CN111013663B - 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 the core leg 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 capacity, good reversibility, good heat 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 catalyst based on the transition metal-boron 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 in the present invention is 1.
Further preferably, the transition metal-boron is selected from one of Fe-B, co-B, ni-B, niFe-B, niCo-B, feCo-B and FeCoNi-B.
Further preferably, the transition metal salt according to the invention is selected from CoCl 2 •6H 2 O、NiCl 2 •6H 2 O、FeSO 4 •7H 2 One or more of O.
Further preferably, the catalyst carrier of the present invention is selected from Al 2 O 3 、SiO 2 And graphene.
Further preferably, the molar ratio of the transition metal salt to the cetyltrimethylammonium chloride is 1.5-2; the mass ratio of the hexadecyl trimethyl ammonium chloride to the catalyst carrier to the deionized water is 1:2 to 5:2 to 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 MgH 2 、YH 3 、LaH 3 、GdH 3 、NaAlH 4 One or more of them.
Further preferably, the borohydride solution according to the invention is selected from NaBH 4 Solutions or KBH 4 One 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-material ratio is 4:1, the rotating speed is 250rpm;
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 to carry out ultrasonic treatment for about 30min after completing the dropwise adding, carrying out centrifugal separation, washing with 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: 0.5-2, mixing and grinding for about 5 min to prepare the transition metal-boron-based catalyst TM-B-MH for catalyzing the hydrogen absorption and desorption of the liquid organic hydrogen carrier.
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 discharge.
Drawings
FIG. 1 shows Co-B/Al prepared in example 1 of the present invention 2 O 3 -YH 3 The (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 invention 2 O 3 -YH 3 CatalysisNKinetic profile of hydrogen sorption by ethyl carbazole.
FIG. 3 is a schematic diagram of the device for testing the hydrogen absorption and desorption kinetic curve 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 selected from one of Fe-B, co-B, ni-B, niFe-B, niCo-B, feCo-B and FeCoNi-B.
The transition metal salt is selected from CoCl 2 •6H 2 O、NiCl 2 •6H 2 O、FeSO 4 •7H 2 One or more of O.
The catalyst carrier is selected from Al 2 O 3 、SiO 2 And graphene.
The metal hydride includes LiH, mgH 2 、YH 3 、LaH 3 、GdH 3 、NaAlH 4 One or more of them.
Example 1
1) Reducing the size of the metal hydride to below 500 nm: will YH 3 Ball-milling for 10h in 4bar hydrogen atmosphere, wherein the ball-material ratio is 4:1, rotational speed 250rpm.
2) 47.6 mg CoCl was added to the beaker 2 •6H 2 O, 100 mg of cetyltrimethylammonium chloride, 220 mg of gamma-Al 2 O 3 And 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 treatment 4 And (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 combined with equal mass of previously ball milled YH in glove box 3 Mixing and grinding for 5 min to prepare Co-B/Al 2 O 3 -YH 3 The 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 H 2 Under 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 H 2 The hydrogen is discharged for 7 hours for more than 5.5 wt% (the hydrogen yield is 95%), 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 LaH 3 Ball-milling for 10h in 4bar hydrogen atmosphere, wherein the ball-material ratio is 4:1, rotational speed 250rpm.
2) 47.5 mg NiCl was added to the beaker 2 •6H 2 O, 100 mg of cetyltrimethylammonium chloride, 220 mg of SiO 2 And 2.5 mL of deionized water, performing ultrasonic treatment for 30min, and then slowly adding 1.5 mL of 0.18 mol/L KBH while performing ultrasonic treatment 4 And (3) continuing to perform ultrasonic treatment for 30min after the solution is completely dripped, performing centrifugal separation, washing twice with deionized water and ethanol respectively, and then performing vacuum drying. It was mixed with the previously ball-milled LaH in a glove box 3 According to the following steps of 1: mixing and grinding for 5 min at the mass ratio of 0.5 to prepare Ni-B/SiO 2 -LaH 3 A 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 H 2 Under 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 H 2 The hydrogen is discharged for 12 hours for more than 5.4 wt% (hydrogen yield 95%). The apparatus for testing the hydrogen absorption and desorption kinetic curve 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 GdH 3 Ball-milling for 10h in 4bar hydrogen atmosphere, wherein the ball-material ratio is 4:1, rotational speed 250rpm.
2) Adding 55.6 mg of FeSO into a beaker 4 •7H 2 O, 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 treatment 4 Continuing to perform ultrasonic treatment for 30min after the solution is dripped, centrifuging, and removingWashing with ionized water and ethanol twice, and vacuum drying. It was ball milled with GdH in a glove box 3 According to the following steps of 1:2 for 5 min to prepare Fe-B/rGO-GdH 3 A 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 H 2 Under 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 H 2 The hydrogen discharge for 20 hours under the condition (1) is more than 5.5 wt percent (the hydrogen yield is 95 percent). 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 250rpm.
2) 47.6 mg of CoCl was added to the beaker 2 •6H 2 O, 150 mg of hexadecyltrimethylammonium 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 treatment 4 And (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 7 MPa H 2 Under 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 H 2 The hydrogen evolution for 4 h exceeds 5.5 wt% (hydrogen yield 95%).
Example 5
1) Reducing the size of the metal hydride to below 500 nm: mgH is added 2 Ball-milling for 10h in 4bar hydrogen atmosphere, wherein the ball-material ratio is 4:1, rotational speed 250rpm.
2) 47.6 mg of CoCl was added to the beaker 2 •6H 2 O, 150 mg of cetyltrimethylammonium chloride, 300 mg of gamma-Al 2 O 3 And 2 mL of deionized water, sonicate30min, then slowly dripping 2.5 mL of 0.18 mol/L NaBH while carrying out ultrasonic treatment 4 And (3) continuing to perform ultrasonic treatment for 30min after the solution is completely dripped, performing centrifugal separation, washing twice with deionized water and ethanol respectively, and then performing vacuum drying. It was mixed with an equal mass of previously ball-milled MgH in a glove box 2 Mixing and grinding for 5 min to prepare Co-B/Al 2 O 3 -MgH 2 A 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 7 MPa H 2 Under 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 H 2 The 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 NaAlH 4 Ball-milling for 10h in 4bar hydrogen atmosphere, wherein the ball-material ratio is 4:1, rotational speed 250rpm.
2) 47.6 mg of CoCl was added to the beaker 2 •6H 2 O, 100 mg of cetyltrimethylammonium chloride, 220 mg of gamma-Al 2 O 3 And 2.5 mL of deionized water, performing ultrasonic treatment for 30min, and then slowly dripping 1.5 mL of 0.18 mol/L NaBH while performing ultrasonic treatment 4 And (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 box 4 Mixing and grinding for 5 min to prepare Co-B/Al 2 O 3 -NaAlH 4 A catalyst.
Catalyzing the catalystNEvaluation of Hydrogen absorption and desorption Performance of-Ethylcarbazole (NEC), hydrogen absorption reaction being performed at 180 ℃ under 10 MPa H 2 Under the condition of (1) completely reacting for 1H, and the corresponding hydrogen releasing reaction can be carried out at 200 ℃ and 0.1 MPa H 2 The hydrogen is discharged for more than 5.5 wt% in 4 h 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 changed properly, and the surfactant can be cetyl trimethyl ammonium bromide and the like besides the cetyl trimethyl ammonium chloride.
In the above process for preparing the target catalyst, the grinding conditions may be appropriately changed, or the metal hydride after ball milling and the general liquid organic hydrogen carrier hydrogenation or dehydrogenation catalyst may be mixed by ball milling or other methods.
Claims (1)
1. A preparation method of a transition metal-boron-based catalyst for catalyzing hydrogen absorption and desorption of a liquid organic hydrogen carrier is characterized by comprising the following steps: 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-material ratio is 4:1, the rotating speed is 250rpm;
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 in a beaker according to a proportion, carrying out ultrasonic treatment for 30min, then slowly dropwise adding a borohydride solution with the concentration of 0.15-0.2 mol/L in proportion while carrying out ultrasonic treatment, continuing to carry out ultrasonic treatment for 30min after completing the dropwise addition, carrying out centrifugal separation, washing twice with the deionized water and ethanol 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: 0.5-2, mixing and grinding for 5 min to prepare the transition metal-boron-based catalyst for catalyzing hydrogen absorption and hydrogen desorption of the liquid organic hydrogen carrier;
wherein the molar ratio of the transition metal salt to the hexadecyl trimethyl ammonium chloride is 1.5-2; the mass ratio of the hexadecyl trimethyl ammonium chloride to the catalyst carrier to the deionized water is 1:2 to 5:25; or the mass ratio of the hexadecyl trimethyl ammonium chloride to the catalyst carrier to the deionized water is 1:2 to 5:13.3; or the mass ratio of the hexadecyl trimethyl ammonium chloride to the catalyst carrier to the deionized water is 1:2 to 5:33.3; the molar ratio of the transition metal salt to the borohydride is 1: 1-2;
the transition metal salt is selected from CoCl 2 •6H 2 O、NiCl 2 •6H 2 O、FeSO 4 •7H 2 One or more of O;
the catalyst carrier is selected from Al 2 O 3 、SiO 2 Or graphene;
the borohydride solution is selected from NaBH 4 Solutions or KBH 4 One of the solutions;
the transition metal-boron is selected from one of Fe-B, co-B, ni-B, niFe-B, niCo-B, feCo-B or FeCoNi-B;
the metal hydride includes LiH, mgH 2 、YH 3 、LaH 3 、GdH 3 、NaAlH 4 To (3) is provided.
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