CN113019408A - Preparation method and application of ammonia borane hydrolysis hydrogen production catalyst - Google Patents
Preparation method and application of ammonia borane hydrolysis hydrogen production catalyst Download PDFInfo
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- CN113019408A CN113019408A CN202110268315.4A CN202110268315A CN113019408A CN 113019408 A CN113019408 A CN 113019408A CN 202110268315 A CN202110268315 A CN 202110268315A CN 113019408 A CN113019408 A CN 113019408A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 77
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 73
- 239000001257 hydrogen Substances 0.000 title claims abstract description 73
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 71
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 45
- JBANFLSTOJPTFW-UHFFFAOYSA-N azane;boron Chemical compound [B].N JBANFLSTOJPTFW-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 230000007062 hydrolysis Effects 0.000 title abstract description 11
- 238000006460 hydrolysis reaction Methods 0.000 title abstract description 11
- 229910003158 γ-Al2O3 Inorganic materials 0.000 claims abstract description 44
- 238000000034 method Methods 0.000 claims abstract description 32
- 238000010438 heat treatment Methods 0.000 claims abstract description 22
- 229910003178 Mo2C Inorganic materials 0.000 claims abstract description 20
- 239000011259 mixed solution Substances 0.000 claims abstract description 20
- 239000000243 solution Substances 0.000 claims abstract description 18
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims abstract description 16
- 239000008103 glucose Substances 0.000 claims abstract description 16
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 15
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims abstract description 15
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 15
- 229940078494 nickel acetate Drugs 0.000 claims abstract description 15
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 14
- 239000000843 powder Substances 0.000 claims abstract description 14
- 238000002161 passivation Methods 0.000 claims abstract description 13
- 239000007787 solid Substances 0.000 claims abstract description 13
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- 238000003756 stirring Methods 0.000 claims abstract description 10
- 230000008569 process Effects 0.000 claims abstract description 8
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims abstract description 7
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 7
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 7
- 238000000227 grinding Methods 0.000 claims abstract description 6
- 239000002904 solvent Substances 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 5
- 238000007789 sealing Methods 0.000 claims abstract description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 239000007789 gas Substances 0.000 claims description 12
- 229910052750 molybdenum Inorganic materials 0.000 claims description 10
- 229910052759 nickel Inorganic materials 0.000 claims description 10
- 239000011261 inert gas Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 230000003197 catalytic effect Effects 0.000 claims description 3
- 238000007598 dipping method Methods 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052593 corundum Inorganic materials 0.000 claims description 2
- 238000011068 loading method Methods 0.000 claims description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 2
- 230000003301 hydrolyzing effect Effects 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 10
- 229910052573 porcelain Inorganic materials 0.000 abstract description 6
- QIJNJJZPYXGIQM-UHFFFAOYSA-N 1lambda4,2lambda4-dimolybdacyclopropa-1,2,3-triene Chemical compound [Mo]=C=[Mo] QIJNJJZPYXGIQM-UHFFFAOYSA-N 0.000 abstract description 5
- 229910039444 MoC Inorganic materials 0.000 abstract description 5
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 238000001308 synthesis method Methods 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
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- 238000004321 preservation Methods 0.000 description 12
- 229910003296 Ni-Mo Inorganic materials 0.000 description 11
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 description 11
- 229910002092 carbon dioxide Inorganic materials 0.000 description 10
- 238000003860 storage Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 7
- 229910000510 noble metal Inorganic materials 0.000 description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000001816 cooling Methods 0.000 description 5
- 239000012153 distilled water Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 238000011161 development Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- -1 molybdate ions Chemical class 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000006136 alcoholysis reaction Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910000085 borane Inorganic materials 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
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- 239000003755 preservative agent Substances 0.000 description 2
- 230000002335 preservative effect Effects 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 229910001151 AlNi Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- WZMUUWMLOCZETI-UHFFFAOYSA-N azane;borane Chemical compound B.N WZMUUWMLOCZETI-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000011278 co-treatment Methods 0.000 description 1
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- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 229960001031 glucose Drugs 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
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- 229910052703 rhodium Inorganic materials 0.000 description 1
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- 239000011343 solid material Substances 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 238000000527 sonication Methods 0.000 description 1
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- 238000005979 thermal decomposition reaction Methods 0.000 description 1
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- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/20—Carbon compounds
- B01J27/22—Carbides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0266—Processes for making hydrogen or synthesis gas containing a decomposition step
- C01B2203/0277—Processes for making hydrogen or synthesis gas containing a decomposition step containing a catalytic decomposition step
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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- General Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
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Abstract
The invention discloses a preparation method and application of a catalyst for hydrogen production by ammonia borane hydrolysis. The invention relates to the technical field of molybdenum carbide material preparation and hydrogen production. The method comprises the following steps: (1) dissolving ammonium paramolybdate, nickel acetate and glucose in ammonia water, and stirring until the ammonium paramolybdate, the nickel acetate and the glucose are completely dissolved to form a uniform blue mixed solution; (2) dropwise adding the uniform solution obtained in the step (1) into a container containing metal oxide, uniformly stirring, and sealing the solvent; (3) standing the mixed solution subjected to ultrasonic treatment in the step (2) for second preset time, and drying the mixed solution after standing; (4) grinding the solid obtained in the step (3) into fine powder, putting the fine powder into a porcelain boat, and carrying out staged heating treatment and passivation to obtain Ni-Mo2C/γ‑Al2O3A catalyst. The invention provides an operationSimple process, easy control, safety, environmental protection, low synthesis temperature and easy mass production2And (C) a synthesis method of the catalyst.
Description
Technical Field
The invention relates to a preparation method of a supported catalyst and the technical field of ammonia borane hydrogen production, in particular to supported Ni-Mo2And C, a preparation method of the catalyst.
Background
Environmental problems associated with the excessive use of fossil energy have attracted a great deal of attention. Meanwhile, due to the limited reserves and non-renewable properties of fossil energy, people are forced to continuously search for novel clean energy. The hydrogen energy is known as green energy in 21 st century by the characteristics of cleanness, high efficiency, wide source and high energy density, and will occupy important position in the future energy system. The hydrogen energy is used for replacing fossil energy, and is one of the best ways to solve the future energy shortage and environmental pollution and promote the sustainable development of human society. Because hydrogen is combustible and easy to explode, the safe and efficient storage and preparation of hydrogen are the key for restricting the development of hydrogen energy economy. At present, the storage modes of hydrogen mainly include low-temperature liquid hydrogen storage, high-pressure gaseous hydrogen storage and chemical solid hydrogen storage. The former two methods cannot meet the requirements of people in daily production and life at present due to the limitations of safety, technology and the like. In view of this, researchers have begun to look at solid-state hydrogen storage, i.e., storage of hydrogen in solid materials by physical or chemical adsorption. Ammonia borane (NH) in chemical solid-state hydrogen storage materials3BH3AB) has the advantages of high hydrogen storage density (19.6 wt% of hydrogen storage content), safety and no toxicity at normal temperature and pressure, moderate chemical stability and the like, and is widely concerned. After AB stores hydrogen, hydrogen gas needs to be released for utilization. At present, three hydrogen releasing modes of ammonia borane are mainly adopted, namely hydrogen production by high-temperature thermal decomposition, hydrogen production by alcoholysis and hydrogen production by hydrolysis. Compared with pyrolysis hydrogen production and alcoholysis hydrogen production, AB hydrolysisThe hydrogen production has the advantages of mild reaction conditions, low hydrogen production cost and the like, and is the most important mode for producing hydrogen by using ammonia borane at present. The ammonia borane has high solubility in water and can stably exist in an aqueous solution, after a proper catalyst is added, decomposition reaction can be carried out under 298K to release hydrogen, and products can be dissolved in water while hydrogen is produced, so that toxic gas is hardly generated. Noble metals (Pt, Rh, Ru, Au and Pd) show excellent ammonia borane hydrolysis hydrogen production performance, but the noble metal resources are scarce and high in cost, so that the large-scale application of the noble metals is limited. Therefore, the development of non-noble metal catalysts is imperative. Among non-noble metals, Ni-based and Co-based catalysts have good hydrogen production effect on ammonia borane catalysis, but the hydrogen production efficiency is far from the use requirement. Molybdenum carbide has properties similar to those of noble metals and is of great interest to researchers in hydrogenation reactions, hydrogen production reactions and CO2The molybdenum carbide is widely applied to the catalytic fields of catalytic reduction and the like, and meanwhile, the molybdenum carbide is low in price, so that the molybdenum carbide is expected to be a substitute of a noble metal catalyst with the most potential.
At present, the preparation of transition metal carbide materials (TMCs) usually adopts a temperature programmed carbonization mode of metal oxides in a gas phase, wherein the gas phase is mainly H2With hydrocarbons (CH)4、C2H6CO, etc.). But CH is present during this preparation4、H2Etc. cause potential hazards and high costs. Therefore, a synthetic method which is simple and convenient to operate and is economical is yet to be developed.
Disclosure of Invention
In view of the drawbacks of the prior art, it is an object of the present invention to provide a novel catalyst that enables efficient hydrogen production, i.e. a high TOF value in the hydrogen production process. Therefore, the inventor of the application has carried out a great deal of experiments, and finally finds out a method which can realize the TOF value as high as 80.9mol by combining various different metal and non-metal materials in various different waysH2·molNi -1·min-1The catalyst for hydrogen production.
The catalyst prepared by the method has high TOF value, greatly reduced cost and huge effectGreat social value and commercial promotion value. The materials used in the method are all cheap and easily available materials, and comprise nickel acetate, ammonium paramolybdate, glucose and gamma-Al2O3. Preparation of supported Ni-Mo from these materials2The C catalyst can obviously reduce the cost and threshold of hydrogen production, and the invention adopts CO with weak oxidizability for the first time2The synthesized catalyst is passivated as an oxidizing agent.
Specifically, the invention provides a preparation method of ammonia borane hydrolysis hydrogen production catalyst, which is characterized in that the catalyst is gamma-Al2O3Loaded Ni-Mo2C catalyst, said method comprising mixing Ni and Mo in a predetermined ratio2C is loaded on carrier by one-step dipping method, Ni and Mo2The loading amount of C is calculated by the mass fraction of the whole catalyst; the carrier is gamma-Al2O3。
Preferably, the method comprises the steps of:
(1) dissolving ammonium paramolybdate, nickel acetate and glucose in ammonia water, and stirring until the ammonium paramolybdate, the nickel acetate and the glucose are completely dissolved to form a uniform blue mixed solution;
(2) dropwise adding the uniform solution obtained in the step (1) into a container containing metal oxide, uniformly stirring, sealing the solvent, and performing ultrasonic treatment for a preset time;
(3) standing the mixed solution subjected to ultrasonic treatment in the step (2) for second preset time, and drying the mixed solution after standing to obtain a tan solid;
(4) grinding the solid obtained in the step (3) into fine powder, placing the fine powder in a tube furnace, and carrying out stage-type heating treatment and passivation under inert gas and specific passivation gas to obtain Ni-Mo2C/γ-Al2O3A catalyst.
Preferably, Ni and Mo in the catalyst2C. The carrier mass is respectively: 8-12 parts, 25-35 parts and 55-65 parts.
Preferably, the Ni, Mo2C. The mass fractions of the carrier were 10 wt%, 30 wt% and 60 wt%, respectively.
Preferably, in the step (1), the concentration of the ammonia water is 25-28%.
Preferably, the inert gas is Ar and the specific passivation gas is CO2。
Preferably, in the step (4), the temperature programming heat treatment is to heat up to 300 ℃ at a speed of 2 ℃/min, perform heat preservation treatment for 1h, heat up to 400 ℃ at a speed of 2 ℃/min, perform heat preservation for 1h, then heat up to 720 ℃ at a speed of 2 ℃/min, and perform heat preservation treatment for 3 h.
Preferably, in step (4), the passivation method is to cool the tube furnace to 120-2Gas, passivation treatment time is 2 h.
In another aspect, the present invention provides a gamma-Al2O3Loaded Ni-Mo2The application of the C ammonia borane hydrogen production catalyst is characterized in that the Ni-Mo2The catalyst for producing hydrogen from ammonia borane is used for carrying out catalytic treatment on the process of producing hydrogen from ammonia borane, and the application comprises the following steps: (1) mixing Ni-Mo2C/γ-Al2O3The catalyst is placed in a container, mixed with water and vibrated uniformly; (2) preparing ammonia borane alkali solution; (3) adding the solution prepared in the step (2) into the solution prepared in the step (1).
More specifically, the application method is as follows: with the prepared Ni-Mo2C/γ-Al2O3The material is used as a catalyst for producing hydrogen from ammonia borane, the solvent is distilled water, and the hydrogen is collected by adopting a drainage and gas collection method.
10mg of catalyst is put into a round-bottom flask, 2.5mL of distilled water is added, ultrasonic treatment is carried out for 2min, the mixture is put into a 30 ℃ water bathtub for preheating, and the rotating speed of a magnetic stirrer is 568 r/min. 0.2g NaOH is placed in a beaker, 2.5mL water is added, ultrasonic treatment is carried out until the NaOH solution is completely dissolved, 45mg ammonia borane is added into the NaOH solution, and the beaker is shaken to completely dissolve the ammonia borane. The solution was added to a round bottom flask and hydrogen was collected by draining gas. And when the first bubble emerges from the air outlet, timing is started, and timing is carried out once every 5mL until the reaction is finished.
The invention has the advantages that:
(1) Ni-Mo in the invention2C/γ-Al2O3The preparation method of the catalyst has obvious advantages compared with the prior scheme (such as the scheme mentioned in the background art). The catalyst synthesized by the method has simple process, easy control and easy operation.
(2) Ni-Mo synthesized by the invention2C/γ-Al2O3The catalyst particles are more uniform and fine, and Ni and Mo are uniformly dispersed on the carrier, and the specific surface area is large and is 132.2m2The catalyst has rich mesoporous structure, and is beneficial to the diffusion of reactants and the exposure of active sites in the catalytic reaction process.
(3) The method is more beneficial to Ni and Mo in the preparation process2And C, dissolving nickel acetate, ammonium molybdate and glucose in ammonia water in the dipping process, and fully mixing in the solution. Since the ammonia water can complex Ni2+And molybdate ions, Ni and Mo are well dispersed in the solution. During the drying process, NH is added3And H2The evaporation of O, Ni and Mo precursors can achieve the effect of sufficient contact.
(4) The catalyst prepared by the method has high porosity and good ammonia borane hydrogen production performance, and the TOF value of the catalyst for catalyzing ammonia borane hydrogen production can reach 80.9molH2·molNi -1·min-1Obviously higher than the prior similar method.
Drawings
FIG. 1 shows Ni-Mo prepared in the examples of the present invention2C/γ-Al2O3Powder X-ray diffraction (XRD) pattern of the catalyst. In the figure, 34.5 degrees, 37.9 degrees, 39.5 degrees, 52.2 degrees, 61.6 degrees, 69.6 degrees and 74.7 degrees are Mo2The standard diffraction peak of C is consistent with that of standard card JCPDS No.00-011 and 0680. Meanwhile, AlNi is also contained in the spectrogram3Alloy and Al2O3The diffraction peak of (2) appears, and no obvious metal Ni diffraction peak is observed in the spectrogram.
FIG. 2 shows Ni-Mo prepared by the present invention2C/γ-Al2O3Scanning Electron Microscope (SEM) images of the catalyst. As can be seen from FIG. 2, Ni and Mo2C particles are fine and uniformly dispersed in gamma-Al2O3On a carrier.
FIG. 3 shows the mesoporous Ni-Mo prepared by the present invention2C/γ-Al2O3N of catalyst at 77K temperature2Isothermal adsorption-desorption curve diagram; the specific surface area of the catalyst prepared by the invention is calculated to be 132.2m2/g。
FIG. 4 shows Ni-Mo films prepared in examples of the present invention2C/γ-Al2O3And (4) obtaining a pore size distribution diagram of the catalyst according to an isothermal desorption curve. As can be seen from the figure, the pore diameters are intensively distributed at about 6.1nm, which shows that the prepared catalyst material has typical mesoporous structure characteristics.
FIG. 5 shows Ni-Mo2C/γ-Al2O3Ammonia borane hydrogen production curve of the catalyst. TOF value of ammonia borane hydrogen production catalyzed by the catalyst can reach 80.9molH2·molNi -1·min-1。
FIG. 6 shows a sample of a sample which has not undergone CO2Passivated 10Ni30Mo2C/γ-Al2O3The ammonia borane hydrolysis hydrogen production performance of the catalyst is shown in a diagram.
Detailed Description
The chemical reagents used in the invention are: nickel acetate (Ni (CH)3COO)2·4H2O), ammonium paramolybdate ((NH)4)6Mo7O24·4H2O), glucose, gamma-Al2O3Ammonia (25-28%), argon (Ar) and carbon dioxide (CO)2) Ammonia borane (NH)3BH3) Sodium hydroxide (NaOH), distilled water.
The Ni-Mo of the invention is illustrated by way of example2C/γ-Al2O3The preparation and application of the catalyst are further illustrated, and the carrier used in the invention is not limited to gamma-Al2O3Other metal oxides such as SiO2、ZrO2And the like apply equally.
Example 1: Ni-Mo2C/γ-Al2O3Preparation and passivation of the catalyst
(1) 0.2598g of ammonium paramolybdate, 0.2120g of nickel acetate and 0.1547g of glucose are weighed by an electronic balance, placed in a 10mL small beaker, 1.5mL of ammonia water is weighed by a measuring cylinder, added into the beaker, and stirred until the ammonia water is completely dissolved to form a uniform mixed solution;
(2) weighing 0.3g of gamma-Al2O3And placed in a 25mL small beaker. Then dripping the blue mixed solution obtained in the step (1) into gamma-Al2O3The small beaker is uniformly stirred by a glass rod, then is sealed by a preservative film, is placed in an ultrasonic instrument for ultrasonic treatment for 20min, and then the mixed solution is kept stand for 12 h. The mixture after standing was then dried in an oven at 110 ℃ for 24h to give a tan solid. Grinding the obtained solid into fine powder by an agate mortar, putting the fine powder into a porcelain boat, putting the porcelain boat into a tube furnace, heating to 300 ℃ at the heating rate of 2 ℃/min in the atmosphere of Ar (100mL/min), carrying out heat preservation treatment for 1h, heating to 400 ℃ at the heating rate of 2 ℃/min, carrying out heat preservation treatment for 1h, then heating to 720 ℃ at the speed of 2 ℃/min, carrying out heat preservation treatment for 3h, naturally cooling the tube furnace to 135 ℃ in the atmosphere of Ar, and then switching to CO2(100mL/min) for 2h, and finally placing the tube furnace in CO2Cooling to room temperature in the atmosphere of (100mL/min) to obtain Ni-Mo2C/γ-Al2O3A catalyst powder.
(2) For prepared Ni-Mo2C/γ-Al2O3The catalyst is characterized by surface appearance, phase structure and physical and chemical properties:
XRD was used for the analysis of the crystal phase, and the specific results are shown in FIG. 1;
the appearance of the sample is observed by SEM, and the specific result is shown in FIG. 2;
with N2The specific surface area and the pore size distribution are analyzed by isothermal adsorption-desorption, and specific results are shown in figures 3 and 4. Example 2: Ni-Mo of the invention2C/γ-Al2O3Performance test as ammonia borane hydrogen production catalyst:
(1) preparation of the catalyst:
10mg of Ni-Mo prepared according to the invention2C/γ-Al2O3Placing the catalyst into a 50mL single-mouth round-bottom flask, measuring 2.5mL of distilled water by using a measuring cylinder, pouring the distilled water into the round-bottom flask containing the catalyst, and placing the round-bottom flask into the round-bottom flaskUltrasonic treating in ultrasonic instrument for 2min, and placing in 30 deg.C constant temperature water bath.
(2) Preparation of ammonia borane aqueous solution:
0.2g of NaOH was accurately weighed out and placed in a 25mL beaker, 2.5mL of water was added thereto, and the mixture was dissolved completely by sonication for 30 seconds, and then 45mg of ammonia borane was added to the beaker and stirred until the ammonia borane was completely dissolved.
(3) Adding the solution obtained in the step (2) into the round-bottom flask obtained in the step (1), collecting hydrogen by adopting a drainage gas-collecting method, using a 100mL measuring cylinder when collecting hydrogen, starting timing when a first bubble is emitted from a gas outlet, and timing once every 5mL of collected hydrogen until the reaction is finished. FIG. 5 shows the ammonia borane hydrogen production performance of the catalyst.
In conclusion, the Ni-Mo of the invention2The catalyst C takes nickel acetate as a nickel source, ammonium paramolybdate as a molybdenum source, glucose as a carbon source according to the proportion of Ni and Mo2The mass ratio of C is 1:3, Mo2C, preparing materials according to the mass ratio of 1:7 of the substances C and glucose, dissolving the materials in ammonia water, and stirring and dissolving to obtain a mixed solution; dropwise adding the mixed solution into the gamma-Al solution2O3The mixture is ultrasonically treated for 20min and dried at 110 ℃ for 24h to obtain a tan solid; placing the obtained solid product in argon protective atmosphere, performing heat treatment at 720 ℃ for 3h, and then performing CO treatment2Passivating gas at 135 deg.C (with proper floating temperature) for 2h to obtain the gamma-Al2O3Loaded Ni-Mo2And C, a catalyst. Ni and Mo prepared by the method of the invention2The catalyst has small C particle size, uniformly distributed particles on a metal oxide carrier, high porosity, large specific surface area and good ammonia borane hydrogen production performance, and the TOF value of the ammonia borane hydrogen production catalyzed by the catalyst can reach 80.9mol according to data in a figureH2·molNi -1·min-1。
Comparative example 1
The inventors of the present application also synthesized 30Ni10Mo in exactly the same manner as in example 12C/γ-Al2O3And 10NiMo2And C, a catalyst.
(1) Using an electronic balance to balance Ni and Mo2C、γ-Al2O3Weighing ammonium paramolybdate, nickel acetate and glucose with corresponding mass according to the mass fractions of 30 wt%, 10 wt% and 60 wt% of the carrier, placing the ammonium paramolybdate, nickel acetate and glucose into a 10mL small beaker, weighing 1.5mL ammonia water by using a measuring cylinder, adding the ammonia water into the beaker, and stirring until the ammonia water is completely dissolved to form a uniform mixed solution;
(2) weighing 0.3g of gamma-Al2O3And placed in a 25mL small beaker. Then dripping the blue mixed solution obtained in the step (1) into gamma-Al2O3The small beaker is uniformly stirred by a glass rod, then is sealed by a preservative film, is placed in an ultrasonic instrument for ultrasonic treatment for 20min, and then the mixed solution is kept stand for 12 h. The mixture after standing was then dried in an oven at 110 ℃ for 24h to give a tan solid. Grinding the obtained solid into fine powder by an agate mortar, putting the fine powder into a porcelain boat, putting the porcelain boat into a tube furnace, heating to 300 ℃ at the heating rate of 2 ℃/min in the atmosphere of Ar (100mL/min), carrying out heat preservation treatment for 1h, heating to 400 ℃ at the heating rate of 2 ℃/min, carrying out heat preservation treatment for 1h, then heating to 720 ℃ at the speed of 2 ℃/min, carrying out heat preservation treatment for 3h, naturally cooling the tube furnace to 135 ℃ in the atmosphere of Ar, and then switching to CO2(100mL/min) for 2h, and finally placing the tube furnace in CO2Cooling to room temperature in the atmosphere of (100mL/min) to obtain Ni-Mo2C/γ-Al2O3Catalyst powder
For the synthesized catalyst, the ammonia borane hydrolysis hydrogen production performance is tested by adopting the same condition.
Among all the synthesized catalysts, though 30Ni10Mo2C/γ-Al2O3The catalyst shows a faster hydrogen production rate, but the TOF value of the hydrogen production is 58.3molH2·molNi -1·min-1Significantly lower than 10Ni30Mo2C/γ-Al2O3。
It can be seen from the comparative example that the proportion of the raw materials has a great influence on the hydrogen production performance.
Comparative example 2
In the same manner as in step (1) of example 1, the inventors synthesized 10NiMo2C catalyst, wherein, Ni, Mo2The mass fractions of C were 10 wt% and 90 wt%, respectively, and step (2) was omitted.
For the synthesized catalyst, the ammonia borane hydrolysis hydrogen production performance is tested by adopting the same condition.
The results demonstrate that 10NiMo is not loaded with alumina2C shows poor ammonia borane hydrolysis hydrogen production activity.
The hydrogen production efficiency of comparative example 1 and comparative example 2 is shown in fig. 6 in comparison with that of example 1.
Comparative example 3
In this example, the same material ratios and processes as in example 1 were used except that the CO conversion was omitted in the final stage2The passivation process of (1).
Specifically, in this example, the catalyst prepared was 10Ni30Mo2C/γ-Al2O3Wherein Ni and Mo2C、γ-Al2O3The mass fractions of the carrier were 10 wt%, 30 wt%, and 60 wt%, respectively. The preparation method comprises the following steps:
(1) dissolving ammonium paramolybdate, nickel acetate and glucose in ammonia water, and stirring until the ammonium paramolybdate, the nickel acetate and the glucose are completely dissolved to form a uniform blue mixed solution, wherein the concentration of the ammonia water is 25-28%;
(2) dropwise adding the uniform solution obtained in the step (1) into a container containing metal oxide, uniformly stirring, sealing the solvent, and then placing the solvent into an ultrasonic instrument for ultrasonic treatment for preset time;
(3) standing the mixed solution subjected to ultrasonic treatment in the step (2) for second preset time, and drying the mixed solution after standing to obtain a tan solid;
(4) grinding the solid obtained in the step (3) into fine powder, putting the fine powder into a porcelain boat, and performing stage-type heating treatment in a tube furnace under inert gas to obtain Ni-Mo2C/γ-Al2O3A catalyst.
In the step (4), the temperature programming heat treatment is carried out by heating to 300 ℃ at the speed of 2 ℃/min, carrying out heat preservation treatment for 1h, heating to 400 ℃ at the speed of 2 ℃/min, carrying out heat preservation for 1h, then heating to 720 ℃ at the speed of 2 ℃/min, and carrying out heat preservation treatment for 3 h. And naturally cooling the reaction tube to room temperature, and taking out to obtain the target catalyst.
FIG. 6 shows that CO did not pass through the comparative example2Passivated 10Ni30Mo2C/γ-Al2O3The ammonia borane hydrolysis hydrogen production performance of the catalyst is shown in a graph, and compared with the passivated curves in the graphs in FIGS. 6 and 5, the invention is obviously shown to adopt CO2The passivated hydrogen production effect has obvious advantages. TOF value of hydrogen production is 38.3molH2·molNi -1·min-1The value is obviously lower than that of the CO2Passivating the resulting 10Ni30Mo2C/γ-Al2O3A catalyst.
While the principles of the invention have been described in detail in connection with the preferred embodiments thereof, it will be understood by those skilled in the art that the foregoing embodiments are merely illustrative of exemplary implementations of the invention and are not limiting of the scope of the invention. The details of the embodiments are not to be interpreted as limiting the scope of the invention, and any obvious changes, such as equivalent alterations, simple substitutions and the like, based on the technical solution of the invention, can be interpreted without departing from the spirit and scope of the invention.
Claims (9)
1. The preparation method of the catalyst for preparing hydrogen by hydrolyzing ammonia borane is characterized in that the catalyst is gamma-Al2O3Loaded Ni-Mo2C catalyst, said method comprising mixing Ni and Mo in a predetermined ratio2C is loaded on carrier by one-step dipping method, Ni and Mo2The loading amount of C is calculated by the mass fraction of the whole catalyst; the carrier is gamma-Al2O3。
2. The preparation method of the ammonia borane hydrogen production catalyst according to claim 1, characterized by comprising the following steps:
(1) dissolving ammonium paramolybdate, nickel acetate and glucose in ammonia water, and stirring until the ammonium paramolybdate, the nickel acetate and the glucose are completely dissolved to form a uniform blue mixed solution;
(2) dropwise adding the uniform solution obtained in the step (1) into a container containing metal oxide, uniformly stirring, sealing the solvent, and performing ultrasonic treatment for a preset time;
(3) standing the mixed solution subjected to ultrasonic treatment in the step (2) for second preset time, and drying the mixed solution after standing to obtain a tan solid;
(4) grinding the solid obtained in the step (3) into fine powder, placing the fine powder in a tube furnace, and carrying out stage-type heating treatment and passivation under inert gas and specific passivation gas to obtain Ni-Mo2C/γ-Al2O3A catalyst.
3. The method according to claim 1, wherein Ni and Mo are contained in the catalyst2C. The carrier mass is respectively: 8-12 parts, 25-35 parts and 55-65 parts.
4. The method according to claim 1, wherein the Ni, Mo2C. The mass fractions of the carrier were 10 wt%, 30 wt% and 60 wt%, respectively.
5. The method according to claim 2, wherein the concentration of the aqueous ammonia in the step (1) is 25 to 28%.
6. The method according to claim 2, wherein in the step (4), the inert gas is Ar, and the specific passivation gas is CO2。
7. The method according to claim 2, wherein in the step (4), the temperature-programmed heating treatment is carried out by raising the temperature at a rate of 2 ℃/min to 300 ℃ for 1 hour, raising the temperature at a rate of 2 ℃/min to 400 ℃ for 1 hour, then raising the temperature at a rate of 2 ℃/min to 720 ℃ for 3 hours.
8. The method according to claim 7, wherein in step (4), the passivation method is carried out at the step of raising the temperatureAfter the heat treatment, the tube furnace was naturally cooled to 120 ℃ and 145 ℃, and then switched to CO2Gas, passivation treatment time is 2 h.
9. Gamma-Al2O3Loaded Ni-Mo2The application of the C ammonia borane hydrogen production catalyst is characterized in that the Ni-Mo2The catalyst for producing hydrogen from ammonia borane is used for carrying out catalytic treatment on the process of producing hydrogen from ammonia borane, and the application comprises the following steps: (1) mixing Ni-Mo2C/γ-Al2O3The catalyst is placed in a container, mixed with water and vibrated uniformly; (2) preparing ammonia borane alkali solution; (3) adding the solution prepared in the step (2) into the solution prepared in the step (1).
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