtain 30Ni/100Al 2 O 3 ；
(2) 100g of the above Ni/Al was weighed 2 O 3 Placing in a rotary evaporation bottle, dissolving 1.54g ruthenium chloride and 1.48g cobalt nitrate hexahydrate in 55ml deionized water to obtain ruthenium solution, adding into the rotary evaporation bottle, rotary evaporating for dehydration, dehydrating at 120 deg.C for 4h, and calcining at 350 deg.C for 2h to obtain 0.3Co/0.5Ru/30Ni/100Al 2 O 3 A catalyst.
Example 3
(1) Weighing 200g of pseudo-boehmite (the content of alumina is 75%) and placing the pseudo-boehmite in a kneading machine, then adding 140.2g of nickel oxalate, kneading for 20min, then mixing 5g of concentrated nitric acid with 110g of deionized water, then adding the mixture into the kneading machine, kneading for 30min, then extruding and molding by a strip extruder, dehydrating and drying at 120 ℃, roasting at 400 ℃ to obtain 30Ni/100Al 2 O 3 ；
(2) 100g of the above Ni/Al was weighed 2 O 3 Placing in a rotary evaporation bottle, dissolving 2.5g palladium dichloride, 9.9g cobalt nitrate hexahydrate and 0.9g yttrium nitrate hexahydrate in 51ml deionized water to obtain a metal solution, then adding into the rotary evaporation bottle, carrying out rotary evaporation dehydration, dehydrating at 120 ℃, drying for 4h, roasting at 350 ℃ for 2h to obtain 0.2Y/2Co/1.5Pd/30Ni/100Al 2 O 3 A catalyst.
Example 4
(1) 552g of aluminum nitrate nonahydrate and 198g of nickel nitrate hexahydrate were added to a beaker containing 800ml of deionized water, stirred and completely dissolved, and then the beaker was placed in a 40 ℃ water bath and mechanically stirred. Adding 2ml/L ammonia water into the beaker dropwise, stopping adding the ammonia water when the pH of the solution in the beaker is about 8, continuing stirring for 30min, filtering and washing the precipitate, dehydrating and drying at 120 ℃ for 4h, and roasting at 500 ℃ for 3h to obtain 27Ni/Al 2 O 3 。
100g of the above Ni/Al was weighed 2 O 3 Placing the solution into a rotary evaporation bottle, dissolving 2.5g of palladium dichloride and 2.2g of yttrium nitrate hexahydrate in 55ml of deionized water to obtain a metal solution, then adding the metal solution into the rotary evaporation bottle, and performing rotary evaporation and dehydration. Dehydrating at 120 deg.C for 4h, and calcining at 350 deg.C for 2h to obtain 0.5Y/1.5Pd/26Ni/100Al 2 O 3 A catalyst.
Comparative example 1
1) Weighing 200g of pseudoboehmite (the content of alumina is 75%) and placing the pseudoboehmite in a kneading machine, then mixing 5g of concentrated nitric acid and 100g of deionized water and adding the mixture into the kneading machine, kneading for 30min, extruding and molding by a strip extruding machine, dehydrating at 120 ℃, drying, and roasting at 400 ℃ to obtain 100Al 2 O 3 ；
(2) 100g of the above Al was weighed 2 O 3 Placing in a rotary evaporation bottle, dissolving 3.3g of palladium dichloride in 55ml of deionized water to obtain a metal solution, then adding into the rotary evaporation bottle, and performing rotary evaporation for dehydration. Drying and dehydrating at 120 ℃ for 4h, and roasting at 300 ℃ for 2h to obtain 2Pd/100Al 2 O 3 A catalyst.
Comparative example 2
1) Weighing 200g of pseudo-boehmite (the content of alumina is 75%) and placing the pseudo-boehmite in a kneading machine, then mixing 5g of concentrated nitric acid with 100g of deionized water and adding the mixture into the kneading machine, kneading for 30min, extruding and molding by a strip extruding machine, dehydrating at 120 ℃, drying, and roasting at 400 ℃ to obtain 100Al 2 O 3 ；
(2) 100g of the above Al was weighed 2 O 3 Placing the solution in a rotary evaporation bottle, dissolving 74.4g of nickel nitrate hexahydrate in 35ml of deionized water to obtain a metal solution, adding the metal solution into the rotary evaporation bottle, and performing rotary evaporation to remove water. Drying and dehydrating at 120 ℃ for 4h, and roasting at 300 ℃ for 2h to obtain 15Ni/100Al 2 O 3 A catalyst.
Hydrogenation or dehydrogenation performance test of the catalyst: after crushing the catalysts prepared in examples 1 to 4 and comparative examples 1 to 2, 5g of the catalyst having a size of 20 to 40 mesh was sieved out and charged into a fixed bed reactor. The catalyst is kept at the constant temperature of 300 ℃ for 4 hours in the pure hydrogen atmosphere at normal pressure in the reactor, and then the temperature is reduced to the reaction condition for carrying out the hydrogenation or dehydrogenation performance test of the N-ethyl carbazole. The hydrogenation reaction is carried out at 200 ℃ and 7MPa, and the dehydrogenation reaction is carried out at 170 ℃ and normal pressure. Unhydrogenated N-ethylcarbazole or fully hydrogenated 12-N-ethylcarbazole was added to the reactor at a rate of 0.06ml/min by means of a liquid transfer pump. The hydrogen gas inlet flow rate during the hydrogenation reaction is 100ml/min. After the hydrogenation and dehydrogenation reactions were completed, the compositions of the residual liquid phase and the generated gas were qualitatively and quantitatively analyzed by GC-MS and gas chromatography, respectively, and the results are shown in tables 1 and 2, respectively.
TABLE 1
| Numbering | Catalyst and process for producing the same | N-ethylcarbazole hydroconversion/%) | N-ethylcarbazole selectivity/%) |
| Example 1 | 0.3Co/0.5Ru/40Ni/100Al2O3 | 89 | 100 |
| Example 2 | 0.3Co/0.5Ru/30Ni/100Al2O3 | 87 | 100 |
| Example 3 | 0.2Y/2Co/1.5Pd/30Ni/100Al2O3 | 92 | 100 |
| Example 4 | 0.5Y/1.5Pd/26Ni/100Al2O3 | 85 | 100 |
| Comparative example 1 | 2Pd/100Al2O3 | 57 | 100 |
| Comparative example 2 | 15Ni/100Al2O3 | 37 | 99 |
TABLE 2
| Numbering | Catalyst and process for preparing same | Dehydrogenation conversion/% of N-ethylcarbazole | N-ethylcarbazole selectivity/%) |
| Example 1 | 0.3Co/0.5Ru/40Ni/100Al2O3 | 87 | 99.9 |
| Example 2 | 0.3Co/0.5Ru/30Ni/100Al2O3 | 83 | 99.8 |
| Example 3 | 0.2Y/2Co/1.5Pd/30Ni/100Al2O3 | 88 | 99.9 |
| Example 4 | 0.5Y/1.5Pd/26Ni/100Al2O3 | 81 | 99.8 |
| Comparative example 1 | 2Pd/100Al2O3 | 52 | 99.5 |
| Comparative example 2 | 15Ni/100Al2O3 | 29 | 97.1 |
As can be seen from the results in tables 1 and 2, the examples of the present invention have high hydrogenation and dehydrogenation activities. More unexpectedly, the catalyst prepared by the embodiment has high selectivity of the organic liquid in hydrogenation and dehydrogenation reactions, namely the decomposition rate of the hydrogen storage organic liquid in the hydrogenation and dehydrogenation processes is low, and the purity of the hydrogen product is high. In later-stage industry, the organic hydrogen storage liquid needs hydrogenation and dehydrogenation for multiple times of recycling, the decomposition rate of the organic liquid is low, the recycling service life of the organic liquid is longer, and the use cost is lower.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (16)
1. A catalyst for hydrogenation and dehydrogenation of organic hydrogen storage liquid, which is characterized by comprising a carrier, a main active component and an auxiliary active component, wherein the carrier is one or two of aluminum oxide, silicon oxide and titanium oxide; the main active component comprises non-noble metal and noble metal, the non-noble metal is nickel, the noble metal is one or two of ruthenium, rhodium and palladium, and the auxiliary active component is one or two of yttrium, cobalt and molybdenum;
based on the total weight of the catalyst, the content of the main active component is 25-60wt%, and the content of the auxiliary active component is 1-3wt%;
the weight ratio of the main active component to the auxiliary active component is more than 5;
in the main active component, the weight ratio of non-noble metal to noble metal is more than 10.
2. The catalyst according to claim 1, wherein the weight ratio of the main active component to the co-active component is greater than 10.
3. A catalyst according to claim 1 or claim 2, wherein the co-active component comprises both cobalt and yttrium in a weight ratio of cobalt to yttrium greater than 3.
4. The catalyst of claim 1, wherein the catalyst is 0.2Y/2Co/1.5Pd/30Ni/100Al 2 O 3 。
5. A method of preparing a catalyst for hydrogenation and dehydrogenation of an organic hydrogen storage liquid according to any of claims 1-4, characterized in that the method of preparation comprises the steps of:
adding alkali liquor into the mixed solution of the non-noble metal precursor and the carrier precursor, and precipitating to obtain a precipitate;
sequentially filtering, washing, drying and first roasting the precipitate to obtain a catalyst precursor I;
mixing the catalyst precursor with a mixed solution of a noble metal precursor and an auxiliary active component precursor, performing rotary evaporation dehydration, and performing second roasting to obtain the catalyst;
the non-noble metal precursor is selected from nickel nitrate, nickel sulfate, nickel chloride, nickel oxalate or nickel acetate;
the carrier precursor comprises one or two of an aluminum oxide precursor, a silicon oxide precursor and a titanium oxide precursor;
the noble metal precursor is selected from one or two of soluble salts of ruthenium, rhodium and palladium;
the auxiliary active component precursor is selected from one or two of soluble salts of yttrium, cobalt and molybdenum.
6. The preparation method according to claim 5, wherein the alumina precursor is selected from at least one of aluminum nitrate, aluminum sulfate, aluminum chloride, aluminum hydroxide and pseudoboehmite, and the alumina content of the pseudoboehmite is 60-85wt%; the silicon oxide precursor is selected from at least one of silicon oxide, silica sol, tetraethoxysilane and methyl orthosilicate; the titanium oxide precursor is selected from at least one of titanium hydroxide, titanium oxide, titanium chloride, titanium oxychloride and metatitanic acid;
and/or the alkali liquor is ammonia water or sodium hydroxide;
and/or the pH of the precipitate is 6-11.
7. The preparation method according to claim 5 or 6, wherein the temperature of the first roasting is 300-700 ℃ and the time is 0.5-10h;
and/or the temperature of the rotary evaporation dehydration is 80-150 ℃, and the time is 1-24h;
and/or the temperature of the second roasting is 250-600 ℃ and the time is 0.5-10h.
8. The production method according to claim 5 or 6, wherein the production method further comprises: after the second roasting, carrying out reduction reaction on the roasted sample to obtain the catalyst;
wherein the reduction reaction is carried out in a hydrogen atmosphere, the temperature of the reduction is 200-450 ℃, and the time is 1-48h;
reducing by adopting a reducing agent in the reduction reaction at 160-350 ℃ for 2-30h;
the reducing agent is sodium borohydride.
9. The production method according to claim 7, wherein the production method further comprises: after the second roasting, carrying out reduction reaction on the roasted sample to obtain the catalyst;
wherein the reduction reaction is carried out in a hydrogen atmosphere, the reduction temperature is 200-450 ℃, and the reduction time is 1-48h;
reducing by adopting a reducing agent in the reduction reaction at 160-350 ℃ for 2-30h;
the reducing agent is sodium borohydride.
10. A method of preparing a catalyst for hydrogenation and dehydrogenation of an organic hydrogen storage liquid according to any of claims 1-4, characterized in that the method of preparation comprises the steps of:
carrying out first kneading on the non-noble metal precursor and the carrier precursor, adding an acid solution or an alkali solution, carrying out second kneading, and sequentially carrying out extrusion molding, drying and third roasting to obtain a catalyst precursor;
mixing the catalyst precursor with a mixed solution of a noble metal precursor and an auxiliary active component precursor, carrying out rotary evaporation dehydration, and carrying out fourth roasting to obtain the catalyst;
the non-noble metal precursor is selected from nickel nitrate, nickel sulfate, nickel chloride, nickel oxalate or nickel acetate;
the carrier precursor comprises one or two of an aluminum oxide precursor, a silicon oxide precursor and a titanium oxide precursor;
the noble metal precursor is selected from one or two of soluble salts of ruthenium, rhodium and palladium;
the auxiliary active component precursor is selected from one or two of soluble salts of yttrium, cobalt and molybdenum.
11. The preparation method according to claim 10, wherein the alumina precursor is selected from at least one of aluminum nitrate, aluminum sulfate, aluminum chloride, aluminum hydroxide and pseudoboehmite, and the alumina content of the pseudoboehmite is 60-85wt%; the silicon oxide precursor is selected from at least one of silicon oxide, silica sol, ethyl orthosilicate and methyl orthosilicate; the titanium oxide precursor is selected from at least one of titanium hydroxide, titanium oxide, titanium chloride, titanium oxychloride and metatitanic acid;
and/or, the acid solution is selected from hydrochloric acid, nitric acid, sulfuric acid or glacial acetic acid;
and/or the alkali solution is selected from ammonia water or ammonium carbonate.
12. The production method according to claim 10 or 11, wherein the first kneading time is 10 to 90min;
and/or the second kneading time is 10-90min;
and/or the temperature of the third roasting is 300-700 ℃, and the time is 0.5-10h;
and/or the temperature of the fourth roasting is 250-600 ℃, and the time is 0.5-10h.
13. A method of hydrogenating and dehydrogenating an organic hydrogen storage liquid, the method comprising: the organic hydrogen storage liquid is alternately subjected to hydrogenation reaction and dehydrogenation reaction in the presence of the catalyst of any one of claims 1 to 4 or the catalyst prepared by the preparation method of any one of claims 5 to 12, so as to realize the storage and release of hydrogen.
14. The method of claim 13, said organic hydrogen storage liquid being dibenzyltoluene, cyclohexane, methylcyclohexane, decalin, quinoline, carbazole, N-methylcarbazole, N-ethylcarbazole, or N-propylcarbazole.
15. The method of claim 14, wherein the organic hydrogen storage liquid is N-ethyl carbazole at a space velocity of 0.1-4 mL/(g-h).
16. The process of any one of claims 13-15, wherein the hydrogenation reaction conditions are: the reaction temperature is 140-250 ℃, and the hydrogen pressure is 3-10MPa;
and/or, the dehydrogenation reaction conditions are: the reaction temperature is 140-250 ℃, and the hydrogen pressure is 0.01-1.5MPa.
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