CN109225284B - Hydrogen storage material decomposition and desorption system - Google Patents

Hydrogen storage material decomposition and desorption system Download PDF

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CN109225284B
CN109225284B CN201710559516.3A CN201710559516A CN109225284B CN 109225284 B CN109225284 B CN 109225284B CN 201710559516 A CN201710559516 A CN 201710559516A CN 109225284 B CN109225284 B CN 109225284B
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hydrogen
catalyst
storage material
hydrogen storage
catalytic
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CN109225284A (en
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陈勇
彭成云
陈倩倩
侯春朝
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Technical Institute of Physics and Chemistry of CAS
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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
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
    • B01J27/1853—Phosphorus; Compounds thereof with iron group metals or platinum group metals with iron, cobalt or nickel
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/745—Iron
    • 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
    • C01B3/0005—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes
    • C01B3/001—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes characterised by the uptaking medium; Treatment thereof
    • 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
    • C01B3/0005—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes
    • C01B3/001—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes characterised by the uptaking medium; Treatment thereof
    • C01B3/0015—Organic compounds; Solutions thereof
    • 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
    • Y02E60/32—Hydrogen storage
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

Abstract

The invention discloses a hydrogen storage material decomposition hydrogen releasing bodyA system comprising a hydrogen storage material, a catalyst and a solvent; the catalyst is a mixture of more than two metal compounds mixed according to any proportion. The invention provides a cheap and stable hydrogen desorption system for catalyzing the decomposition of hydrogen storage materials, and the raw materials for preparing the catalyst are cheap; the catalyst has stable property, and has high hydrogen release efficiency when being applied to a catalytic hydrogen storage material; the catalytic hydrogen release system of the invention is heterogeneous catalytic reaction, which is convenient for recycling the catalyst; if the catalytic hydrogen release system is carried out in an organic solvent, the catalytic reaction can be carried out at the temperature below 273K; in the catalytic hydrogen release system, when the used hydrogen storage material is ammonia borane and methanol is used as a solvent, NH obtained after alcoholysis4B(OCH3)4Under certain conditions, ammonia borane can be obtained again.

Description

Hydrogen storage material decomposition and desorption system
Technical Field
The invention relates to the technical field of hydrogen fuel cells. And more particularly to a hydrogen storage material decomposition and desorption system.
Background
With the development of industry and the proliferation of population, fossil fuel is gradually exhausted and the environment is gradually deteriorated, and the development and storage of new clean energy becomes a new focus of the development of each country. Hydrogen is highly regarded as the cleanest energy source. Chemical hydrogen storage materials that are highly safe have received much attention in the last decade due to the high cost and high risk faced by direct storage of hydrogen.
The chemical hydrogen storage material can stably exist in a solid or liquid form at room temperature, and releases hydrogen under the condition of heating or adding a catalyst. Among them, hydrogen gas is most commonly released from hydrogen storage materials in water, ionic liquids or organic solvents using catalysts. The catalyst is metal nanoparticles, non-metal compound (Ni)2P, CoP, CoB, CoNiP, Co-Ni-B), metal complexes and small amounts of oxides.
The method and the catalyst have achieved certain research results on hydrogen release of the hydrogen storage material, but have the following disadvantages: metal nano particles and non-metal compounds are easy to oxidize, and the metal complex is difficult to prepare and low in efficiency; the ionic liquid is high in cost when used as a solvent; if using catalysisThe agent for catalyzing the hydrogen storage material to hydrolyze and release hydrogen is influenced by the temperature of the system, and the system is frozen when the temperature is lower than 273K; no matter water or ionic liquid is adopted, the recovery and the reutilization of products after the hydrogen storage material is dehydrogenated are not facilitated, and particularly ammonia borane (NH)3BH3，AB)。
Therefore, it is desirable to provide a system for decomposing and releasing hydrogen from a hydrogen storage material which is stable, efficient, inexpensive, recyclable, and has a wide range of use conditions.
Disclosure of Invention
It is an object of the present invention to provide a hydrogen storage material decomposition and hydrogen evolution system.
In order to achieve the purpose, the invention adopts the following technical scheme:
a hydrogen storage material decomposition hydrogen release system comprises a hydrogen storage material, a catalyst and a solvent; the catalyst is a mixture obtained by grinding more than two metal compounds according to any proportion. The catalyst is obtained by mixing more than two metal compounds, and the metal compounds have a synergistic effect, so that the catalytic decomposition hydrogen release efficiency is improved under the synergistic effect of the mutual cooperation of the metal compounds.
Preferably, the grinding means includes, but is not limited to, manual grinding and ball mill grinding. The purpose of the grinding of the invention is to ensure that a plurality of metal compounds have close surface contact with each other, so that atoms of the plurality of metal compounds generate interaction, and the improvement of the catalytic efficiency is promoted.
Preferably, the hydrogen storage material is ammonia borane, borohydride, hydrazine hydrate, hydrazine borane, formic acid or acetic acid.
Preferably, the hydrogen storage material, catalyst and solvent are mixed in any proportion. The hydrogen can be generated by mixing the three components.
Preferably, the catalyst is powder formed by uniformly mixing more than two metal compounds, and the dosage of the metal compounds is any proportion; the mixing mode is a conventional mode, and grinding, powder dispersion in a solvent and ultrasonic waves are preferred. In the invention, different metal compounds are ground together to generate a synergistic effect on a contact surface; one metal compound is used as a carrier of the other metal compound, and the dispersion effect is good.
Preferably, the catalyst is a mixture of two metal compounds mixed in any ratio. In the research process, the technical personnel of the invention find that the mass ratio of the metal compounds influences the catalytic rate and needs to be matched according to the actual situation. For example, in certain embodiments of the invention, the catalyst is CoP and Cu3P, CoP and Cu3The mass ratio of P is 7:3, the obtained catalytic rate is optimal. The catalyst is Fe (OH)3And Cu (OH)2Of Fe (OH)3And Cu (OH)2The mass ratio of (A) to (B) is 6.5: at 3.5, the optimum catalytic rate is obtained.
Preferably, the metal compound in the catalyst is a metal phosphide, a metal hydroxide, a metal sulfide, a metal nitride, a metal carbide, a metal oxide, a metal selenide, a metal phosphate, a metal molybdate, a metal tungstate, a metal oxyhydroxide, or a metal carbonate. The method for preparing the different metal compounds described in the present invention is not limited.
Preferably, the metal of the metal compound in the catalyst is manganese, iron, cobalt, nickel, copper, molybdenum, tungsten, indium, antimony, gallium, tin, aluminum, zinc, cadmium or titanium. The metal in the invention is cheap metal, so that the price is low and the cost is saved.
Preferably, the metal compound has the formula MxRyOr MxPnOyWherein M is Mn, Fe, Co, Ni, Cu, Mo, W, In, Sb, Ga, Sn, Al, Zn, Cd or Ti, R is P, OH, S, N, C, O, Se, OOH, (MoO)n、(WO)nOr (CO)3P represents phosphorus, O represents oxygen, 0<x<20，0<y<30，0<n<10. Further, in some embodiments of the present invention, for example, x has a value range of: 0<x<18、0<x<16、0<x<14、0<x<12、0<x<10、0<x<8、0<x<6、0<x<4、0<x<2、2<x<20、4<x<20、6<x<20、8<x<20、10<x<20、12<x<20、14<x<20、16<x<20、18<x<20、2<x<18、4<x<16、6<x<14、8<x<12, etc.; the value range of y is as follows: 0<y<28、0<y<26、0<y<24、0<y<22、0<y<20、0<y<18、0<y<16、0<y<14、0<y<12、0<y<10、0<y<8、0<y<6、0<y<4、0<y<2、2<y<30、4<y<30、6<y<30、8<y<30、10<y<30、12<y<30、14<y<30、16<y<30、18<y<30、20<y<30、22<y<30、24<y<30、26<y<30、28<y<30、2<y<28、4<y<26、6<y<24、8<y<22、10<y<20、12<y<18、14<y<16, etc.; the value range of n is as follows: 0<n<8、0<n<6、0<n<4、0<n<2、2<n<10、4<n<10、6<n<10、8<n<10、2<n<8、4<n<6, and the like.
Preferably, the metal phosphide has the formula MxPyWherein M is Mn, Fe, Co, Ni, Cu, Mo, W, In, Sb, Ga, Sn, Al, Zn, Cd or Ti, P represents phosphorus, and the value ranges of x and y are defined as above; further, the metal phosphide is specifically Ni2P、NiP、Ni12P5、Ni5P4、Ni7P3、Ni3P、NiP2、FeP、Fe2P、FeP2、FeP4、Fe3P、CoP2、CoP4、CoP3、CoP2、CoP、Co2P、Cu3P、Cu2P7、CuP2、MnP、MnP4、Mn5.6P3、Mn2P、WP、WP2、WP4、TiP、InP、InP3、Sn3P、MoP、Mo4P3、MoP4、MoP2Or Mo8P5And the like.
Preferably, the metal hydroxide has the formula Mx(OH)yWherein M is Mn, Fe, Co, Ni, Cu, Mo, W, In, Sb, Ga, Sn, Al, Zn, Cd or Ti, and the value ranges of x and y are as defined above; further, the metal hydroxide is specifically Fe (OH)3、Co(OH)2、Mn(OH)2、Ni(OH)2、Mn(OH)4、Ni(OH)3、Fe(OH)2、Cu(OH)2、Sn(OH)2Or Al (OH)3And the like.
Preferably, the metal sulfide has the formula MxSyWherein M is Mn, Fe, Co, Ni, Cu, Mo, W, In, Sb, Ga, Sn, Al, Zn, Cd or Ti, S is sulfur, and the value ranges of x and y are defined as above; further, the metal sulfide is specifically Mo3S4、MoS2、Mo2S3、Mo7S8、Mo15S19、CoS、CoS2、Co4S3、Co9S8、Co3S4、NiS、Ni9S8、Ni3S2、Ni7S6、NiS2、CdS、FeS、FeS2、Fe3S4、Cu7S4、Cu2S、CuS2、Cu8S5、Cu7S4Or Cu9S8And the like.
Preferably, the metal nitride has the formula MxNyWherein M is Mn, Fe, Co, Ni, Cu, Mo, W, In, Sb, Ga, Sn, Al, Zn, Cd or Ti, N is nitrogen, and the value ranges of x and y are defined as above; further, the metal nitride is specifically Mo3S4For example: WN, W2N、Mo16N7、Mo2N、MoN、Mo5N6、MnN、Mn3N2、Mn4N、Mn6N2.58、Fe3N、Fe2N、FeN、Fe4N、Co2N、CoN、Co2N0.67、Co5.47N、Ni3N、Ni4N、CuN3、Cu3N、Cu4N or InN, etc.
Preferably, the metal carbide has the formula MxCyWherein M is Mn, Fe, Co, Ni, Cu, Mo, W, In, Sb, Ga, Sn, Al, Zn, Cd or Ti, C is carbon, and x and y have valuesRanges are as previously defined; further, the metal carbide is specifically FeC and Fe3C、Fe5C2、Fe2C、Fe7C3、Mn5C2、Mn7C3、Mn15C4、MnC8、Co2C、Co3C、CoC8、Ni3C、WC、W2C、CW3Or CuC8And the like.
Preferably, the metal oxide has the formula MxOyWherein M is Mn, Fe, Co, Ni, Cu, Mo, W, In, Sb, Ga, Sn, Al, Zn, Cd or Ti, O is oxygen, and the value ranges of x and y are defined as above; further, the metal oxide is specifically Mo4O11、MoO2、MoO3、Mo9O26、CoO、Co2O3、Co3O4、NiO、Ni2O3、FeO、Fe2O3、Fe3O4、CuO、Cu2O、Cu4O3、MnO、MnO2、Mn3O4、Mn2O3、Mn5O8、WO3、WO2、W5O14、SnO2、SnO、Sn2O3、Sn3O4、TiO2、TiO、Ti3O5、Ti4O7、Ti6O11、Ti2O3、Al2O3CdO or CdO2And the like.
Preferably, the metal selenide has the formula MxSeyWherein M is Mn, Fe, Co, Ni, Cu, Mo, W, In, Sb, Ga, Sn, Al, Zn, Cd or Ti, Se is selenium, and the value ranges of x and y are defined as above; further, the metal selenide is specifically MnSe or MnSe2、FeSe、FeSe2、Fe7Se2、Fe7Se8、Co9Se8、CoSe、CoSe2、Ni6Se5、NiSe2、Ni3Se2、NiSe、Ni3Se4、Ni0.85Se、Cu5Se4、Cu2Se、CuSe、Cu7Se4、CuSe2、Cu3Se2、CdSe、MoSe2、Mo15Se19、Mo3Se4、Mo9Se11Or WSe2And the like.
Preferably, the metal oxyhydroxide has the formula Mx(OOH)yWherein M is Mn, Fe, Co, Ni, Cu, Mo, W, In, Sb, Ga, Sn, Al, Zn, Cd or Ti, and the value ranges of x and y are defined as above; further, the metal oxyhydroxide is specifically FeOOH, CoOOH, NiOOH or the like.
Preferably, the metal phosphate has the formula MxPnOyWherein M is Mn, Fe, Co, Ni, Cu, Mo, W, In, Sb, Ga, Sn, Al, Zn, Cd or Ti, P is phosphorus, and the value ranges of x, y and n are as defined above.
Preferably, the metal molybdate has the formula Mx[(MoO)n]yWherein M is Mn, Fe, Co, Ni, Cu, Mo, W, In, Sb, Ga, Sn, Al, Zn, Cd or Ti, Mo is molybdenum, and the value ranges of x, y and n are defined as above.
Preferably, the metal tungstate has the formula Mx[(WO)n]yWherein M is Mn, Fe, Co, Ni, Cu, Mo, W, In, Sb, Ga, Sn, Al, Zn, Cd or Ti, W is tungsten, and the value ranges of x, y and n are as defined above.
Preferably, the metal carbonate has the formula Mx[(CO)3]yWherein M is Mn, Fe, Co, Ni, Cu, Mo, W, In, Sb, Ga, Sn, Al, Zn, Cd or Ti, C is carbon, and the value ranges of x, y and n are as defined above.
Preferably, the solvent is an organic solvent and/or water. The solvent in the system can be water alone, or can be mixed with the organic solvent in any proportion, and can be the organic solvent alone. Preferably, when the solvent is an organic solvent, the catalytic reaction can be carried out at a temperature below 273K, so that the application range of the system is widened.
Preferably, the organic solvent is methanol, ethanol, ethylene glycol, glycerol or propanol. The organic solvent in the present invention not only provides protons for hydrogen generation, but also enables the catalytic reaction to proceed at a temperature of 273K or less.
Preferably, the hydrogen storage material decomposition and desorption system further comprises a base. The technicians of the invention find that the addition of alkali can improve the catalytic rate of the catalyst and shorten the induction period. The base in the present invention provides OH-，OH-Can promote the hydrogen generation rate and shorten the induction period, and the base can partially ionize OH in the solvent-The other part is hydrolyzed to generate OH-。
Preferably, the alkali in the hydrogen storage material decomposition hydrogen desorption system is NaOH, KOH, LiOH, CsOH, ammonia water and Na2CO3、NaHCO3、K2CO3Or KHCO3。
Preferably, the concentration of the alkali in the solvent is more than or equal to 0.0001 mol/L; the base content can continue to increase after reaching a saturation concentration in the solvent, which is theoretically of no economic value. Therefore, more preferably, the concentration of the base in the solvent is from 0.0001mol/L to a saturated concentration. Further, in some embodiments of the present invention, for example, the concentration of the alkali in the solvent is 0.0001-2 mol/L, 0.0001-1.5 mol/L, 0.0001-1 mol/L, 0.0001-0.7 mol/L, 0.0001-0.6 mol/L, 0.0001-0.5 mol/L, 0.0001-0.4 mol/L, 0.0001-0.3 mol/L, 0.0001-0.2 mol/L, 0.0001-0.1 mol/L, 0.1-0.7 mol/L, 0.2-0.7 mol/L, 0.3-0.7 mol/L, 0.4-0.7 mol/L, 0.5-0.7 mol/L, 0.6-0.7 mol/L, 0.7-2 mol/L, 0.8-2 mol/L, 0.9-2 mol/L, 0.5-0.7 mol/L, 0.6-0.7 mol/L, 0.7-2 mol/L, 0.8-2 mol/L, 0.9-0.1-0.5 mol/L, 0.5-0.7 mol/L, 0.5-0.7 mol/L, 0.5mol/L, 0.7mol/L, 0.5-0.2 mol/L, 0.7mol/L, 0.5-0.2 mol/L, 0.7mol/L, 0.5-2 mol/L, 0.2mol/L, 0.5-2 mol/L, 0.2mol/L, 0.7mol/L, 0.5mol/L, 0.7mol/L, 0.2mol/L, 0.5mol/L, 0.7mol/L, 0.2L, 0.5mol/L, 0.5-0.7 mol/L, 0.2L, 0.7mol/L, 0.5-0.7 mol/L, 0.5mol/L, 0.7mol/L, or 2L, 0.7, 0.6 to 0.7 mol/L.
The invention aims to overcome the primary technical problem of how to obtain a hydrogen storage material decomposition and desorption system which is stable, efficient, cheap, recyclable and wide in use condition. In order to overcome the technical problems, the invention adopts a plurality of stable metal compounds as the catalyst, and the metal compounds are mutually matched and act synergistically, thereby not only solving the problem that most of single metal compounds can not catalyze the hydrogen storage material to discharge hydrogen, but also improving the catalysis rate. In addition, the solvent in the invention is organic solvent and/or water, thus widening the application range of the system.
In addition, unless otherwise specified, all starting materials for use in the present invention are commercially available, and any range recited herein includes any value between the endpoints and any subrange between the endpoints and any value between the endpoints or any subrange between the endpoints.
The invention has the following beneficial effects:
1) the invention provides a cheap and stable hydrogen storage material decomposition and desorption system, and raw materials for preparing the catalyst are cheap.
2) The invention adds alkali into the hydrogen storage material decomposition and desorption system, which can improve the catalytic rate of the catalyst and shorten the induction period.
3) The catalyst has stable property and high hydrogen desorption efficiency when being applied to catalyzing hydrogen storage materials.
4) The catalytic hydrogen discharge system of the invention is heterogeneous catalytic reaction, which is convenient for recycling the catalyst.
5) When the catalytic hydrogen release system of the present invention is carried out in an organic solvent, the catalytic reaction can be carried out at a temperature of 273K or less.
6) In the catalytic hydrogen release system of the present invention, ammonia borane (NH) is used as the hydrogen storage material3BH3AB) and methanol as solvent, NH obtained after alcoholysis4B(OCH3)4Under certain conditions, ammonia borane (NH) can be recovered3BH3AB), thereby can recycle ammonia borane, reduce cost.
Drawings
The following describes embodiments of the present invention in further detail with reference to the accompanying drawings.
FIG. 1 shows CoP and Cu in different ratios prepared in examples 1-4 of the present invention3Mixed powder diffraction (XRD) spectrum of P.
FIG. 2 shows the curves of the hydrogen evolution volume over time during the catalytic alcoholysis for the systems of examples 1-4 and comparative examples 1-2 of the present invention.
FIG. 3 shows the curves of hydrogen evolution volume over time during catalytic alcoholysis for systems of examples 5-10 of the present invention.
FIG. 4 shows Cu (OH), one of the materials prepared in example 12 of the present invention2Transmission Electron Microscopy (TEM) images of (a).
FIG. 5 shows Fe (OH), one of the materials prepared in example 12 of the present invention3Transmission Electron Microscopy (TEM) images of (a).
FIG. 6 shows Fe (OH) in a mass ratio of 6.5:3.5 prepared in example 12 of the present invention3And Cu (OH)2Powder diffraction (XRD) spectrum of (a).
FIG. 7 shows Fe (OH) in a mass ratio of 6.5:3.5 prepared in example 12 of the present invention3And Cu (OH)2Transmission Electron Microscope (TEM) image of the mixed powder of (a).
FIG. 8 shows the volume of hydrogen evolved over time during catalytic alcoholysis for systems of examples 11-15 of the present invention.
FIG. 9 shows the volume of hydrogen evolved over time during catalytic alcoholysis for the systems of example 12 and example 15 according to the present invention.
FIG. 10 shows the plot of hydrogen evolution volume over time during catalytic alcoholysis for systems of examples 16-20 of the present invention.
FIG. 11 shows the curves of ln rate as a function of ln [ Cat ] during the catalytic alcoholysis process for systems of examples 16-20 of the present invention.
FIG. 12 shows a Transmission Electron Microscopy (TEM) image of the catalyst recovered in example 29 of the present invention.
FIG. 13 shows the plot of hydrogen evolution volume over time during catalytic alcoholysis for systems of examples 21-24 of the present invention.
FIG. 14 shows the plot of ln rate versus ln [ AB ] during catalytic alcoholysis for systems of examples 21-24 of the invention.
FIG. 15 shows the volume of hydrogen evolved over time during catalytic alcoholysis for systems of examples 25-28 of the present invention.
FIG. 16 shows the plot of ln rate as a function of the reciprocal temperature during catalytic alcoholysis for systems of examples 25-28 of the present invention.
FIG. 17 shows a plot of hydrogen evolution volume over time during catalytic alcoholysis for the system of example 29 of the present invention.
FIG. 18 shows a plot of hydrogen evolution volume over time during catalytic alcoholysis for the system of example 56 of the present invention.
Detailed Description
In order to more clearly illustrate the invention, the invention is further described below with reference to preferred embodiments and the accompanying drawings. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and is not to be taken as limiting the scope of the invention.
The hydrogen decomposition and desorption system of the hydrogen storage material is used for decomposing and desorbing hydrogen and comprises the following steps:
a multi-mouth reaction container with a magnetic stirrer is fixed in a constant-temperature water bath kettle, after a catalyst is added, the outlet of the reactor is sealed by a plug and the like, and the last remaining outlet is connected with a gas measuring pipe filled with water by a rubber pipe, so that the complete device is ensured to have no gas exchange with the surrounding environment. The solution containing the hydrogen storage material is injected into the syringe through a rubber plug, and the volume of the gas discharging water at different times is recorded. The hydrogen generated was detected by Shimadzu DC-14C gas chromatography using a 0.5nm molecular sieve column (3 m.times.2 mm), thermal conductivity cell detector (TCD) and argon as carrier gas.
Examples 1 to 4 and comparative examples 1 to 2
A hydrogen generation system for decomposing hydrogen storage material is disclosed, which is characterized in that the influence of the mass proportion of metal compounds in a catalyst on the catalytic rate is measured, namely the dosage proportion of the metal compounds in the catalyst of the system is changed, and the hydrogen generation rate of the system is calculated as shown in Table 1.
The system comprises 50mg of ammonia borane, 5mL of mixed solution comprising sodium hydroxide and methanol, and 10mg of CoP and Cu3P is catalyst mixed according to different mass ratios; wherein the concentration of sodium hydroxide in the mixed solution of sodium hydroxide and methanol is 0.6 mol/L;
CoP and Cu3Preparation of catalysts with P mixed according to different proportions: CoP and CoP of different mass ratiosCu3And P is respectively and uniformly mixed in platinum grinding, and then each sample is fully ground to obtain the catalyst after full grinding. The obtained catalyst was subjected to powder diffraction, and the results obtained are shown in FIG. 1, from which FIG. 1, CoP and Cu were found3No chemical reaction occurs between P, only simple physical mixing, Cu3The diffraction peak of P in the mixed phase becomes small, indicating that the crystallinity is deteriorated.
Table 1 different CoP: cu3Hydrogen production rate obtained from P mass ratio
Example numbering CoP：Cu3Mass ratio of P Hydrogen production rate (mL/min)
Comparative example 1 0:10 2.6
Example 1 3:7 6.8
Example 2 5:5 14.1
Example 3 7:3 21.5
Example 4 8:2 15.4
Comparative example 2 10:0 0.3
The hydrogen decomposition and desorption system of the hydrogen storage material is used for decomposing and desorbing hydrogen, when 298K, the catalyst is added into the reaction vessel, the mixed solution of sodium hydroxide and methanol in which ammonia borane is dissolved is injected, and the volume of hydrogen collected by the gas measuring pipe at different moments is recorded. The hydrogen volume per time was plotted against time, as shown in FIG. 2. It can be concluded from the results shown in FIG. 2 that CoP and Cu were changed3The dosage ratio of P can obtain different hydrogen production rates. The hydrogen production rate shows a rule of increasing first and then decreasing with the increase of the mass of the CoP, wherein 7: maximum at time 3.
Further, according to comparative examples 1 and 2, it can be seen that when the metal compound in the catalyst is a single metal compound, the hydrogen production rate is much smaller than that of the mixed metal compound, such as 2.6mL/min when CoP alone is contained in the catalyst and Cu alone is contained in the catalyst3The speed of P is 0.30mL/min, and the speed of the P and the P after mixing is higher than that of the P and P after mixing by taking a single metal compound as a catalyst.
Examples 5 to 10
The method steps are the same as example 2, but the difference is only that the concentration of sodium hydroxide in the system is changed, and the hydrogen production rate of the system is calculated as shown in table 2.
TABLE 2 hydrogen production rates obtained for different sodium hydroxide concentrations in mixed solutions of sodium hydroxide and methanol
Figure BDA0001346685460000091
The hydrogen decomposition and desorption system of the hydrogen storage material is used for decomposing and desorbing hydrogen, when 298K, the catalyst is added into the reaction vessel, the mixed solution of sodium hydroxide and methanol in which ammonia borane is dissolved is injected, and the volume of hydrogen collected by the gas measuring pipe at different moments is recorded. The hydrogen volume per time was plotted against time, as shown in FIG. 3. From the results shown in FIG. 3, it can be understood that as the concentration of sodium hydroxide increases, the rate of hydrogen gas generation per unit time exhibits a rule of increasing and then decreasing, and when the concentration of sodium hydroxide exceeds 0.6mol/L, the rate decreases, and therefore, there is a case where part of sodium hydroxide is not dissolved.
Examples 11 to 15 and comparative examples 3 to 4
A hydrogen generation system by hydrogen storage material decomposition is used for measuring the influence of the mass proportion of metal compounds in a catalyst on the catalytic rate, namely the dosage proportion of the metal compounds in the catalyst of the system is changed, as shown in a table 3, and the hydrogen generation rate of the system is calculated.
The system comprises 50mg of ammonia borane, 5mL of a mixed solution comprising sodium hydroxide and methanol, 10mg of Fe (OH)3And Cu (OH)2Catalysts mixed according to different mass ratios; wherein the concentration of the sodium hydroxide in the mixed solution of the sodium hydroxide and the methanol is 0.5 mol/L.
Fe(OH)3And Cu (OH)2The preparation of (1): adding 250mg of sodium citrate, 2.0g of sodium hydroxide and 80mL of distilled water into a round-bottom flask, and stirring to dissolve to obtain a mixed solution 1; dissolving 1g of copper nitrate (or ferric nitrate) in 20mL of distilled water to obtain a mixed solution 2; slowly dropwise adding the mixed solution 2 into the mixed solution 1, stirring at room temperature for 1h after dropwise adding, centrifugally collecting precipitate in the mixture, washing the precipitate with a large amount of distilled water, and fully drying and dewatering at 340K to obtain Cu (OH)2Or Fe (OH)3For the obtained Cu (OH)2And Fe (OH)3Transmission Electron Microscopy (TEM) was performed, and the results obtained are shown in FIGS. 4 and 5.
Fe(OH)3And Cu (OH)2Preparation of catalysts mixed in different proportions: mixing Fe (OH) with different mass ratios3And Cu (OH)2And respectively uniformly stirring in platinum grinding, fully grinding each sample, and obtaining the catalyst after fully grinding. Wherein for Fe (OH)3And Cu (OH)2In a mass ratio of 6.5:3.5The results obtained by performing powder diffraction (XRD) and Transmission Electron Microscopy (TEM) are shown in FIGS. 6 and 7, and Cu (OH) can be found from FIGS. 6 and 72And Fe (OH)3After grinding together, Cu (OH)2The stripe structure of (D) was destroyed (TEM), and the diffraction peak in (XRD) disappeared, indicating that Cu (OH)2Crystallinity is impaired.
TABLE 3 different Fe (OH)3：Cu(OH)2Hydrogen production rate obtained by mass ratio
Example numbering Fe(OH)3：Cu(OH)2Mass ratio of Hydrogen production rate (ml/min)
Comparative example 3 10:0 0
Example 11 7:3 27.9
Example 12 6.5:3.5 37.1
Example 13 6:4 28.4
Example 14 5:5 18.0
Example 15 3:7 9.4
Comparative example 4 0:10 1.7
The hydrogen decomposition and desorption system of the hydrogen storage material is used for decomposing and desorbing hydrogen, when 298K, the catalyst is added into the reaction vessel, the mixed solution of sodium hydroxide and methanol in which ammonia borane is dissolved is injected, and the volume of hydrogen collected by the gas measuring pipe at different moments is recorded. The hydrogen volume per time was plotted against time, as shown in FIG. 8. From the results shown in FIG. 8, it can be concluded that the changes in Fe (OH)3And Cu (OH)2Different hydrogen production rates can be obtained according to the mass ratio. Hydrogen production rate following Cu (OH)2The mass increase of (a) exhibits a law of increasing first and decreasing second, with a ratio of 6.5: maximum at 3.5.
Further, according to comparative examples 3 and 4, it can be seen that when the metal compound in the catalyst is a single metal compound, the hydrogen production rate is much smaller than that of the mixed metal compound, such as when Fe (OH) alone is used in the catalyst30mL/min, indicating Fe (OH)3Cannot catalyze hydrogen storage material to release hydrogen, and is Cu (OH) alone2The concentration is 0.30mL/min, and the mixing rate of the two is higher than that of the single metal compound as the catalyst.
Example 15
The hydrogen producing system for hydrogen storing material decomposition is similar to that in example 12 except that the concentration of sodium hydroxide in the solvent is 0 and the hydrogen producing rate is calculated. The hydrogen decomposition and desorption system of the hydrogen storage material is used for decomposing and desorbing hydrogen, and the volume of the hydrogen collected by the gas measuring pipe at different times is recorded. The hydrogen volume per time was plotted against time, as shown in FIG. 9. From the results shown in fig. 9, it can be concluded that sodium hydroxide can promote hydrogen gas release from the hydrogen storage material.
Examples 16 to 20
The method steps are the same as example 12, but the method is different from the method steps in the embodiment in that the amount of the catalyst in the system is changed, and the hydrogen production rate of the system is calculated as shown in the table 4.
TABLE 4 hydrogen production rates obtained for catalysts of different masses
Example numbering Mass of catalyst (mg) Time (min) required for complete hydrogen release Hydrogen production rate (ml/min)
Example 16 2.5 15.5 7.6
Example 17 5 5.5 21.3
Example 18 7.5 4 29.5
Example 12 10 3.2 36.7
Example 19 15 2.1 55.9
Example 20 20 1.7 69.8
The hydrogen decomposition and desorption system of the hydrogen storage material is used for decomposing and desorbing hydrogen, when 298K, the catalyst is added into the reaction vessel, the mixed solution of sodium hydroxide and methanol in which ammonia borane is dissolved is injected, and the volume of hydrogen collected by the gas measuring pipe at different moments is recorded. The hydrogen volumes were plotted against time, respectively, as shown in FIG. 10. The catalytic hydrogen release rate under different catalyst amounts is respectively calculated through the part of each curve close to the straight line, the natural logarithm is taken for 6 catalytic hydrogen release rates and 6 catalyst particle concentrations to obtain 6 ln rates and 6 ln [ Cat ], the curve of the ln rates to the ln [ Cat ] is shown in FIG. 11, the slope of the curve is 0.902, which indicates that the catalytic alcoholysis reaction is a first-order reaction for the catalyst. Thus, in this system, the effect of the amount of catalyst used on the catalytic alcoholysis rate is: the alcoholysis rate of ammonia borane increases with increasing catalyst usage.
Examples 21 to 24
The method steps are the same as example 12, except that the amount of the hydrogen storage material in the system is changed, the amount of the catalyst in the system is 7mg, and the hydrogen production rate of the system is calculated as shown in Table 5.
TABLE 5 Hydrogen production rates obtained for hydrogen storage materials of varying masses
Figure BDA0001346685460000111
Figure BDA0001346685460000121
The hydrogen decomposition and desorption system of the hydrogen storage material is used for decomposing and desorbing hydrogen, when 298K, the catalyst is added into the reaction vessel, the mixed solution of sodium hydroxide and methanol in which ammonia borane is dissolved is injected, the volume of the hydrogen collected by each gas measuring pipe at different time is recorded, and the hydrogen volume and the time are respectively used as curves, as shown in FIG. 13. The catalytic hydrogen release rate under different AB amounts is calculated by the part of each curve close to the straight line, then 4 ln rates are obtained by taking the natural logarithm of the 4 catalytic hydrogen release rates respectively, and 4 ln AB obtained by taking the natural logarithm of the concentration of the 4 ammonia boranes by the ln rates are taken as curves, as shown in FIG. 14, the slope of the curve is 0.515, which indicates that the catalytic alcoholysis reaction is 0.5 grade reaction for AB. Thus, in this system, the effect of the amount of ammonia borane used on the rate of catalytic alcoholysis is: the alcoholysis rate slowly increases with increasing amounts of ammonia borane.
Examples 25 to 28
A hydrogen storage material decomposition and hydrogen release system is used for measuring the influence of temperature on the catalytic rate, namely the method steps are the same as the example 12, only the temperature is changed, and the hydrogen production rate of the system is calculated as shown in the table 6.
TABLE 6 hydrogen production rates obtained at different temperatures
ExamplesNumbering Temperature (K) Time (min) required for complete hydrogen release Hydrogen production rate (ml/min)
Example 12 298 5.6 20.8
Example 25 303 4.05 29.1
Example 26 308 3 40.3
Example 27 313 3.42 34.7
Example 28 317 3.1 38.6
The hydrogen decomposition and desorption system of the hydrogen storage material is used for decomposing and desorbing hydrogen, a catalyst is added into a reaction vessel under different temperature conditions, then a mixed solution of sodium hydroxide and methanol in which ammonia borane is dissolved is injected, the volume of hydrogen collected by each gas measuring tube at different moments is recorded, the volume of the hydrogen is plotted against time, as shown in fig. 15, the catalytic hydrogen desorption rate under different catalyst amounts is respectively calculated by the part of each curve close to a straight line, and then the catalytic hydrogen desorption rate is converted into a rate constant. The natural logarithm of 5 rate constants was taken to obtain 5 ln κ, and finally the activation energy of the reaction in this system was calculated to be about 47.6KJ/mol from the slope of the curve as shown in fig. 16 by plotting the reciprocal of ln κ versus temperature according to the Arrhenius equation. In the system, the influence of the reaction temperature on the catalytic hydrolysis rate is as follows: the alcoholysis rate of ammonia borane increases with increasing temperature.
Example 29
A hydrogen storage material decomposition and hydrogen desorption system is used for measuring the recycling condition of a catalyst in the system, namely, the system comprises 50mg of ammonia borane, 5mL of mixed solution comprising sodium hydroxide and methanol, and 10mg of recovered catalyst Fe (OH) of examples 16-203And Cu (OH)2(ii) a Wherein the concentration of the sodium hydroxide in the mixed solution of the sodium hydroxide and the methanol is 0.5 mol/L.
The hydrogen decomposition and desorption system of the hydrogen storage material is used for decomposing and desorbing hydrogen, at 298K, the recovered catalyst is added into a reaction vessel, the mixed solution of sodium hydroxide and methanol with ammonia borane dissolved is injected, and the volume of hydrogen collected by each gas measuring pipe at different moments is recorded. After the recovered catalyst is used for catalyzing and releasing hydrogen, the catalyst is recovered and washed again for the next cycle.
The volume of hydrogen and the corresponding time during each reuse were recorded separately for 6 reuses of the above recovered catalyst. The hydrogen volume at each time was plotted against time, as shown in fig. 17, where one plot represents one cycle. It can be concluded from the results shown in fig. 17 that the recovered catalyst still remains highly active for catalyzing alcoholysis of ammonia borane. The catalyst of the invention can be recycled, and is economical and environment-friendly.
Examples 30 to 35
The hydrogen producing system for decomposing hydrogen storing material includes measuring the effect of sodium hydroxide concentration in the system solvent on the catalytic rate, altering the sodium hydroxide concentration in the system solvent and calculating the hydrogen producing rate.
The system comprises 50mg of hydrazine hydrate, 5mL of a mixed solution containing sodium hydroxide and methanol, 10mg of FeP and Ni2P is a powder catalyst obtained by mixing and grinding according to the mass ratio of 3: 2; wherein the concentration of the sodium hydroxide in the mixed solution of the sodium hydroxide and the methanol is 0, 0.1mol/L, 0.3mol/L, 0.5mol/L, 0.6mol/L and 0.7mol/L in sequence.
The hydrogen decomposition and desorption system of the hydrogen storage material is used for decomposing and desorbing hydrogen, when 298K, the catalyst is added into the reaction vessel, the mixed solution of sodium hydroxide and methanol in which hydrazine hydrate is dissolved is injected, the volume of hydrogen collected by the gas measuring pipe at different moments is recorded, and the result is similar to that of the embodiment 5-10.
Examples 36 to 39 and comparative examples 5 to 6
The hydrogen producing system for hydrogen storing material includes measuring the effect of the mass ratio of metal compound in catalyst on the catalytic rate, altering the amount ratio of metal compound in catalyst, and calculating the hydrogen producing rate.
The system comprises 50mg of ammonia borane, 5mL of a mixed solution comprising sodium hydroxide and methanol, 10mg of Co (OH)2Mixing and grinding CuO to obtain a powder catalyst according to different mass ratios; wherein the concentration of sodium hydroxide in the mixed solution of sodium hydroxide and methanol is 0.6 mol/L; co (OH)2And CuO in the mass ratios of 3:7, 5:5, 7:3 and 8:2 (examples 36 to 39), 0:10 and 10:0 (comparative examples 5 to 6) in this order.
A hydrogen decomposition and desorption system of a hydrogen storage material is used for decomposing and desorbing hydrogen, when 298K is reached, a catalyst is added into a reaction vessel, a mixed solution of sodium hydroxide and methanol with ammonia borane dissolved is injected, the volume of hydrogen collected by a gas measuring pipe at different moments is recorded, and the result is similar to that of examples 1-4 and comparative examples 1-2.
Examples 40 to 45
The hydrogen producing system for hydrogen storing material includes measuring the influence of the catalyst amount on the catalytic rate, changing the catalyst amount in the system catalyst, and calculating the hydrogen producing rate.
The system comprises 50mg of hydrazine borane, 5mL of mixed solution comprising sodium hydroxide and methanol, prepared from MnC8And Cu2Powder catalyst obtained by mixing and grinding Se according to a ratio of 4:6；
Wherein the concentration of sodium hydroxide in the mixed solution of sodium hydroxide and methanol is 0.6 mol/L;
the mass of the catalyst is sequentially 2.5mg, 5mg, 7.5mg, 10mg, 15mg and 20 mg.
The hydrogen decomposition and desorption system of the hydrogen storage material is used for decomposing and desorbing hydrogen, when 298K, the catalyst is added into the reaction vessel, the mixed solution of sodium hydroxide and methanol in which hydrazine borane is dissolved is injected, the volume of hydrogen collected by the gas measuring pipe at different moments is recorded, and the result is similar to that of the examples 16-20.
Examples 46 to 50
The hydrogen producing system for hydrogen storing material includes measuring the effect of alkali solution consumption on the catalytic rate, changing the alkali solution consumption and calculating the hydrogen producing rate.
The system comprises 50mg of ammonia borane, 5mL of mixed solution comprising sodium borohydride and methanol, and 10mg of WO3And Sn (OH)2Mixing and grinding the obtained powder catalyst according to the ratio of 3: 7;
wherein the concentration of sodium borohydride in the mixed solution of sodium borohydride and methanol is 0, 0.1mol/L, 0.3mol/L, 0.5mol/L, 0.6mol/L and 0.7mol/L in sequence;
the hydrogen decomposition and desorption system of the hydrogen storage material is used for decomposing and desorbing hydrogen, when 298K, the catalyst is added into the reaction vessel, the mixed solution of sodium borohydride and methanol with ammonia borane dissolved in the mixed solution is injected, the volume of hydrogen collected by the gas measuring pipe at different moments is recorded, and the result is similar to that of the embodiment 5-10.
Examples 51 to 54
The hydrogen decomposing and releasing system for hydrogen storing material has measured the influence of the hydrogen storing material amount on the catalytic rate, i.e. the hydrogen producing rate is calculated while changing the hydrogen storing material amount.
The system comprises ammonia borane, 5mL of mixed solution comprising sodium hydroxide and methanol, and 7mg of Co3S4And Cu (CO)3Mixing and grinding the obtained powder catalyst according to the mass ratio of 1: 9; wherein the concentration of sodium hydroxide in the mixed solution of sodium hydroxide and methanol is 0.6 mol/L; the dosage of the ammonia borane is 50mg, 60mg,70mg、80mg。
The hydrogen decomposition and desorption system of the hydrogen storage material is used for decomposing and desorbing hydrogen, when 298K, the catalyst is added into the reaction vessel, the mixed solution of sodium hydroxide and methanol in which ammonia borane is dissolved is injected, the volume of hydrogen collected by each gas measuring pipe at different moments is recorded, and the obtained experimental result is similar to that of the experimental results of the examples 21-24.
Example 55
The method steps of a hydrogen storage material decomposition hydrogen release system are the same as those of example 1, the difference is only that the temperature of the catalytic reaction of the system is changed to 260K, the hydrogen production rate of the system is calculated, the obtained experimental result is similar to that of example 1, and the catalytic reaction can be carried out at the temperature below 273K by adopting an organic solvent.
Example 56
The method steps are the same as example 12, except that the type of the solvent in the system is changed, the hydrogen production rate of the system is calculated as shown in table 7, and the hydrogen volume per time is plotted against time respectively as shown in fig. 18.
TABLE 7 hydrogen production rates obtained for different solvent species
Example numbering Kind of solvent Hydrogen production rate (ml/min)
Example 56 Water (W) 7.6
Example 12 Methanol 37.1
As can be seen from the table, when the solvent is an organic solvent, the obtained hydrogen production rate is high.
It should be understood that the above-mentioned embodiments of the present invention are only examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention, and it will be obvious to those skilled in the art that other variations or modifications may be made on the basis of the above description, and all embodiments may not be exhaustive, and all obvious variations or modifications may be included within the scope of the present invention.

Claims (5)

1. A hydrogen storage material decomposition hydrogen desorption system is characterized in that the hydrogen storage material decomposition hydrogen desorption system comprises a hydrogen storage material, a catalyst and a solvent; the catalyst is a mixture obtained by grinding more than two metal compounds according to any proportion;
the metal compound in the catalyst is CoP and Cu3P、Fe(OH)3、Cu(OH)2、Co(OH)2、CuO、Co3S4、CuCO3、WO3、Sn(OH)2、MnC8、Cu2Se、FeP、Ni2Any one of P; the solvent is methanol, ethanol, glycol, glycerol or propanol.
2. The system of claim 1, wherein the hydrogen storage material is ammonia borane, borohydride, hydrazine hydrate, hydrazine borane, formic acid, or acetic acid.
3. The system of claim 1, wherein said hydrogen storage material decomposition and desorption system further comprises a base.
4. According to claim3, the hydrogen storage material decomposition hydrogen desorption system is characterized in that the alkali in the hydrogen storage material decomposition hydrogen desorption system is NaOH, KOH, LiOH, CsOH, ammonia water and Na2CO3、NaHCO3、K2CO3Or KHCO3。
5. The system of claim 3, wherein the concentration of the base in the solvent is 0.0001mol/L or more.
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