CN111013663A - Transition metal-boron-based catalyst for catalyzing hydrogen absorption and hydrogen desorption of liquid organic hydrogen carrier and preparation method thereof - Google Patents
Transition metal-boron-based catalyst for catalyzing hydrogen absorption and hydrogen desorption of liquid organic hydrogen carrier and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of hydrogen storage and catalysis, and particularly relates to a transition metal-boron-based catalyst for catalyzing hydrogen absorption and hydrogen desorption of a liquid organic hydrogen carrier and a preparation method thereof. The catalyst comprises a catalyst carrier and an active catalytic component loaded on the catalyst carrier, wherein the active catalytic component is a mixed component of transition metal-boron and metal hydride; the transition metal-boron is prepared by the reaction of transition metal salt and borohydride solution. Compared with the prior art, the invention has the following advantages: (1) the catalyst has simple preparation process, easy operation and amplification and easy application; (2) the catalyst prepared by the invention has excellent performance, can achieve the performance of a noble metal catalyst under the condition of not using noble metals, and can obviously reduce the use cost of the liquid organic hydrogen carrier by using the same catalyst for hydrogen absorption and hydrogen desorption.
Description
Technical Field
The invention belongs to the technical field of hydrogen storage and catalysis, and particularly relates to a transition metal-boron-based catalyst for catalyzing hydrogen absorption and hydrogen desorption of a liquid organic hydrogen carrier and a preparation method thereof.
Background
At present, the energy crisis and the environmental pollution problem are becoming more serious, energy conversion by replacing fossil energy with renewable energy is urgent. The hydrogen energy source, a clean and renewable secondary energy source, is considered as a core pillar in energy transformation. However, the development of hydrogen energy sources is limited by the lack of a sufficiently efficient and safe way of storing hydrogen. The liquid organic hydrogen carrier is one of the most potential hydrogen storage materials at present due to the advantages of high hydrogen storage amount, good reversibility, good thermal conductivity and the like, however, the liquid organic hydrogen carrier generally has the defects of slow hydrogen absorption and desorption kinetics and the need of using expensive noble metal catalysts, and different catalysts are often needed in the hydrogen absorption and desorption processes. For example, for N-ethyl carbazole, which is one of the most promising liquid organic hydrogen carriers, Ru-based catalysts and Pd-based catalysts are the best catalysts for hydrogen absorption reaction and hydrogen desorption reaction, respectively.
Therefore, one of the major bottlenecks in catalytic hydrogenation and catalytic dehydrogenation technologies for liquid organic hydrogen carriers is the high cost associated with the use of noble metal catalysts.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a transition metal-boron-based catalyst for catalyzing hydrogen absorption and hydrogen desorption of a liquid organic hydrogen carrier and a preparation method thereof. The transition metal-boron-based catalyst can simultaneously catalyze efficientlyNThe catalytic performances of hydrogen absorption and hydrogen desorption reactions of liquid organic hydrogen carriers such as-ethyl carbazole and the like are respectively comparable to or even superior to those of noble metal catalysts, so that the use cost of the liquid organic hydrogen carriers can be greatly reduced, and the practical application of the liquid organic hydrogen carriers is promoted.
In order to achieve the purpose, the invention adopts the following technical scheme:
a transition metal-boron based catalyst for catalyzing hydrogen absorption and hydrogen desorption of a liquid organic hydrogen carrier comprises a catalyst carrier and an active catalytic component loaded on the catalyst carrier, wherein the active catalytic component is a mixed component of transition metal-boron and a metal hydride, and the transition metal-boron is prepared by reacting a transition metal salt with a borohydride solution.
Preferably, the transition metal-boron of the invention is prepared by the following preparation steps: the preparation method comprises the following steps of ultrasonically dispersing transition metal salt, hexadecyl trimethyl ammonium chloride, a catalyst carrier and deionized water, slowly dropwise adding a borohydride solution under an ultrasonic condition, continuing to perform ultrasonic treatment after dropwise adding, performing centrifugal separation, cleaning, and finally performing vacuum drying.
More preferably, the mass ratio of the transition metal-boron to the metal hydride is 1: 0.5-2.
Further preferably, the transition metal-boron is selected from one of Fe-B, Co-B, Ni-B, NiFe-B, NiCo-B, FeCo-B, FeCoNi-B.
Further preferably, the transition metal salt according to the invention is selected from CoCl2•6H2O、NiCl2•6H2O、FeSO4•7H2One or more of O.
Further preferably, the catalyst carrier of the present invention is selected from Al2O3、SiO2And graphene.
Further preferably, the molar ratio of the transition metal salt to the hexadecyl trimethyl ammonium chloride is 1: 1.5-2; the mass ratio of the hexadecyl trimethyl ammonium chloride to the catalyst carrier to the deionized water is 1: 2-5: 2-5; the molar ratio of the transition metal salt to the borohydride is 1:1 to 2.
Further preferably, the metal hydride of the present invention comprises a metal selected from the group consisting of LiH and MgH2、YH3、LaH3、GdH3、NaAlH4One or more of them.
Further preferably, the borohydride solution according to the invention is selected from NaBH4Solutions ofOr KBH4One of the solutions.
Another object of the present invention is to provide a method for preparing a transition metal-boron based catalyst for catalyzing hydrogen absorption and desorption of a liquid organic hydrogen carrier, the method comprising the steps of:
1) reducing the size of the metal hydride to below 500 nm: ball-milling metal hydride in 4bar hydrogen atmosphere for 2h, wherein the ball-to-material ratio is 4: 1, the rotating speed is 250 rpm;
2) preparation of transition metal-boron: adding 0.2-0.5 mmol of transition metal salt, hexadecyl trimethyl ammonium chloride, a catalyst carrier and deionized water according to the proportion in claim 7 into a beaker, carrying out ultrasonic treatment for about 30min, slowly dropwise adding a borohydride solution with the concentration of 0.15-0.2 mol/L according to the proportion while carrying out ultrasonic treatment, continuing the ultrasonic treatment for about 30min after finishing the dropwise adding, carrying out centrifugal separation, washing with the deionized water and ethanol twice respectively, and then carrying out vacuum drying;
3) preparation of the catalyst: mixing the transition metal-boron prepared in the step 2) and the Metal Hydride (MH) ball-milled in advance in the step 1) according to a mass ratio of 1: and (3) mixing and grinding for about 5 min by 0.5-2 to prepare the transition metal-boron-based catalyst TM-B-MH for catalyzing hydrogen absorption and hydrogen desorption of the liquid organic hydrogen carrier.
Compared with the prior art, the invention has the following advantages:
(1) the catalyst of the invention has simple preparation process, easy operation and amplification and easy application.
(2) The catalyst prepared by the invention has excellent performance, can achieve the performance of a noble metal catalyst under the condition of not using noble metals, and can obviously reduce the use cost of the liquid organic hydrogen carrier by using the same catalyst for hydrogen absorption and hydrogen desorption.
Drawings
FIG. 1 shows Co-B/Al prepared in example 1 of the present invention2O3-YH3The (a) X-ray diffraction spectrum, (b) X-ray photoelectron spectrum, and (c) transmission electron micrograph.
FIG. 2 shows Co-B/Al prepared in example 1 of the present invention2O3-YH3CatalysisN-kinetic profile of hydrogen uptake and desorption of ethyl carbazole.
FIG. 3 is a schematic diagram of the apparatus for testing hydrogen absorption/desorption kinetics curves of the liquid organic hydrogen carrier.
Detailed Description
The present invention will be described in further detail with reference to specific examples.
The invention relates to a transition metal-boron-based catalyst for catalyzing hydrogen absorption and hydrogen desorption of a liquid organic hydrogen carrier, which comprises a carrier and an active catalytic component loaded on the carrier, wherein the active catalytic component is a mixed component of transition metal-boron and metal hydride; wherein, the transition metal-boron is prepared by the reaction of transition metal salt and borohydride solution.
Wherein the transition metal-boron is one selected from Fe-B, Co-B, Ni-B, NiFe-B, NiCo-B, FeCo-B, FeCoNi-B.
The transition metal salt is selected from CoCl2•6H2O、NiCl2•6H2O、FeSO4•7H2One or more of O.
The catalyst carrier is selected from Al2O3、SiO2And graphene.
The metal hydride includes LiH, MgH2、YH3、LaH3、GdH3、NaAlH4One or more of them.
Example 1
1) Reducing the size of the metal hydride to below 500 nm: will YH3Ball-milling for 10h in 4bar hydrogen atmosphere, wherein the ball-material ratio is 4: 1, rotational speed 250 rpm.
2) 47.6 mg CoCl was added to the beaker2•6H2O, 100 mg of cetyltrimethylammonium chloride, 220 mg of gamma-Al2O3And 2.5 mL of deionized water, performing ultrasonic treatment for 30min, and then slowly dropwise adding 1.5 mL of 0.18 mol/L NaBH while performing ultrasonic treatment4And (3) continuing ultrasonic treatment for 30min after the solution is dripped, performing centrifugal separation, washing twice with deionized water and ethanol respectively, and then vacuumizing and drying. Ball-milling the mixture with equal mass in a glove boxYH of3Mixing and grinding for 5 min to prepare Co-B/Al2O3-YH3The catalyst, X-ray diffraction spectrum, X-ray photoelectron spectrum and transmission electron micrograph of the catalyst are shown in figure 1.
Catalyzing the catalystNEvaluation of Hydrogen absorption and desorption Performance of-Ethylcarbazole (NEC), kinetic graph shown in FIG. 2, Hydrogen absorption reaction at 180 deg.C and 10 MPa H2Under the condition of (1), the reaction is completed within 2H, and the corresponding hydrogen release reaction can be carried out at 200 ℃ and 0.1 MPa H2The hydrogen is discharged for more than 5.5 percent (the hydrogen yield is 95 percent) after 7 hours under the condition of (1), and the reaction rate and the selectivity are not obviously reduced after three hydrogen absorption and discharge cycles. The schematic diagram of the device for testing the hydrogen absorption and desorption kinetic curve of the liquid organic hydrogen carrier is shown in figure 3.
Example 2
1) Reducing the size of the metal hydride to below 500 nm: mixing LaH3Ball-milling for 10h in 4bar hydrogen atmosphere, wherein the ball-material ratio is 4: 1, rotational speed 250 rpm.
2) 47.5 mg of NiCl was added to the beaker2•6H2O, 100 mg of cetyltrimethylammonium chloride, 220 mg of SiO2And 2.5 mL of deionized water, performing ultrasonic treatment for 30min, and then slowly dropwise adding 1.5 mL of 0.18 mol/L KBH while performing ultrasonic treatment4And (3) continuing ultrasonic treatment for 30min after the solution is dripped, performing centrifugal separation, washing twice with deionized water and ethanol respectively, and then vacuumizing and drying. It was ball-milled with LaH previously in a glove box3According to the following steps of 1:0.5 for 5 min to obtain Ni-B/SiO2-LaH3A catalyst.
Catalyzing the catalystNEvaluation of Hydrogen absorption and desorption Performance of-Ethylcarbazole (NEC) the hydrogen absorption reaction of which can be carried out at 180 ℃ under 10 MPa H2Under the condition of (1), the reaction is completed within 6H, and the corresponding hydrogen release reaction can be carried out at 200 ℃ and 0.1 MPa H2The hydrogen is discharged for 12 hours for more than 5.4 wt% (the hydrogen yield is 95%). The apparatus for testing the hydrogen absorption and desorption kinetics curves of the liquid organic hydrogen carrier is the same as that of example 1.
Example 3
1) Reducing the size of the metal hydride to below 500 nm: will GdH3At 4band performing ball milling for 10 hours in an ar hydrogen atmosphere, wherein the ball-to-material ratio is 4: 1, rotational speed 250 rpm.
2) Adding 55.6 mg of FeSO into a beaker4•7H2O, 100 mg of hexadecyl trimethyl ammonium chloride, 220 mg of reduced graphene (rGO) and 2.5 mL of deionized water, performing ultrasonic treatment for 30min, and slowly dropwise adding 1.5 mL of 0.18 mol/L NaBH while performing ultrasonic treatment4And (3) continuing ultrasonic treatment for 30min after the solution is dripped, performing centrifugal separation, washing twice with deionized water and ethanol respectively, and then vacuumizing and drying. It was ball milled with GdH in a glove box3According to the following steps of 1: 2 for 5 min to prepare Fe-B/rGO-GdH3A catalyst.
Catalyzing the catalystNEvaluation of Hydrogen absorption and desorption Performance of-Ethylcarbazole (NEC) the hydrogen absorption reaction of which can be carried out at 180 ℃ under 10 MPa H2Under the condition of (1), the reaction is completed within 16H, and the corresponding hydrogen release reaction can be carried out at 200 ℃ and 0.1 MPa H2The hydrogen is discharged for 20 h for more than 5.5 wt% (hydrogen yield 95%). The apparatus for testing the hydrogen absorption and desorption kinetics curves of the liquid organic hydrogen carrier is the same as that of example 1.
Example 4
1) Reducing the size of the metal hydride to below 500 nm: ball-milling LiH in a hydrogen atmosphere of 4bar for 10h, wherein the ball-to-material ratio is 4: 1, rotational speed 250 rpm.
2) 47.6 mg CoCl was added to the beaker2•6H2O, 150 mg of hexadecyl trimethyl ammonium chloride, 300 mg of reduced graphene and 5 mL of deionized water, performing ultrasonic treatment for 30min, and then slowly dropwise adding 2 mL of 0.18 mol/L NaBH while performing ultrasonic treatment4And (3) continuing ultrasonic treatment for 30min after the solution is dripped, performing centrifugal separation, washing twice with deionized water and ethanol respectively, and then vacuumizing and drying. Mixing and grinding the mixed material with LiH which is equal in mass and is ball-milled in advance in a glove box for 5 min to prepare the Co-B/rGO-LiH catalyst.
The catalyst is subjected to performance evaluation of catalyzing 2-methylindole hydrogen absorption and desorption, and the hydrogen absorption reaction can be carried out at 180 ℃ and 7MPa H2Under the condition of (1), the reaction is completed within 2H, and the corresponding hydrogen release reaction can be carried out at 200 ℃ and 0.1 MPa H2The hydrogen is discharged for more than 5.5 wt% in 4h under the condition (the hydrogen yield is 95%).
Example 5
1) Reducing the size of the metal hydride to below 500 nm: MgH is added2Ball-milling for 10h in 4bar hydrogen atmosphere, wherein the ball-material ratio is 4: 1, rotational speed 250 rpm.
2) 47.6 mg CoCl was added to the beaker2•6H2O, 150 mg of cetyltrimethylammonium chloride, 300 mg of gamma-Al2O3And 2 mL of deionized water, performing ultrasonic treatment for 30min, and then slowly dropwise adding 2.5 mL of 0.18 mol/L NaBH while performing ultrasonic treatment4And (3) continuing ultrasonic treatment for 30min after the solution is dripped, performing centrifugal separation, washing twice with deionized water and ethanol respectively, and then vacuumizing and drying. It was mixed with an equal mass of previously ball-milled MgH in a glove box2Mixing and grinding for 5 min to prepare Co-B/Al2O3-MgH2A catalyst.
The catalyst is subjected to performance evaluation of catalyzing naphthalene hydrogen absorption and desorption, and the hydrogen absorption reaction can be carried out at 150 ℃ and 7MPa H2Under the condition of (1), the reaction is completely carried out for 20H, and the corresponding hydrogen release reaction can be carried out at 300 ℃ and 0.1 MPa H2The hydrogen release for 18 h under the condition (1) is over 7.0 wt percent (the hydrogen yield is 96 percent).
Example 6
1) Reducing the size of the metal hydride to below 500 nm: adding NaAlH4Ball-milling for 10h in 4bar hydrogen atmosphere, wherein the ball-material ratio is 4: 1, rotational speed 250 rpm.
2) 47.6 mg CoCl was added to the beaker2•6H2O, 100 mg of cetyltrimethylammonium chloride, 220 mg of gamma-Al2O3And 2.5 mL of deionized water, performing ultrasonic treatment for 30min, and then slowly dropwise adding 1.5 mL of 0.18 mol/L NaBH while performing ultrasonic treatment4And (3) continuing ultrasonic treatment for 30min after the solution is dripped, performing centrifugal separation, washing twice with deionized water and ethanol respectively, and then vacuumizing and drying. This was mixed with an equal mass of previously ball-milled NaAlH in a glove box4Mixing and grinding for 5 min to prepare Co-B/Al2O3-NaAlH4A catalyst.
Catalyzing the catalystNEvaluation of Hydrogen absorption and desorption Performance of-Ethylcarbazole (NEC) the hydrogen absorption reaction of which can be carried out at 180 ℃ under 10 MPa H2Under the condition of (1) for 1 h,the corresponding hydrogen releasing reaction can be carried out at 200 ℃ and 0.1 MPa H2The hydrogen is discharged for more than 5.5 wt% in 4h under the condition (the hydrogen yield is 95%).
In the above method for reducing the particle size of the metal hydride, the ball milling conditions may be appropriately changed, or the metal hydride having a small particle size may be obtained by a method such as bottom-up synthesis.
In the process of preparing the target catalyst, the charging amount of each raw material can be properly changed, and the surfactant can be cetyl trimethyl ammonium bromide and the like besides cetyl trimethyl ammonium chloride.
In the above process of preparing the target catalyst, the grinding conditions may be appropriately changed, or the metal hydride after ball milling and a general liquid organic hydrogen carrier may be mixed by ball milling or the like to hydrogenate or dehydrogenate the catalyst.
Claims (10)
1. A transition metal-boron based catalyst for catalyzing hydrogen uptake and desorption by a liquid organic hydrogen carrier, the catalyst comprising a catalyst carrier and an active catalytic component supported on the catalyst carrier, wherein: the active catalytic component is a mixed component of transition metal-boron and metal hydride; the transition metal-boron is prepared by the reaction of transition metal salt and borohydride solution.
2. The transition metal-boron based catalyst for catalyzing the absorption and desorption of hydrogen from a liquid organic hydrogen carrier of claim 1 wherein: the transition metal-boron is prepared by the following preparation steps: the preparation method comprises the following steps of ultrasonically dispersing transition metal salt, hexadecyl trimethyl ammonium chloride, a catalyst carrier and deionized water, slowly dropwise adding a borohydride solution under an ultrasonic condition, continuing to perform ultrasonic treatment after dropwise adding, performing centrifugal separation, cleaning, and finally performing vacuum drying.
3. The transition metal-boron based catalyst for catalyzing the absorption and desorption of hydrogen from a liquid organic hydrogen carrier of claim 1 wherein: the mass ratio of the transition metal-boron to the metal hydride is 1: 0.5-2.
4. A transition metal-boron based catalyst for catalyzing the absorption and desorption of hydrogen from a liquid organic hydrogen carrier in accordance with claim 1, wherein: the transition metal-boron is selected from one of Fe-B, Co-B, Ni-B, NiFe-B, NiCo-B, FeCo-B or FeCoNi-B.
5. A transition metal-boron based catalyst for catalyzing the absorption and desorption of hydrogen from a liquid organic hydrogen carrier according to claim 2 wherein: the transition metal salt is selected from CoCl2•6H2O、NiCl2•6H2O、FeSO4•7H2One or more of O.
6. A transition metal-boron based catalyst for catalyzing the absorption and desorption of hydrogen from a liquid organic hydrogen carrier according to claim 2 wherein: the catalyst carrier is selected from Al2O3、SiO2Or one of graphene.
7. A transition metal-boron based catalyst for catalyzing the absorption and desorption of hydrogen from a liquid organic hydrogen carrier according to claim 2 wherein: the molar ratio of the transition metal salt to the hexadecyl trimethyl ammonium chloride is 1: 1.5-2; the mass ratio of the hexadecyl trimethyl ammonium chloride to the catalyst carrier to the deionized water is 1: 2-5: 2-5; the molar ratio of the transition metal salt to the borohydride is 1:1 to 2.
8. A transition metal-boron based catalyst for catalyzing the absorption and desorption of hydrogen from a liquid organic hydrogen carrier in accordance with claim 1, wherein: the metal hydride includes LiH, MgH2、YH3、LaH3、GdH3、NaAlH4One or more of them.
9. A method according to claim 1 or 2 forTransition metal-boron based catalyst for catalyzing hydrogen absorption and desorption of a liquid organic hydrogen carrier, characterized in that: the borohydride solution is selected from NaBH4Solutions or KBH4One of the solutions.
10. A process for preparing a transition metal-boron based catalyst for catalyzing the absorption and desorption of hydrogen from a liquid organic hydrogen carrier according to any one of claims 1 to 8, wherein: the preparation steps are as follows:
1) reducing the size of the metal hydride to below 500 nm: ball-milling metal hydride in 4bar hydrogen atmosphere for 2h, wherein the ball-to-material ratio is 4: 1, the rotating speed is 250 rpm;
2) preparation of transition metal-boron: adding 0.2-0.5 mmol of transition metal salt, hexadecyl trimethyl ammonium chloride, a catalyst carrier and deionized water into a beaker according to the proportion in claim 7, carrying out ultrasonic treatment for about 30min, slowly dropwise adding a borohydride solution with the concentration of 0.15-0.2 mol/L according to the proportion in claim 7 while carrying out ultrasonic treatment, continuing the ultrasonic treatment for about 30min after the dropwise adding is finished, carrying out centrifugal separation, washing with the deionized water and ethanol twice respectively, and then carrying out vacuum drying;
3) preparation of the catalyst: mixing the transition metal-boron prepared in the step 2) and the metal hydride ball-milled in advance in the step 1) according to the mass ratio of 1: and (3) mixing and grinding for about 5 min by 0.5-2 to prepare the transition metal-boron-based catalyst for catalyzing hydrogen absorption and hydrogen desorption of the liquid organic hydrogen carrier.
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