WO2020224584A1 - 有机储氢原料脱氢催化剂以及该催化剂的载体、储氢合金、和提供高纯度氢气的方法 - Google Patents

有机储氢原料脱氢催化剂以及该催化剂的载体、储氢合金、和提供高纯度氢气的方法 Download PDF

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WO2020224584A1
WO2020224584A1 PCT/CN2020/088740 CN2020088740W WO2020224584A1 WO 2020224584 A1 WO2020224584 A1 WO 2020224584A1 CN 2020088740 W CN2020088740 W CN 2020088740W WO 2020224584 A1 WO2020224584 A1 WO 2020224584A1
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hydrogen
weight
hydrogen storage
catalyst
carrier
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PCT/CN2020/088740
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English (en)
French (fr)
Inventor
林伟
杨雪
宋海涛
孙敏
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中国石油化工股份有限公司
中国石油化工股份有限公司石油化工科学研究院
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Application filed by 中国石油化工股份有限公司, 中国石油化工股份有限公司石油化工科学研究院 filed Critical 中国石油化工股份有限公司
Priority to US17/595,035 priority Critical patent/US20220258133A1/en
Priority to JP2021566301A priority patent/JP2022531799A/ja
Priority to AU2020268228A priority patent/AU2020268228A1/en
Priority to EP20802908.2A priority patent/EP3967396A4/en
Priority to CA3139546A priority patent/CA3139546A1/en
Priority to KR1020217040048A priority patent/KR20220005090A/ko
Publication of WO2020224584A1 publication Critical patent/WO2020224584A1/zh

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    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
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    • 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
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    • C01B3/24—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds of hydrocarbons
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    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
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    • F17C1/00—Pressure vessels, e.g. gas cylinder, gas tank, replaceable cartridge
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
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    • F17C11/00—Use of gas-solvents or gas-sorbents in vessels
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
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    • F17C7/00—Methods or apparatus for discharging liquefied, solidified, or compressed gases from pressure vessels, not covered by another subclass
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    • C01P2006/80—Compositional purity
    • 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
    • Y02P90/00—Enabling technologies with a potential contribution to greenhouse gas [GHG] emissions mitigation
    • Y02P90/45—Hydrogen technologies in production processes

Definitions

  • the present invention relates to a catalyst used for dehydrogenation of organic hydrogen storage raw materials to generate hydrogen, a carrier of the catalyst and a preparation method thereof; the present invention also relates to a hydrogen storage alloy and a preparation method thereof; the present invention also relates to a method for providing high purity Hydrogen method, an efficient distributed method for producing high-purity and high-pressure hydrogen, a system for providing high-purity and high-pressure hydrogen, a mobile hydrogen supply system and a distributed hydrogen supply device.
  • Hydrogen exists in gaseous form under normal conditions, and is flammable, explosive, and easy to diffuse. In practical applications, people must give priority to the safety, high efficiency and no leakage of hydrogen storage and transportation. Transportation brings great difficulties. Therefore, hydrogen energy utilization needs to solve the problem of hydrogen storage and transportation.
  • Hydrogen is directly transported from the production site to the hydrogen refueling station through high-pressure gaseous state.
  • the transportation cost is relatively high, and long-distance transportation also has certain traffic safety hazards; the use of high-pressure gaseous hydrogen storage, the high cost of hydrogen storage tanks, large area, and Larger security risks.
  • a method of providing high-purity hydrogen comprising:
  • the organic liquid hydrogen storage raw material is contacted and reacted with a dehydrogenation catalyst to obtain a dehydrogenation reaction product containing hydrogen;
  • the reaction temperature of the contact reaction between the organic liquid hydrogen storage raw material and the dehydrogenation catalyst is 150-450°C (for example, 200-400°C, 300-350°C);
  • the weight hourly space velocity of the contact reaction of the organic liquid hydrogen storage raw material with the dehydrogenation catalyst is 0.5-50 h -1 (for example, 1-45 h -1 , 2-30 h -1 );
  • the contact reaction pressure of the organic liquid hydrogen storage raw material and the dehydrogenation catalyst is 0.03-5MPa (gauge pressure) (for example, 0.3-5MPa, 0.1-3MPa, 0.5-2MPa or 0.2-1.6MPa);
  • the organic liquid hydrogen storage raw material is mixed with hydrogen and then contacted with the dehydrogenation catalyst, and the hydrogen-to-hydrocarbon ratio (the molar ratio of hydrogen to the organic liquid hydrogen storage raw material) is 0-10 (for example, 0-8).
  • the cooling temperature for cooling the dehydrogenation reaction product is lower than the boiling point temperature of the organic substance in the liquid product; preferably, it is lower than the boiling point temperature of the organic substance with the lowest boiling point that is liquid at normal temperature and pressure.
  • the hydrogen-rich gas is a hydrogen-rich gas product or a hydrogen-containing gas obtained by further separation of the hydrogen-rich gas product, and the further separation method includes temperature swing separation, membrane separation, pressure swing adsorption separation or a combination thereof;
  • the mass fraction of hydrogen in the hydrogen-rich gas is ⁇ 80% (for example, 80-99%, preferably ⁇ 85%, more preferably ⁇ 90%).
  • the contact between the hydrogen-rich gas and the hydrogen storage alloy is carried out in one or more hydrogen storage alloy storage containers;
  • the hydrogen storage alloy can be one or more types, and multiple hydrogen storage alloys can be used in combination, and can also be used in series or in parallel or in series and parallel;
  • the pressure at which the hydrogen-rich gas contacts the hydrogen storage alloy is 0.001-5MPa (for example, 0.01-5MPa, 0.03-4MPa, 0.05-5MPa, 0.08-2MPa, 0.05-3MPa, 0.1-1MPa), when the hydrogen storage alloy is stored
  • 0.001-5MPa for example, 0.01-5MPa, 0.03-4MPa, 0.05-5MPa, 0.08-2MPa, 0.05-3MPa, 0.1-1MPa
  • the contact pressure (also called hydrogen absorption pressure) of the final contact with the hydrogen storage alloy is 0.05-5MPa (for example, 0.1-1MPa);
  • the temperature at which the hydrogen-rich gas contacts the hydrogen storage alloy (also called hydrogen absorption temperature) is -70 to 100°C (for example, -50 to 90°C, -30 to 80°C);
  • the temperature of the hydrogen-rich gas is lower than the boiling point temperature of the organic liquid hydrogen storage raw material under normal pressure.
  • the hydrogen storage alloy in the hydrogen storage alloy storage container that contacts the hydrogen last is a hydrogen storage alloy with a high equilibrium pressure according to the order of contacting hydrogen.
  • the hydrogen storage alloy with high equilibrium pressure has at least one temperature point between 150-450°C, and the equilibrium pressure of hydrogen absorption is greater than or equal to 35MPa; preferably, the hydrogen storage alloy in at least one hydrogen storage alloy storage container has a high Hydrogen storage alloy that balances pressure.
  • step (3a) is performed, in which the organic matter in the hydrogen-containing alloy storage container is removed by a purging method (for example, using hydrogen purging,
  • the method is such as: after the hydrogen storage alloy reaches a predetermined adsorption capacity, stop supplying hydrogen-rich gas to the hydrogen storage alloy, let the hydrogen pass through the hydrogen-containing alloy, and transfer the hydrogen-containing alloy and the hydrogen-containing alloy storage container (also called the hydrogen storage alloy storage container)
  • the organic gas in the hydrogen storage alloy is taken out, stored in a storage tank, or absorbed by the hydrogen storage alloy in other hydrogen storage alloy storage containers; among them, the purity of the purging hydrogen gas is preferably greater than 90% by weight, more preferably greater than 95% by weight, for example, greater than 99% by weight).
  • the temperature of the hydrogen released by the hydrogen storage alloy ie, the temperature at which the hydrogen storage alloy is heated, referred to as the hydrogen release temperature
  • the pressure of the released hydrogen is ⁇ 35MPa (for example, 35-100MPa) to obtain high-purity and high-pressure hydrogen
  • the partial pressure of the released hydrogen is 0.1-5 MPa to obtain high-purity hydrogen, wherein the hydrogen release temperature is higher than the hydrogen absorption temperature.
  • the method for providing high-purity hydrogen characterized in that it further comprises causing hydrogen-containing alloys to release hydrogen, and the released hydrogen contacts with different hydrogen storage alloys to form hydrogen-containing alloys, and the process is repeated once Or multiple times, wherein the hydrogen storage alloy used in at least the last repeated process is a hydrogen storage alloy with a high equilibrium pressure.
  • the hydrogen storage alloy is a combination of the first hydrogen storage alloy and the second hydrogen storage alloy
  • the first hydrogen storage alloy is a magnesium-based A 2 B type hydrogen storage alloy for contact with hydrogen-rich gas
  • the second hydrogen storage alloy is used to pressurize the first hydrogen storage hydrogen gas
  • the second hydrogen storage alloy is a hydrogen storage alloy with high equilibrium pressure
  • the second hydrogen storage alloy is rare earth AB 5 type, zirconium titanium AB 2 type, One or more of titanium-based AB-type hydrogen storage alloys;
  • the hydrogen-rich gas first passes through the first hydrogen storage alloy to separate impurities; then the high-purity hydrogen released from the first hydrogen storage alloy is brought into contact with the second hydrogen storage alloy, and then the second hydrogen storage alloy releases hydrogen under high pressure.
  • the hydrogen release temperature of the first hydrogen storage alloy is higher than the hydrogen absorption temperature of the second hydrogen storage alloy, and the temperature difference is preferably ⁇ 100°C (for example, 350°C ⁇ temperature difference ⁇ 150°C);
  • the first hydrogen storage alloy and the second hydrogen storage alloy are in different hydrogen storage alloy storage tanks, and there is a heat exchange system between the first hydrogen storage alloy storage tank and the second hydrogen storage alloy storage tank;
  • the hydrogen absorption temperature at which the hydrogen-rich gas contacts the first hydrogen storage alloy is 20-150°C (for example, 50-100°C), and the hydrogen partial pressure is 0.001-0.1MPa (0.001-0.03MPa);
  • the temperature at which the first hydrogen storage alloy releases hydrogen (hydrogen release temperature) is 150-450°C (for example, 200-350°C), and the hydrogen partial pressure for hydrogen release is 0.1-5MPa (for example, 0.1-1MPa);
  • the hydrogen absorption temperature of the second hydrogen storage alloy to absorb hydrogen is -70 to 100°C (for example, -30 to 100°C), and the hydrogen partial pressure for hydrogen absorption is 0.1 to 5 MPa (for example, 0.1 to 1 MPa),
  • the hydrogen release temperature of the second hydrogen storage alloy is 150-450°C (for example, 200-350°C), and the hydrogen partial pressure for hydrogen release is ⁇ 35 MPa (for example, 35-100 MPa).
  • the organic liquid hydrogen storage raw material is an organic compound containing a ring in the molecule, which optionally contains a heteroatom, and the heteroatom may be on the ring;
  • saturated or unsaturated hydrocarbons containing cycloalkane rings such as saturated or unsaturated hydrocarbons containing cycloalkane rings that do not contain heterocyclic atoms, more specifically, the total number of aromatic and cycloalkane rings is less than or equal to 2 and contains no hetero Saturated or unsaturated hydrocarbons containing cycloalkane rings with ring atoms, for example, cyclohexane, methylcyclohexane, decalin, bicyclohexane; and saturated or unsaturated hydrocarbons containing cycloalkane rings containing heteroatoms,
  • nitrogen-containing heterocyclic compounds, and nitrogen/boron-containing heterocyclic compounds said nitrogen-containing heterocyclic compounds include decahydrocarbazole, dodecahydroethylcarbazole, indoline, 4-aminopiperidine, Piperidine-4-carboxyamine, perhydro-4,7-phenanthroline, 2-methyl-1,2,3,
  • It also includes introducing the released hydrogen into a hydrogen storage tank to store hydrogen; or the obtained high-purity and high-pressure hydrogen can be directly used for hydrogen fuel cell vehicle filling.
  • An efficient distributed method for producing high-purity and high-pressure hydrogen comprising:
  • the liquid organic hydrogen storage raw material is subjected to a dehydrogenation reaction in the presence of a dehydrogenation catalyst to obtain a dehydrogenation reaction product including hydrogen;
  • the dehydrogenation reaction product is cooled and separated to obtain a hydrogen-rich stream and an organic liquid;
  • Hydrogen purging removes the organic matter in the hydrogen storage alloy storage container; wherein the purity of the purged hydrogen is preferably greater than 90% by weight (for example, greater than 95% by weight, greater than 99% by weight);
  • the hydrogen-containing alloy is heated to release hydrogen to obtain high-pressure hydrogen and the obtained high-pressure hydrogen is supplied to a hydrogen device or a high-pressure hydrogen storage tank for storage.
  • a system for providing high-purity and high-pressure hydrogen including:
  • Organic liquid hydrogen storage raw material storage and supply device used to store organic liquid hydrogen storage raw materials and provide organic liquid hydrogen storage raw materials to the dehydrogenation reactor;
  • Dehydrogenated liquid storage device for storing liquid products obtained after dehydrogenation of organic liquid hydrogen storage raw materials
  • Dehydrogenation reactor device for dehydrogenation reaction of organic liquid hydrogen storage raw materials under the action of dehydrogenation catalyst to obtain dehydrogenation reaction product including hydrogen;
  • Cooling separation device for separating dehydrogenation reaction products to obtain hydrogen-rich gas products and liquid products
  • a hydrogen storage-hydrogen supply device which includes a hydrogen storage alloy storage container and a hydrogen storage alloy heating system for contacting hydrogen-rich gas with the hydrogen storage alloy at low temperature and low pressure to absorb hydrogen, and heat dehydrogenation after adsorption saturation;
  • An optional purge device is used to remove organic matter in the hydrogen storage container
  • Hydrogen supply device which supplies high-pressure hydrogen to the hydrogen consuming device or hydrogen storage tank;
  • the system is configured to be integrated and built in a container, used as a container-type hydrogen production system in a hydrogen refueling station, or directly built in a hydrogen refueling station for use;
  • the hydrogen storage-hydrogen supply device includes one or more hydrogen storage alloy storage containers, and a plurality of hydrogen storage alloy storage containers can be connected in parallel or in series or a mixture of parallel and series connections;
  • At least one of the hydrogen storage alloy storage containers is a high-pressure container and/or the hydrogen supply device is a high-pressure-resistant device, for example, its withstand pressure is 35 MPa or more.
  • a mobile hydrogen supply system comprising a transportation vehicle and a system for providing high-purity and high-pressure hydrogen according to any one of the foregoing technical solutions arranged on the transportation vehicle.
  • a distributed hydrogen supply device comprising the system for providing high-purity and high-pressure hydrogen according to any one of the foregoing technical solutions, and optionally a high-pressure hydrogen storage tank.
  • a hydrogen storage alloy or the method, system or device according to any one of the foregoing technical solutions characterized in that the hydrogen storage alloy is rare earth AB 5 type, zirconium titanium AB 2 type, and titanium AB Type, one or more of magnesium-based A 2 B type and vanadium-based solid solution hydrogen storage alloy, of which
  • the molecular expression of the rare earth AB 5 type hydrogen storage alloy is: M m Ni x1 Co x2 Mn x3 Fe x4 Al x5 Sn x6 ,
  • M m is La y1 Ce y2 Nd y3 Pr y4 Y y5 ,
  • 0.4 ⁇ y1 ⁇ 0.99 for example, 0.4 ⁇ y1 ⁇ 0.8
  • 0 ⁇ y2 ⁇ 0.45 for example, 0.1 ⁇ y2 ⁇ 0.45
  • 0 ⁇ y3 ⁇ 0.2 for example, 0 ⁇ y3 ⁇ 0.2
  • 0 ⁇ y4 ⁇ 0.05 E.g., 0 ⁇ y4 ⁇ 0.05
  • 0.01 ⁇ y5 ⁇ 0.1 e.g., 0.01 ⁇ y5 ⁇ 0.05
  • 3 ⁇ x1 ⁇ 5.45 e.g., 3 ⁇ x1 ⁇ 4.9
  • 0 ⁇ x2 ⁇ 1.5 e.g., 0.1 ⁇ x2 ⁇ 1
  • 0 ⁇ x3 ⁇ 0.8 for example, 0.1 ⁇ x3 ⁇ 0.6
  • 0 ⁇ x4 ⁇ 0.8 for example, 0.1 ⁇ x4 ⁇ 0.6
  • 0 ⁇ x5 ⁇ 0.75 for example, 0.05 ⁇ x5 ⁇ 0.5
  • 0 ⁇ x6 ⁇ 0.2 for example, 0 ⁇ x6 ⁇ 0.15)
  • 0 ⁇ x5 ⁇ 0.75 for example, 0.05 ⁇ x5 ⁇ 0.5
  • 0 ⁇ x6 ⁇ 0.2 for example
  • the molecular expression of the zirconium-titanium series AB 2 type hydrogen storage alloy is AB 2 , where
  • 0 ⁇ x1 ⁇ 0.54 for example, 0.01 ⁇ x1 ⁇ 0.3, 0.01 ⁇ x1 ⁇ 0.1
  • 0 ⁇ x2 ⁇ 0.54 for example, 0 ⁇ x2 ⁇ 0.25
  • 0.5 ⁇ x3 ⁇ 1.04 for example, 0.6 ⁇ x3 ⁇ 1
  • 0.05 ⁇ x4 ⁇ 0.58 for example, 0.1 ⁇ x4 ⁇ 0.58
  • 0.01 ⁇ x5 ⁇ 0.2 for example, 0.01 ⁇ x5 ⁇ 0.05
  • 0 ⁇ x6 ⁇ 0.2 for example, 0 ⁇ x6 ⁇ 0.05
  • 0.05 ⁇ y1 ⁇ 1.95 e.g., 0.05 ⁇ y1 ⁇ 1.8
  • 0 ⁇ y2 ⁇ 1.9 e.g., 0 ⁇ y2 ⁇ 1.85
  • 0.05 ⁇ y3 ⁇ 1.95 e.g., 0.1 ⁇ y3 ⁇ 1.95
  • 0 ⁇ y4 ⁇ 1.6 e.g., 0 ⁇ y4 ⁇ 1.5
  • 0 ⁇ y5 ⁇ 0.5 for example, 0 ⁇ y5 ⁇ 0.3
  • 0.1 ⁇ y6 ⁇ 0.5 for example, 0.1 ⁇ y
  • the molecular expression of the titanium AB type hydrogen storage alloy is AB, where
  • 0 ⁇ x1 ⁇ 1.09 e.g., 0.9 ⁇ x1 ⁇ 1.05), 0 ⁇ x2 ⁇ 1.09 (e.g., 0 ⁇ x2 ⁇ 0.5), 0.01 ⁇ x3 ⁇ 0.2 (e.g., 0.01 ⁇ x3 ⁇ 0.05), 0 ⁇ x4 ⁇ 0.2 (E.g., 0 ⁇ x4 ⁇ 0.05), 0.05 ⁇ y1 ⁇ 0.5 (e.g., 0.05 ⁇ y1 ⁇ 0.2), 0 ⁇ y2 ⁇ 0.8 (e.g., 0 ⁇ y2 ⁇ 0.2), 0 ⁇ y3 ⁇ 0.8 (e.g., 0.05 ⁇ y3 ⁇ 0.4, or 0.1 ⁇ y3 ⁇ 0.4), 0.2 ⁇ y4 ⁇ 1 (for example, 0.5 ⁇ y4 ⁇ 0.9), 0 ⁇ y5 ⁇ 0.35 (for example, 0 ⁇ y5 ⁇ 0.1), 0 ⁇ y6 ⁇ 0.45 (for example, 0 ⁇ y6 ⁇ 0.2), 0 ⁇ y7 ⁇ 0.3 (for example, 0 ⁇ y7 ⁇ 0.2),
  • x1 and x2 are not zero at the same time;
  • the molecular expression of the magnesium-based A 2 B hydrogen storage alloy is A 2 B, where
  • 0.7 ⁇ x1 ⁇ 0.95 for example, 0.8 ⁇ x1 ⁇ 0.95, 0.9 ⁇ x1 ⁇ 0.95), 0.05 ⁇ x2 ⁇ 0.3 (for example, 0.05 ⁇ x2 ⁇ 0.2, 0.05 ⁇ x2 ⁇ 0.1), 0.40 ⁇ y1 ⁇ 0.9 (for example, 0.45 ⁇ y1 ⁇ 0.9, 0.5 ⁇ y1 ⁇ 0.8), 0 ⁇ y2 ⁇ 0.5 (e.g., 0 ⁇ y2 ⁇ 0.4), 0 ⁇ y3 ⁇ 0.5 (e.g., 0 ⁇ y3 ⁇ 0.4), 0 ⁇ y4 ⁇ 0.55 (e.g.
  • 0 ⁇ y4 ⁇ 0.4 0 ⁇ y5 ⁇ 0.2 (e.g., 0.01 ⁇ y5 ⁇ 0.2, 0.05 ⁇ y5 ⁇ 0.2), 0 ⁇ y6 ⁇ 0.1 (e.g., 0 ⁇ y6 ⁇ 0.05), 0 ⁇ y7 ⁇ 0.1( For example, 0 ⁇ y7 ⁇ 0.05), 0 ⁇ z1 ⁇ 1 (for example, 0.1 ⁇ z1 ⁇ 1, 0.2 ⁇ z1 ⁇ 0.95), 0 ⁇ z2 ⁇ 0.95 (for example, 0 ⁇ z2 ⁇ 0.9), 0 ⁇ z3 ⁇ 0.3 (E.g., 0 ⁇ z3 ⁇ 0.2), 0 ⁇ z4 ⁇ 0.45 (e.g., 0.05 ⁇ z4 ⁇ 0.45, 0.05 ⁇ z4 ⁇ 0.3), 0.55 ⁇ z1+z2 ⁇ 1 (e.g., 0.7 ⁇ z1+z2 ⁇ 1).
  • the hydrogen storage alloy, method, system or device according to any one of the preceding technical solutions characterized in that the hydrogen storage alloy is selected from the following:
  • the smelting is electric furnace smelting or induction smelting
  • the smelting conditions include: under vacuum or inert atmosphere, the temperature is 1200-3000°C, preferably 1800-2200°C;
  • the pressure of the smelting is 1 ⁇ 10 -5 -1 ⁇ 10 -3 Pa (absolute pressure), preferably 0.5 ⁇ 10 -4 -5 ⁇ 10 -4 Pa (absolute pressure) ;
  • the pressure of the smelting is 0.5-1 bar (for example, 0.6-1 bar, 0.7-1 bar) (gauge pressure),
  • the annealing conditions include: performing under vacuum or an inert atmosphere (such as argon atmosphere), a temperature of 500-900°C (for example, 700-1000°C), and a time of 12-360 hours;
  • an inert atmosphere such as argon atmosphere
  • a temperature of 500-900°C for example, 700-1000°C
  • the method further includes cooling the material obtained by annealing in step (2) and then performing a crushing treatment to obtain a product of 10-400 mesh (for example, 20-400 mesh),
  • the method further includes subjecting the material obtained by annealing in step (2) to activation treatment; preferably, the conditions of the activation treatment include: under vacuum, a temperature of 50-300° C., and a time of 1-10 hours.
  • ⁇ weight percentage of the crystal phase modified metal oxide in the carrier composition/weight percentage of the chemical composition of the modified metal oxide in the carrier composition
  • ⁇ weight percentage of the modified metal oxide on the surface of the carrier composition/weight percentage of the chemical composition of the modified metal oxide in the carrier composition, titanium oxide is calculated as TiO 2 and zirconium oxide is calculated as ZrO 2 .
  • the carrier composition for an organic dehydrogenation catalyst according to any one of the foregoing technical solutions, wherein the mass fraction of alumina in the carrier composition is 80-98.5% (for example, 83-97.5 %). , 85-95% or 90-95%), and the mass fraction of the modified metal oxide is 1.5-20% (for example, 2.5-17%, 5-15%, or 5-10%).
  • the carrier composition for an organic dehydrogenation catalyst according to any one of the preceding technical solutions, wherein the modified metal oxide comprises titanium oxide; in the carrier composition, titanium dioxide
  • the mass fraction of zirconia is 2-20% (such as 2.5-17%, 5-15% or 5-10%), and the mass fraction of zirconium dioxide is 0-8% (such as 0-6%, 0-3% or 1 -6 %); preferably, the modified metal oxide (such as titanium dioxide) is dispersed in a single layer on the alumina matrix.
  • the carrier composition for an organic dehydrogenation catalyst according to any one of the preceding technical solutions, characterized in that, relative to the pure phase of TiO 2 , in the XPS spectrum of the carrier composition, Ti 2P 3
  • the peak at the /2 orbital electron binding energy of 458.8eV is shifted from 0.6-0.7eV to the high binding energy and/or the peak at the Ti 2P 1/2 orbital electron binding energy of 464.5eV is shifted from 0.8-0.9 to the high binding energy. eV.
  • the carrier composition for an organic dehydrogenation catalyst according to any one of the preceding technical solutions, characterized in that the carrier composition has ⁇ -alumina, ⁇ -alumina, ⁇ -alumina or Phase structure of at least one of ⁇ -alumina.
  • the carrier composition for an organic dehydrogenation catalyst according to any one of the foregoing technical solutions, wherein the specific surface area of the carrier composition is 100-350m 2 /g, and the carrier composition The pore volume of the material is 0.3-1.3 mL/g.
  • the alumina matrix is in airflow contact with the modified metal oxide precursor carried by the gas to obtain the alumina matrix supporting the modified metal oxide precursor, and the modified metal oxide precursor is a titanium oxide precursor And/or zirconia precursor;
  • the alumina matrix supporting the modified metal oxide precursor is hydrolyzed and calcined to obtain a carrier composition.
  • the titanium oxide precursor is selected from titanium tetrachloride, (tetra)ethyl titanate, and tetrabutyl titanate. Ester, (tetra) isopropyl titanate, one or more of titanium acetate (preferably titanium tetrachloride); the zirconium oxide precursor is selected from zirconium tetrachloride, zirconium ethoxide, zirconium methoxide, isopropanol Zirconium, one or more of tetrabutyl zirconate (preferably zirconium tetrachloride and/or zirconium methoxide).
  • alumina matrix is selected from the group consisting of ⁇ -alumina, ⁇ -alumina, ⁇ -alumina, and ⁇ -oxidation One or more of aluminum and alumina hydrate.
  • the preparation method of the carrier composition according to any one of the foregoing technical solutions characterized in that the specific surface area of the alumina matrix is 100-350 m 2 /g; preferably, the carrier composition The ratio of the specific surface area to the specific surface area of the alumina matrix is not less than 90%.
  • the gas is an anhydrous inert gas (for example, nitrogen, helium, neon, argon), and
  • the water content in the said anhydrous inactive gas does not exceed 10 ppm; preferably, the content of the modified metal oxide precursor in the modified metal oxide precursor gas stream carried by the gas is 0.1-3g/L ( For example, 0.2-2 g/L), where the content of the modified metal oxide precursor is calculated as the metal oxide.
  • step (1) the temperature of the gas is from room temperature to 350° C. (for example, room temperature (room temperature refers to 15 -40°C) to 300°C, or 15 to 300°C).
  • step (1) The preparation method of the carrier composition according to any one of the foregoing technical solutions, characterized in that the contact pressure in step (1) is 0.05-5 atm (for example, 1-3 atm) (gauge pressure).
  • the alumina matrix is in fluidized state in contact with the gas-carried modified metal oxide precursor gas stream, or It is in contact with the gas flow under stirring;
  • the fluidized state can be, for example, a bubbling bed, a turbulent bed, a fast bed or a transport bed.
  • step (2) the method for hydrolyzing the alumina matrix supporting the modified metal oxide precursor is as follows: The alumina matrix supporting the modified metal oxide precursor is in contact with a gas containing water vapor.
  • the preparation method of the carrier composition according to any one of the preceding technical solutions, characterized in that, in the hydrolysis described in step (2), the ratio of the contact between the gas containing water vapor and the alumina matrix (standard state The ratio of the gas containing water vapor to the bulk volume of the alumina matrix) is 3-80:1 (for example, 5-30:1, or 10-25:1), and the water vapor in the gas containing water vapor accounts for the total volume of the gas The ratio of is 0.1% by volume to 100% by volume (for example, 3% by volume to 100% by volume); the gas other than water vapor in the gas containing water vapor may be an inert gas, nitrogen or air.
  • the preparation method of the carrier composition according to any one of the foregoing technical solutions, characterized in that, for the calcination, the calcination temperature is 350°C-700°C, and the calcination time is 0.5-12 hours (calcination
  • the atmosphere may be oxygen-free or oxygen-containing atmosphere.
  • the oxygen content in the oxygen-containing atmosphere may be 3-100% by volume, for example, air atmosphere or oxygen atmosphere).
  • a catalyst for the dehydrogenation of organic matter to produce hydrogen or the hydrogen storage alloy, method, system or device according to any one of the foregoing technical solutions characterized in that the catalyst contains any one of the foregoing technical solutions.
  • the carrier composition and active components for organic dehydrogenation catalysts are described in detail below.
  • At least one element in the noble metal group preferably, the active component is Pt and optionally at least one element other than Pt in the noble metal group;
  • Ni at least one element of the second metal group, and optionally phosphorus
  • the noble metal group is a group consisting of elements selected from Pt, Pd, Ru, Re, Rh, Ir, Os;
  • the first metal group is a group consisting of elements selected from Sn, V, Mo, Cr, Mn, Fe, Co, Ni, Cu, Ag, Ce, W, Cu, and Ca;
  • the second metal group is a group consisting of elements selected from Zn, Sn, Cu, Fe, Ag, In, Re, Mo, Co, Ca, W;
  • the content of the carrier is 70-99.9% by weight; the content of the active component is 0.1-30% by weight.
  • the active component is (1) At least one element in the precious metal group, in the catalyst, the content of the carrier is 90-99.9% by weight (for example, 92-99.4% by weight, 92-99.5% by weight, 95-99.4% by weight, 98-99.2% by weight, 98.5-99.5 wt%); the content of the active component is 0.1-10 wt% (for example, 0.6-8 wt%, 0.5-8 wt%, 0.6-5 wt%, 0.8-2 wt% or 0.5-1.5 wt%) ;
  • the active component is Pt and optionally at least one element other than Pt in the noble metal group, wherein the content of Pt is 0.1-10% by weight (for example, 0.1-2% by weight, 0.6-10% by weight or 0.6 -0.8% by weight), the content of at least one element other than Pt in the noble metal group is 0-9.9% by weight (for example, 0.1-2% by weight or 0.1-0.8% by weight).
  • the catalyst for the dehydrogenation of organic matter to produce hydrogen according to any one of the preceding technical solutions or the hydrogen storage alloy, method, system or device according to any one of the preceding technical solutions, wherein the active component is (2) Pt and at least one element in the first metal group;
  • the content of the carrier is 75-99.5 wt% (for example, 75-99.4 wt%, 79.9-98.5 wt%), and the content of the active component is 0.5-25 wt% (for example, 0.6-25 wt%, 1.5-20.1% by weight);
  • the content of Pt based on the simple substance is 0.01-10% by weight (for example, 0.2-8% by weight, 0.4-2% by weight, 0.3-0.6% by weight, 0.1-0.7% by weight);
  • the content of at least one element in the first metal group as an oxide is 0.5-20 wt% (for example, 0.5-15 wt% or 1-10 wt%); preferably, at least one element in the first metal group
  • the element is Ni or a combination of Ni and at least one element other than Ni selected from the first metal group, wherein the mass ratio of Pt (calculated as simple substance) to Ni (calculated as NiO) is (0.01:16) to (0.5:0.1).
  • the catalyst for the dehydrogenation of organic matter to produce hydrogen according to any one of the preceding technical solutions or the hydrogen storage alloy, method, system or device according to any one of the preceding technical solutions, wherein the active component is (3) Ni, at least one element of the second metal group, and optionally phosphorus;
  • the content of the carrier is 70-95% by weight (for example, 75-93% by weight, or 75-90% by weight), and the content of the active component as oxide is 5-30% by weight ( For example, 7-25% by weight);
  • the content of nickel based on NiO is 0.5-25% by weight (for example, 5-25% by weight, 6-20% by weight, or 6-11% by weight);
  • the content of at least one element in the second metal group is 0-15% by weight (for example, 0-10% by weight);
  • the content of phosphorus in terms of P 2 O 5 is 0-15% by weight.
  • a preparation method of a catalyst comprising the following steps according to steps (1) and (2) in the preparation method of the carrier composition according to any one of the foregoing technical solutions:
  • the alumina matrix is in airflow contact with the modified metal oxide precursor carried by the gas to obtain the alumina matrix supporting the modified metal oxide precursor, and the modified metal oxide precursor is a titanium oxide precursor And/or zirconia precursor;
  • the preparation method of the catalyst further includes the following steps:
  • the active ingredient is one of the following (1), (2) and (3):
  • At least one element in the noble metal group preferably, the active component is Pt and optionally at least one element other than Pt in the noble metal group;
  • Ni at least one element of the second metal group, and optionally phosphorus
  • the noble metal group is a group consisting of elements selected from Pt, Pd, Ru, Re, Rh, Ir, Os;
  • the first metal group is a group consisting of elements selected from Sn, V, Mo, Cr, Mn, Fe, Co, Ni, Cu, Ag, Ce, W, Cu, and Ca;
  • the second metal group is a group consisting of elements selected from Zn, Sn, Cu, Fe, Ag, In, Re, Mo, Co, Ca, and W.
  • the active component precursor is a soluble salt of the active component (for example, metal nitrate, acetate, metal chloride, metal carbonate, metal acetate complex, metal hydroxide, metal oxalate complex (One or more of high-valent metal acid, high-valent metal salt, metal complex, ammonium salt).
  • a soluble salt of the active component for example, metal nitrate, acetate, metal chloride, metal carbonate, metal acetate complex, metal hydroxide, metal oxalate complex (One or more of high-valent metal acid, high-valent metal salt, metal complex, ammonium salt).
  • the carrier impregnated with the active component precursor is placed in an environment below -40°C for 1 hour to 24 hours; then vacuum drying is performed to remove water adsorbed on the carrier, and then calcined to obtain a catalyst.
  • XRD X-ray diffraction
  • Figure 2 is an X-ray photoelectron spectroscopy (XPS) spectrum, in which 1 is the XPS spectrum of pure TiO2; the other curves are the XPS spectra of carrier compositions with different TiO2 contents (alumina supported titanium oxide) prepared by the method of the present invention
  • M-2, M-4, M-7, and M-8 are the embodiment vectors 2, 4, 7 and 8, respectively.
  • the carrier composition provided by the present invention the electron binding energy (abbreviated as binding energy) of Ti 2P 3/2 orbital at 458.8eV shifts 0.6-0.7eV to the direction of high binding energy, Ti 2P 1/2
  • Figure 3 is a schematic diagram of providing high-purity and high-pressure hydrogen provided by the present invention, in which: 1 is an organic liquid storage tank, 2 is a raw material pump, 3 is a heat exchanger, 4 is a dehydrogenation reactor, and 5 is a heat exchanger, 6 is a hydrogen storage tank, 7 is a one-way valve, 8 is an energy transfer body system, 9 is a purge system, and 10 is a hydrogen storage control system.
  • the pressure mentioned in the present invention refers to gauge pressure, unless otherwise specified.
  • the present invention provides a carrier composition for an organic dehydrogenation catalyst.
  • the carrier composition includes alumina and a modified metal oxide.
  • ⁇ weight percentage of the crystal phase modified metal oxide in the carrier composition/weight percentage of the chemical composition of the modified metal oxide in the carrier composition
  • ⁇ weight percentage of the modified metal oxide on the surface of the carrier composition/weight percentage of the chemical composition of the modified metal oxide in the carrier composition, titanium oxide is calculated as TiO 2 and zirconium oxide is calculated as ZrO 2 .
  • the alumina and the modified metal oxide partly or completely form a carrier composition.
  • the modified metal oxide is supported on the surface of the carrier.
  • the mass fraction of alumina in the carrier composition is 80-98.5% (for example, 83-97.5%, 85-95% or 90-95%), and the mass fraction of the modified metal oxide It is 1.5-20% (e.g. 2.5-17%, 5-15%, or 5-10%).
  • the modified metal oxide includes titanium oxide; in the carrier composition, the mass fraction of titanium dioxide is 2-20% (for example, 2.5-17%, 5-15% or 5-10%), the mass fraction of zirconium dioxide is 0-8% (for example, 0-6%, 0-3% or 1-6%); preferably, the modified metal oxide (for example, titanium dioxide)
  • the single layer is dispersed on the alumina matrix.
  • the content of the modified metal oxide in the 0-5nm thick surface layer of the support surface is higher than 90 atomic number %, preferably higher than 95 atomic number If it is a few %, it is said that the modified metal oxide monolayer is dispersed on the alumina matrix.
  • the peak at the Ti 2P 3/2 orbital electron binding energy of 458.8 eV is shifted by 0.6- to the high binding energy.
  • the peak at 0.7 eV and/or Ti 2P 1/2 orbital electron binding energy of 464.5 eV shifts 0.8-0.9 eV to the high binding energy direction.
  • the carrier composition has a phase structure of at least one of ⁇ -alumina, ⁇ -alumina, ⁇ -alumina or ⁇ -alumina.
  • the specific surface area of the carrier composition is 100-350m 2 /g (for example, 110-340m 2 /g or 130-250m 2 /g or 140-200m 2 /g), so
  • the pore volume of the carrier composition is 0.3-1.3 mL/g (for example, 0.32-1.0 mL/g or 0.35-0.6 mL/g or 0.35-0.8 mL/g).
  • the ratio of the specific surface area of the carrier composition to the specific surface area of the alumina matrix is not less than 90%, that is, the specific surface area of the carrier composition is compared with that of pure alumina (the modified element is not introduced). Alumina), the reduction ratio is ⁇ 10%.
  • the carrier composition provided by the present invention can be used to prepare a catalyst for the dehydrogenation of organic substances to prepare hydrogen, and can also be used for the oxidative dehydrogenation of alkane organic substances to prepare olefins or oxygen-containing organic substances.
  • the catalyst includes the carrier composition provided by the present invention and the active metal component supported on the carrier composition, and the active metal component is an oxide of the active metal and/or a simple substance of the active metal.
  • the active metal is one of the eighth subgroup metal, the seventh subgroup metal, the fifth subgroup metal, the sixth subgroup metal, the first subgroup metal, rare earth elements, alkaline earth metals, and one of the fourth main group metals. Kind or more. It can have higher dehydrogenation activity and/or higher selectivity than a catalyst prepared by using existing supports and the same active metal.
  • the carrier composition provided by the present invention has a relatively low ⁇ value and a relatively high ⁇ value. It can be used as a dehydrogenation catalyst carrier, especially for the dehydrogenation of a cycloalkane ring-containing organic liquid hydrogen storage compound to prepare a hydrogen catalyst, which can improve the dehydrogenation of the catalyst. Hydrogen activity and/or selectivity.
  • the carrier composition preparation method provided by the present invention can obtain the carrier composition provided by the present invention.
  • the obtained carrier composition has a relatively low ⁇ value and a relatively high ⁇ value, and the preparation method is easy to implement.
  • the dehydrogenation catalyst for preparing hydrogen from the organic liquid hydrogen storage compound prepared by using the carrier composition provided by the invention has higher activity and higher hydrogen selectivity.
  • the prepared oxidative dehydrogenation catalyst has higher activity and higher oxidation selectivity.
  • the support provided by the present invention can be used to prepare organic hydrogen storage compound dehydrogenation to prepare hydrogen catalyst, and can also be used as a support for other hydrogen-related reaction catalysts or oxidation catalysts, for example, for organic matter oxidative dehydrogenation catalysts, unsaturated hydrocarbon hydrogenation catalysts, Complete organic oxidation catalyst or NO oxidation catalyst.
  • the present invention provides a method for preparing a carrier composition, including the following steps: (1) contacting an alumina matrix with a gas-carrying modified metal oxide precursor gas stream to obtain a modified metal oxide The alumina matrix of the metal oxide precursor, wherein the modified metal oxide precursor is a titania precursor and/or a zirconia precursor; (2) hydrolyzing the alumina matrix supporting the modified metal oxide precursor And calcining to obtain a carrier composition.
  • the modified metal oxide precursor is preferably a substance that can be gasified to form a gaseous metal oxide precursor at room temperature to 350°C.
  • the titanium oxide precursor is selected from one or more of titanium tetrachloride, (tetra) ethyl titanate, tetrabutyl titanate, (tetra) isopropyl titanate, and titanium acetate (preferably tetrachloride Titanium);
  • the zirconia precursor is selected from one or more of zirconium tetrachloride, zirconium ethoxide, zirconium methoxide, zirconium isopropoxide, tetrabutyl zirconate (preferably zirconium tetrachloride and/or methanol zirconium).
  • the alumina matrix is selected from ⁇ -alumina, ⁇ -alumina, rho-alumina, ⁇ -alumina, hydrated alumina (for example, boehmite, One or more of diaspore, pseudo-boehmite, gibbsite, bayerite, nordstrandite, amorphous aluminum hydroxide), preferably
  • the average particle size (diameter) of the alumina matrix is 5-100 ⁇ m, for example, 5-50 ⁇ m.
  • the specific surface area of the alumina matrix is not less than 100m 2 /g (for example, greater than 100 and not more than 380m 2 /g, 100-350m 2 /g, 125-335m 2 /g); preferably, the ratio of the specific surface area of the carrier composition to the specific surface area of the alumina matrix is not less than 90%, that is, the ratio of the specific surface area of the resulting carrier composition to the alumina matrix is Surface area, the reduction ratio is ⁇ 10%.
  • the pore volume of the alumina matrix is not less than 0.3 mL/g (for example, greater than 0.3 and not more than 1.45 mL/g, 0.3-1.3 mL/g, 0.35-1.2 mL/g, 0.35-1.0 or 0.4-0.8 mL/g).
  • the gas is an anhydrous inert gas (for example, nitrogen, helium, neon, argon), and the water content in the anhydrous inert gas is not More than 10 ppm; preferably, the content of the modified metal oxide precursor in the modified metal oxide precursor gas stream carried by the gas is 0.1-3 g/L (for example, 0.2-2 g/L), wherein the modified metal The oxide precursor content is calculated as metal oxide.
  • anhydrous inert gas for example, nitrogen, helium, neon, argon
  • the water content in the anhydrous inert gas is not More than 10 ppm; preferably, the content of the modified metal oxide precursor in the modified metal oxide precursor gas stream carried by the gas is 0.1-3 g/L (for example, 0.2-2 g/L), wherein the modified metal The oxide precursor content is calculated as metal oxide.
  • the temperature of the gas is from room temperature to 350°C (for example, room temperature (room temperature refers to 15-40°C) to 300°C, or 15 to 300°C ), the contact temperature is 15-350°C (for example, 15-300°C or 15-100°C or 15-200°C or 18-60°C or 15-40°C).
  • the contact pressure in step (1) is 0.05-5 atm (for example, 1-3 atm) (gauge pressure).
  • the ratio of the volumetric flow rate of the gas per minute to the volume of the alumina matrix is 3-80:1 (for example, 5-30:1, 10-25:1);
  • the volume of the gas is based on the volume under standard conditions, and the volume of the alumina matrix is based on the bulk volume.
  • the alumina matrix is in fluidized state in contact with the gas-carrying modified metal oxide precursor gas stream, or in contact with the gas stream under stirring;
  • the state can be, for example, a bubbling bed, a turbulent bed, a fast bed or a transport bed.
  • the alumina matrix is contacted with a gas-carrying modified metal oxide precursor gas stream (also referred to as gas stream), and the alumina matrix is in contact with the gas stream under a fixed bed, or in the flow Contact with the modified metal oxide precursor gas carried by the gas in the chemical state can also be contact with the gas stream under stirring.
  • the contact in the fluidized state can be, for example, a bubbling bed, a turbulent bed, a fast bed or a conveying bed.
  • the ratio of the volumetric flow rate of the gas per minute to the volume of the alumina matrix is 3-80:1, for example, 5-30:1, or 10-25:1.
  • the volume of the gas is based on the volume under standard conditions, and the volume of the alumina matrix is based on the bulk volume.
  • the gas stream is in contact with the alumina substrate in a fluidized bed, and the volumetric space velocity of the contact is 3-80: 1 min -1 , for example, 5-30: 1 min -1 or 10- 25:1 min -1 , wherein the volumetric flow rate of the gas flow is based on the volume of the gas under standard conditions, the alumina matrix is based on the bulk volume, and the fluidized bed may be a bulk Type fluidized bed, bubbling bed or turbulent bed.
  • step (2) the alumina matrix supporting the modified metal oxide precursor is hydrolyzed, and the method is as follows: oxidizing the modified metal oxide precursor The aluminum matrix is in contact with a gas containing water vapor.
  • the hydrolysis in step (2), the contact ratio of the gas containing water vapor to the alumina matrix (the ratio of the gas containing water vapor to the bulk volume of the alumina matrix in the standard state ) Is 3-80:1 (for example, 5-30:1, or 10-25:1), and the ratio of water vapor in the gas containing water vapor to the total gas volume is 0.1% by volume to 100% by volume (for example, 3 Volume%-100% by volume, 10% by volume-70% by volume);
  • the gas other than water vapor in the gas containing water vapor may be an inert gas, nitrogen or air.
  • the hydrolysis time is 1 hour to 50 hours, for example 2 hours to 30 hours (usually, the hydrolysis time is greater than or equal to the loading time, and the loading time refers to oxidation The time that the aluminum matrix is in contact with the modified metal oxide precursor gas stream carried by the gas).
  • the firing atmosphere may be an atmosphere that does not contain oxygen or contains oxygen.
  • the oxygen content in the oxygen-containing atmosphere may be 3-100% by volume, for example, an air atmosphere or an oxygen atmosphere.
  • the firing temperature is 350°C-700°C (such as 400-700°C), and the firing time is 0.5-12 hours (for example, 1-10 hours, or 2-9 hours, or 4-8 hours).
  • the present invention provides a catalyst for the dehydrogenation of organic matter to produce hydrogen, which contains the carrier composition for the dehydrogenation catalyst of the present invention and an active component.
  • the active components may exist in the form of oxides and/or active metal elements.
  • the active component is one of the following (1), (2) and (3): (1) at least one element in the noble metal group, preferably, The active component is Pt and optionally at least one element in the precious metal group other than Pt; (2) Pt and at least one element in the first metal group; (3) Ni, at least one element in the second metal group One element, and optional phosphorus; wherein the noble metal group is a group consisting of elements selected from Pt, Pd, Ru, Re, Rh, Ir, Os; the first metal group is a group consisting of elements selected from Sn, V, Mo, A group consisting of Cr, Mn, Fe, Co, Ni, Cu, Ag, Ce, W, Cu, and Ca; the second metal group is selected from Zn, Sn, Cu, Fe, Ag, In, Re, Mo , Co, Ca, and W elements; in the catalyst, the content of the carrier is 70-99.9% by weight; the content of the active component is 0.1-30%
  • the active component is (1) at least one element in the noble metal group, and in the catalyst, the content of the carrier is 90-99.9% by weight (for example, 92-99.4 % By weight, 92-99.5% by weight, 95-99.4% by weight, 98-99.2% by weight, 98.5-99.5% by weight); the content of active components is 0.1-10% by weight (for example, 0.6-8% by weight, 0.5-8 % By weight, 0.6-5% by weight, 0.8-2% by weight or 0.5-1.5% by weight); preferably, the active component is Pt and optionally at least one element other than Pt in the noble metal group, wherein Pt The content is 0.1-10% by weight (for example, 0.1-2% by weight, 0.6-10% by weight, or 0.6-0.8% by weight), and the content of at least one element other than Pt in the noble metal group is 0-9.9% by weight (for example, 0.1-2% by
  • the active component is (2) Pt and at least one element of the first metal group (for example, one or more of Sn, Ni, Mn, and Cu)
  • the content of the carrier is 75-99.5 wt% (for example, 75-99.4 wt%, 79.9-98.5 wt%), and the content of the active component is 0.5-25 wt% (for example, 0.6-25 wt% , 1.5-20.1% by weight);
  • the content of Pt based on the element is 0.01-10% by weight (for example, 0.2-8% by weight, 0.4-2% by weight, 0.3-0.6% by weight) , 0.1-0.7% by weight);
  • the content of at least one element in the first metal group as an oxide is 0.5-20% by weight (for example, 0.5-15% by weight or 1-10% by weight); preferably, the first At least one element in one metal group is Ni or a combination of Ni and at least one element other than Ni (
  • the content of Pt in the catalyst is 0.1-0.5% by weight, and the content of Ni in terms of oxide is 0.5-15% by weight, for example, 1-10% by weight.
  • the content of elements other than Ni is 0-10% by weight, for example, 1-6% by weight.
  • the active components are more preferably Pt, Ni and Cu.
  • the active component is (3) Ni, at least one element in the second metal group (preferably, Sn, Cu, Zn, Fe, Ag, more preferably, Sn, Ag, Cu and Zn, more preferably Sn, Zn and Cu, still more preferably Sn and Zn), and optionally phosphorus. According to this preferred embodiment, it can have a higher conversion rate and hydrogen generation rate, and can have a higher hydrogen selectivity relative to other active metals.
  • the content of the carrier is 70-95% by weight (for example, 75-93% by weight, or 75-90% by weight), and the content of the active component as oxide is 5-30% by weight ( For example, 7-25% by weight, 10-25% by weight, 8-20% by weight, or 10-16% by weight); in the active component, the content of nickel based on NiO is 0.5-25% by weight (For example, 0.5-20% by weight, 5-25% by weight, 6-20% by weight, 5-15% by weight, 8-10% by weight, or 6-11% by weight); the second metal group as oxide
  • the content of at least one element in P 2 O 5 is 0-15 wt% (for example, 0-10 wt%, 2-6 wt%); the content of phosphorus in terms of P 2 O 5 is 0-15 wt% (for example, 0- 8 wt%, 0-6 wt%).
  • the catalyst for the dehydrogenation of organic compounds of the present invention the hydrogen, the catalyst specific surface area of 100-350m 2 / g (e.g. 120-330m 2 / g), the pore volume of the catalyst is 0.3-1.3mL / g (e.g. 0.35-1.2 mL/g).
  • the present invention provides a method for preparing the catalyst for the dehydrogenation of organic matter to produce hydrogen of the present invention, which comprises the following steps: (1) Oxidizing the alumina matrix and the modified metal carried by the gas Contact with the precursor of the material to obtain an alumina matrix supporting a precursor of a modified metal oxide, the precursor of the modified metal oxide being a precursor of titania and/or a precursor of zirconia; (2) modifying the support The alumina matrix of the metal oxide precursor is hydrolyzed and calcined to obtain the carrier composition; (3) impregnating the carrier composition with the active component precursor solution to obtain the carrier impregnated with the active component precursor; (4) impregnation
  • the carrier of the active component precursor is dried and calcined; preferably, the active component is one of the following (1), (2) and (3): (1) at least one element in the noble metal group, preferably, The active component is Pt and optionally at least one element in the precious metal group other than Pt; (2) Pt and at least one
  • the calcination described in step (4) has a calcination temperature of 400-700°C and a calcination time of 0.5-12 hours.
  • the carrier composition when it is impregnated with the solution of the active component precursor, it usually includes the aforementioned dissolving the active metal component precursor in water and immersing the carrier composition to obtain the impregnated active metal component precursor.
  • the impregnation method can be an existing impregnation method, for example, an equal volume impregnation or excessive impregnation method.
  • the water is one or more of deionized water, distilled water or deionized water.
  • the metal precursor can also be dissolved in water to obtain a metal precursor solution; the metal precursor solution is introduced onto the carrier by co-immersion or step-wise impregnation, and the impregnation can be saturated or supersaturated impregnation.
  • the co-impregnation means that two or more metal elements can be dissolved in deionized water together, and then the impregnating solution is immersed on the carrier, and then dried and roasted.
  • the step-by-step impregnation includes dissolving two or more metal elements in deionized water separately; impregnating the metal impregnation liquid on the carrier separately, and the carrier obtained after each impregnation needs to be dried and roasted, and the sequence of introducing the metal No order is required.
  • a Pt precursor and a precursor of an element in the first metal group can be formulated into a solution to impregnate the carrier composition, or the Pt precursor can be impregnated first, and after drying, the first The precursor of this element in the metal group.
  • the liquid/solid product ratio of the immersion liquid to the carrier during immersion is 0.3-5.0, preferably 0.6-4.0, and the immersion temperature is 10-50°C, preferably 15-40°C.
  • the impregnated solid is allowed to stand at room temperature for 2-10 hours, and the impregnated solid is dried and then calcined.
  • the calcining temperature is preferably 400-700°C, and the calcining time is preferably 0.5-12 hours, such as 1-10 hours or 2-9.
  • the calcination atmosphere has no special requirements.
  • the calcination can be performed in air.
  • the air (standard condition)/catalyst volume ratio during calcination is, for example, 400-1000:1, and the calcination time is preferably 4-8 hours.
  • the active component precursor is a soluble salt of the active component (for example, metal nitrate, acetate, metal chloride, metal carbonate, One or more of metal acetate complexes, metal hydroxides, metal oxalate complexes, high-valent metal acids, high-valent metal salts, metal complexes, and ammonium salts).
  • the high-valent metal acid/high-valent metal salt is, for example, one or more of chloroplatinic acid, ammonium chloroplatinate, tetraammine platinum nitrate, and tetraammine platinum hydroxide.
  • the precursor of phosphorus is one or more of ammonium phosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, phosphoric acid, and metal phosphate.
  • the carrier impregnated with the active component precursor is placed in an environment below -40°C for 1 hour to 24 hours; then vacuum drying is performed to remove the carrier The adsorbed water is then calcined to obtain a catalyst.
  • the present invention provides a hydrogen storage alloy
  • the hydrogen storage alloy is rare earth AB 5 type, zirconium titanium AB 2 type, titanium AB type, magnesium A 2 B type and One or more of vanadium-based solid solution hydrogen storage alloys, of which
  • the molecular expression of the rare earth AB 5 type hydrogen storage alloy is: M m Ni x1 Co x2 Mn x3 Fe x4 Al x5 Sn x6 ,
  • M m is La y1 Ce y2 Nd y3 Pr y4 Y y5 ,
  • 0.4 ⁇ y1 ⁇ 0.99 for example, 0.4 ⁇ y1 ⁇ 0.8
  • 0 ⁇ y2 ⁇ 0.45 for example, 0.1 ⁇ y2 ⁇ 0.45
  • 0 ⁇ y3 ⁇ 0.2 for example, 0 ⁇ y3 ⁇ 0.2
  • 0 ⁇ y4 ⁇ 0.05 E.g., 0 ⁇ y4 ⁇ 0.05
  • 0.01 ⁇ y5 ⁇ 0.1 e.g., 0.01 ⁇ y5 ⁇ 0.05
  • 3 ⁇ x1 ⁇ 5.45 e.g., 3 ⁇ x1 ⁇ 4.9
  • 0 ⁇ x2 ⁇ 1.5 e.g., 0.1 ⁇ x2 ⁇ 1
  • 0 ⁇ x3 ⁇ 0.8 for example, 0.1 ⁇ x3 ⁇ 0.6
  • 0 ⁇ x4 ⁇ 0.8 for example, 0.1 ⁇ x4 ⁇ 0.6
  • 0 ⁇ x5 ⁇ 0.75 for example, 0.05 ⁇ x5 ⁇ 0.5
  • 0 ⁇ x6 ⁇ 0.2 for example, 0 ⁇ x6 ⁇ 0.15).
  • the molecular expression of the zirconium-titanium series AB 2 type hydrogen storage alloy is AB 2 , where
  • 0 ⁇ x1 ⁇ 0.54 for example, 0.01 ⁇ x1 ⁇ 0.3, 0.01 ⁇ x1 ⁇ 0.1
  • 0 ⁇ x2 ⁇ 0.54 for example, 0 ⁇ x2 ⁇ 0.25
  • 0.5 ⁇ x3 ⁇ 1.04 for example, 0.6 ⁇ x3 ⁇ 1
  • 0.05 ⁇ x4 ⁇ 0.58 for example, 0.1 ⁇ x4 ⁇ 0.58
  • 0.01 ⁇ x5 ⁇ 0.2 for example, 0.01 ⁇ x5 ⁇ 0.05
  • 0 ⁇ x6 ⁇ 0.2 for example, 0 ⁇ x6 ⁇ 0.05
  • 0.05 ⁇ y1 ⁇ 1.95 e.g., 0.05 ⁇ y1 ⁇ 1.8
  • 0 ⁇ y2 ⁇ 1.9 e.g., 0 ⁇ y2 ⁇ 1.85
  • 0.05 ⁇ y3 ⁇ 1.95 e.g., 0.1 ⁇ y3 ⁇ 1.95
  • 0 ⁇ y4 ⁇ 1.6 e.g., 0 ⁇ y4 ⁇ 1.5
  • 0 ⁇ y5 ⁇ 0.5 for example, 0 ⁇ y5 ⁇ 0.3
  • 0.1 ⁇ y6 ⁇ 0.5 for example, 0.1 ⁇ y
  • the molecular expression of the titanium AB type hydrogen storage alloy is AB, where
  • 0 ⁇ x1 ⁇ 1.09 e.g., 0.9 ⁇ x1 ⁇ 1.05), 0 ⁇ x2 ⁇ 1.09 (e.g., 0 ⁇ x2 ⁇ 0.5), 0.01 ⁇ x3 ⁇ 0.2 (e.g., 0.01 ⁇ x3 ⁇ 0.05), 0 ⁇ x4 ⁇ 0.2 (E.g., 0 ⁇ x4 ⁇ 0.05), 0.05 ⁇ y1 ⁇ 0.5 (e.g., 0.05 ⁇ y1 ⁇ 0.2), 0 ⁇ y2 ⁇ 0.8 (e.g., 0 ⁇ y2 ⁇ 0.2), 0 ⁇ y3 ⁇ 0.8 (e.g., 0.05 ⁇ y3 ⁇ 0.4, or 0.1 ⁇ y3 ⁇ 0.4), 0.2 ⁇ y4 ⁇ 1 (for example, 0.5 ⁇ y4 ⁇ 0.9), 0 ⁇ y5 ⁇ 0.35 (for example, 0 ⁇ y5 ⁇ 0.1), 0 ⁇ y6 ⁇ 0.45 (for example, 0 ⁇ y6 ⁇ 0.2), 0 ⁇ y7 ⁇ 0.3 (for example, 0 ⁇ y7 ⁇ 0.2), preferably, x1 and x2 are not zero at the same
  • the molecular expression of the magnesium-based A 2 B hydrogen storage alloy is A 2 B, where
  • 0.7 ⁇ x1 ⁇ 0.95 for example, 0.8 ⁇ x1 ⁇ 0.95, 0.9 ⁇ x1 ⁇ 0.95), 0.05 ⁇ x2 ⁇ 0.3 (for example, 0.05 ⁇ x2 ⁇ 0.2, 0.05 ⁇ x2 ⁇ 0.1), 0.4 ⁇ y1 ⁇ 0.9 (for example, 0.45 ⁇ y1 ⁇ 0.9, 0.5 ⁇ y1 ⁇ 0.8), 0 ⁇ y2 ⁇ 0.5 (e.g., 0 ⁇ y2 ⁇ 0.4), 0 ⁇ y3 ⁇ 0.5 (e.g., 0 ⁇ y3 ⁇ 0.4), 0 ⁇ y4 ⁇ 0.55 (e.g.
  • 0 ⁇ y4 ⁇ 0.4 0 ⁇ y5 ⁇ 0.2 (e.g., 0.01 ⁇ y5 ⁇ 0.2, 0.05 ⁇ y5 ⁇ 0.2), 0 ⁇ y6 ⁇ 0.1 (e.g., 0 ⁇ y6 ⁇ 0.05), 0 ⁇ y7 ⁇ 0.1( For example, 0 ⁇ y7 ⁇ 0.05), 0 ⁇ z1 ⁇ 1 (for example, 0.1 ⁇ z1 ⁇ 1, 0.2 ⁇ z1 ⁇ 0.95), 0 ⁇ z2 ⁇ 0.95 (for example, 0 ⁇ z2 ⁇ 0.9), 0 ⁇ z3 ⁇ 0.3 (E.g., 0 ⁇ z3 ⁇ 0.2), 0 ⁇ z4 ⁇ 0.45 (e.g., 0.05 ⁇ z4 ⁇ 0.45, 0.05 ⁇ z4 ⁇ 0.3), 0.55 ⁇ z1+z2 ⁇ 1 (e.g., 0.7 ⁇ z1+z2 ⁇ 1).
  • the hydrogen storage alloy of the present invention is selected from:
  • the hydrogen storage alloy of the present invention is selected from:
  • the present invention provides a method for preparing the hydrogen storage alloy of the present invention, wherein the method includes the following steps: (1) Weigh each hydrogen storage alloy in a way to achieve the composition of the hydrogen storage alloy The raw materials are mixed; (2) the material obtained by mixing in step (1) is smelted and then annealed; wherein, the smelting is electric furnace smelting or induction smelting; preferably, the smelting conditions include: in a vacuum or an inert atmosphere The temperature is 1200-3000°C, preferably 1800-2200°C; more preferably, it is carried out under vacuum, the pressure of the smelting is 1 ⁇ 10 -5 -1 ⁇ 10 -3 Pa (absolute pressure), preferably 0.5 ⁇ 10 -4 -5 ⁇ 10 -4 Pa (absolute pressure); more preferably, it is performed under an inert atmosphere, and the pressure of the smelting is 0.5-1 bar (for example, 0.6-1 bar, 0.7-1 bar) (Gauge pressure); the annea
  • the present invention provides a method for providing high-purity hydrogen, the method comprising: (1) contacting and reacting an organic liquid hydrogen storage raw material with a dehydrogenation catalyst to obtain a dehydrogenation reaction product containing hydrogen; (2) Cool the dehydrogenation reaction products to obtain liquid products and hydrogen-rich gas products, and collect the liquid products; (3) Contact hydrogen-rich gas with hydrogen storage alloy to obtain hydrogen-containing alloy, and collect unadsorbed gas; (3a) Optionally, removing organic matter in the hydrogen-containing alloy storage container; (4) heating the hydrogen-containing alloy to release hydrogen.
  • the catalyst for the dehydrogenation of organic matter to produce hydrogen of the present invention and/or the hydrogen storage alloy of the present invention are used.
  • the reaction temperature of the contact reaction of the organic liquid hydrogen storage raw material with the dehydrogenation catalyst is 150-450°C (for example, 200-400°C, 300-350°C);
  • the weight hourly space velocity of the organic liquid hydrogen storage raw material in contact with the dehydrogenation catalyst is 0.5-50 h -1 (for example, 1-45 h -1 , 2-30 h -1 );
  • the organic liquid hydrogen storage raw material is in contact with the dehydrogenation catalyst to react
  • the pressure is 0.03-5MPa (gauge pressure) (for example, 0.3-5MPa, 0.1-3MPa, 0.5-2MPa or 0.2-1.6MPa); optionally, the organic liquid hydrogen storage raw material is mixed with hydrogen and then contacted with the dehydrogenation catalyst,
  • the hydrogen-to-hydrocarbon ratio (the molar ratio of hydrogen to the organic liquid hydrogen storage raw material) is 0-10 (for example, 0-8).
  • the introduction of hydrogen is beneficial to reduce coke formation in the dehydrogenation reaction.
  • the cooling temperature at which the dehydrogenation reaction product is cooled is lower than the boiling temperature of the organic matter in the liquid product; preferably, it is liquid at room temperature and pressure lower than that The boiling point temperature of the lowest boiling point organics.
  • the hydrogen-rich gas is a hydrogen-rich gas product or a hydrogen-containing gas obtained by further separation of the hydrogen-rich gas product, and the further separation method Including temperature swing separation, membrane separation, pressure swing adsorption separation or their combination; the mass fraction of hydrogen in the hydrogen-rich gas is ⁇ 80% (for example, 80-99%, preferably ⁇ 85%, more preferably ⁇ 90% ).
  • the contact between the hydrogen-rich gas and the hydrogen storage alloy is performed in one or more hydrogen storage alloy storage containers;
  • the hydrogen storage alloy may be One or more, multiple hydrogen storage alloys can be used in combination, or in series or in parallel or in series and parallel;
  • the pressure at which the hydrogen-rich gas contacts the hydrogen storage alloy is 0.001-5MPa (for example, 0.01- 5MPa, 0.03-4MPa, 0.05-5MPa, 0.08-2MPa, 0.05-3MPa, 0.1-1MPa), when there are multiple hydrogen storage alloy storage containers, and there are hydrogen storage containers in series, follow the hydrogen-rich gas flow direction, and finally
  • the contact pressure (also called hydrogen absorption pressure) of contacting the hydrogen storage alloy is 0.05-5 MPa (for example, 0.1-1 MPa);
  • the contact temperature of the hydrogen-rich gas and the hydrogen storage alloy also called hydrogen absorption temperature
  • the hydrogen storage alloy storage container that contacts the hydrogen there are one or more hydrogen storage alloy storage containers, wherein according to the order of contacting hydrogen, the hydrogen storage alloy storage container that contacts the hydrogen last
  • the hydrogen storage alloy is a hydrogen storage alloy with a high equilibrium pressure.
  • the hydrogen storage alloy with a high equilibrium pressure has at least one temperature point between 150-450°C, and the equilibrium pressure of hydrogen absorption is greater than or equal to 35MPa; preferably Yes, the hydrogen storage alloy in at least one hydrogen storage alloy storage container is a hydrogen storage alloy with a high equilibrium pressure.
  • High-purity and high-pressure hydrogen can be obtained through the hydrogen storage alloy with high equilibrium pressure, and the obtained high-purity and high-pressure hydrogen can be directly used for hydrogen fuel cell vehicle filling.
  • step (3a) is performed, in which the organic matter in the hydrogen-containing alloy storage container is removed by a purge method.
  • the method such as: after the hydrogen storage alloy reaches a predetermined adsorption capacity, stop supplying hydrogen-rich gas to the hydrogen storage alloy, let the hydrogen pass through the hydrogen-containing alloy, and transfer the hydrogen-containing alloy and the hydrogen-containing alloy storage container (also called The organic gas in the hydrogen storage alloy storage container) is taken out and introduced into the storage tank for storage or absorbed by the hydrogen storage alloy in other hydrogen storage alloy storage containers; wherein preferably, the purging hydrogen has a purity greater than 90% by weight, more preferably greater than 95% by weight, for example greater than 99% by weight.
  • the temperature of hydrogen released by the hydrogen storage alloy ie, the temperature at which the hydrogen storage alloy is heated, referred to as the hydrogen release temperature
  • the temperature of the released hydrogen The pressure is ⁇ 35 MPa (for example, 35-100 MPa) to obtain high-purity high-pressure hydrogen, or the partial pressure of the released hydrogen is 0.1-5 MPa to obtain high-purity hydrogen, wherein the hydrogen release temperature is higher than the hydrogen absorption temperature.
  • the method for providing high-purity hydrogen gas according to the present invention further includes allowing hydrogen-containing alloys to release hydrogen, and the released hydrogen contacts with different hydrogen storage alloys to form hydrogen-containing alloys.
  • the process is repeated one or more times, wherein the process is repeated at least the last time
  • the hydrogen storage alloy used is a hydrogen storage alloy with a high equilibrium pressure.
  • the hydrogen storage alloy is a combination of a first hydrogen storage alloy and a second hydrogen storage alloy; the first hydrogen storage alloy is the magnesium-based A 2 B type storage alloy described in the present invention.
  • Hydrogen alloy is used for hydrogen-rich gas contact
  • the second hydrogen storage alloy is used to pressurize the first hydrogen storage hydrogen
  • the second hydrogen storage alloy is a hydrogen storage alloy with a high equilibrium pressure
  • the second hydrogen storage alloy is the invention
  • the hydrogen-rich gas first passes through the first hydrogen storage alloy for impurity separation; then the first storage alloy
  • the high-purity hydrogen released by the hydrogen alloy comes into contact with the second hydrogen storage alloy, and then the second hydrogen storage alloy releases hydrogen under high pressure
  • the hydrogen release temperature of the first hydrogen storage alloy is higher than the hydrogen absorption temperature of the second hydrogen storage alloy, and the temperature difference
  • ⁇ 100°C for example, 350°C ⁇
  • the organic liquid hydrogen storage raw material is an organic compound containing a ring in the molecule, which optionally contains heteroatoms, and the heteroatoms may be on the ring; for example, containing the ring Saturated or unsaturated hydrocarbons of an alkane ring, such as saturated or unsaturated hydrocarbons containing a cycloalkane ring without heterocyclic atoms, more specifically, those containing no heterocyclic atoms with the total number of aromatic rings and cycloalkanes being less than or equal to 2 Saturated or unsaturated hydrocarbons of cycloalkane ring, for example, cyclohexane, methylcyclohexane, decalin, bicyclohexane; and saturated or unsaturated hydrocarbons containing cycloalkane ring containing heteroatoms, for example, nitrogen-containing Heterocyclic compounds, and nitrogen/boron heterocyclic compounds, the nitrogen-containing heteroatoms, the nitrogen-containing heteroatoms, the nitrogen-containing hetero
  • the method for providing high-purity hydrogen according to the present invention further includes introducing the released hydrogen into a hydrogen storage tank to store the hydrogen; or the obtained high-purity and high-pressure hydrogen can be directly used for hydrogen fuel cell vehicle filling.
  • the present invention provides a high-efficiency distributed method for producing high-purity and high-pressure hydrogen.
  • the method includes: in a dehydrogenation reactor, liquid organic hydrogen storage raw materials are carried out in the presence of a dehydrogenation catalyst The dehydrogenation reaction obtains a dehydrogenation reaction product including hydrogen; in a cooling separation device, the dehydrogenation reaction product is cooled and separated to obtain a hydrogen-rich stream and an organic liquid; in a hydrogen storage alloy storage container, the hydrogen-rich stream or purified The hydrogen-rich stream is contacted with the hydrogen storage alloy to obtain the hydrogen-containing alloy; the hydrogen purging removes the organic matter in the hydrogen storage alloy storage container; wherein the purity of the purging hydrogen is preferably greater than 90% by weight (for example, greater than 95% by weight, greater than 99% by weight) %); The hydrogen-containing alloy is heated to release hydrogen to obtain high-pressure hydrogen and the obtained high-pressure hydrogen is supplied to a hydrogen device or high-pressure hydrogen storage tank for storage.
  • the present invention provides a system for providing high-purity and high-pressure hydrogen, including: organic liquid hydrogen storage raw material storage and supply device for storing organic liquid hydrogen storage raw materials and providing organic liquid hydrogen storage materials to the dehydrogenation reactor Liquid hydrogen storage raw material; dehydrogenated liquid storage device, used to store the liquid product obtained after the dehydrogenation of the organic liquid hydrogen storage raw material; dehydrogenation reactor device, used to carry out the organic liquid hydrogen storage raw material under the action of the dehydrogenation catalyst
  • the dehydrogenation reaction obtains a dehydrogenation reaction product including hydrogen; a cooling separation device for separating the dehydrogenation reaction product to obtain a hydrogen-rich gas product and a liquid product; a hydrogen storage-hydrogen supply device, which includes a hydrogen storage alloy storage container, and hydrogen storage
  • the alloy heating system is used to contact the hydrogen-rich gas and the hydrogen storage alloy to absorb hydrogen at low temperature and low pressure, and heat to dehydrogenate after the adsorption is saturated; the optional purging device is used to remove the organic
  • the present invention provides a system for providing high-purity and high-pressure hydrogen, in which: 1 is an organic liquid storage tank, 2 is a raw material pump, 3 is a heat exchanger, 4 is a dehydrogenation reactor, and 5 is a heat exchanger.
  • Heater 6 is a hydrogen storage tank, 7 is a one-way valve, 8 is an energy transfer body system, 9 is a purge system, and 10 is a hydrogen storage control system.
  • the organic liquid raw material storage system described in Figure 3 includes organic liquid storage The tank (1) and the raw material pump (2) connected to the organic liquid dehydrogenation reactor, the organic liquid storage tank is provided with an organic liquid raw material inlet and an organic liquid raw material outlet; the organic liquid dehydrogenation reaction system includes an organic liquid The liquid heat exchanger (3) and the dehydrogenation reactor (4), the organic liquid heat exchanger is connected to the outlet and inlet of the organic liquid dehydrogenation reactor, and is used for cooling the outlet gas of the reactor and preheating the raw materials; The outlet gas of the reactor can undergo further heat exchange and cooling (5), and after cooling, the hydrogen-rich material can be separated.
  • the hydrogen-rich stream can pass through one or more of the membrane separation device and the pressure swing adsorption device; the purification
  • the booster system includes one or more sets of hydrogen storage tanks (6), and each set of hydrogen storage tanks is connected to a set of backflow prevention devices (7).
  • the hydrogen storage tanks are connected in parallel to at least one hydrogen supply pipeline, including at least one Energy delivery system (8), used to provide energy to each hydrogen storage tank to resolve hydrogen from solid hydrogen storage materials, including at least a set of vacuum pumps (9) and a purge system, used to remove impurity gases in the hydrogen storage tank For removal, the inlet and outlet of the hydrogen storage tank are connected to a flow meter, including a control system (10), which controls the hydrogen absorption and desorption time of each hydrogen storage tank and the start-up time of the energy delivery system according to the hydrogen production volume of the dehydrogenation reaction . Use the hydrogen storage tank inlet flowmeter to calculate the total hydrogen absorption of the hydrogen storage alloy.
  • a control system (10) which controls the hydrogen absorption and desorption time of each hydrogen storage tank and the start-up time of the energy delivery system according to the hydrogen production volume of the dehydrogenation reaction .
  • the present invention provides a mobile hydrogen supply system, including a transport vehicle and a system for providing high-purity and high-pressure hydrogen according to the present invention provided on the transport vehicle.
  • the present invention provides a distributed hydrogen supply device, including the system for providing high-purity and high-pressure hydrogen according to the present invention, and optionally a high-pressure hydrogen storage tank.
  • the method for preparing high-purity hydrogen provided by the present invention can efficiently provide high-purity hydrogen, and can provide high-purity and high-pressure hydrogen when a hydrogen storage alloy with high equilibrium pressure is used.
  • the present invention may also have at least one of the following beneficial technical effects, and preferably has multiple beneficial technical effects:
  • the method of the present invention can have higher dehydrogenation efficiency of organic liquid hydrogen storage compounds.
  • Hydrogen storage metal has better hydrogen absorption efficiency in the presence of organic matter.
  • the dehydrogenation catalyst for producing hydrogen from organic matter dehydrogenation provided by the present invention has the advantages of higher dehydrogenation activity, hydrogen selectivity and/or hydrogen generation rate.
  • the dehydrogenation catalyst for hydrogen production from organic matter dehydrogenation provided by the present invention can replace part of precious metals with non-noble metals, can reduce the amount of precious metals, and maintain high dehydrogenation activity, hydrogen selectivity and/or hydrogen generation rate.
  • the catalyst provided by the present invention can be used for the dehydrogenation of organic hydrogen storage compounds to produce hydrogen, especially for the dehydrogenation of organic substances containing rings, such as cycloalkane rings or heteroatom-containing rings, to produce hydrogen. It has high conversion rate, selectivity and/ Or hydrogen generation rate.
  • the percentage of the crystalline phase modified metal oxide can be measured by the following method: the Rietveld model corrected by X-ray diffraction and phase filtering, and the crystalline phase modified metal is calculated by the fitting method.
  • the weight percentage of oxides refer to RVSiriwardane, JAPoston, G. Evans, Jr. Ind. Eng. Chem. Res. 33 (1994), 2810-2818 for phase filtering, see RIQAS Rietveld Analysis for the revised Rietveld model, Operation Manual, Material Data, Inc., Berkley, CA (1999).
  • the chemical composition percentage of the modified metal oxide is the total content of the modified metal oxide in the carrier composition, and the chemical composition percentage of the modified metal oxide can be X-ray Fluorescence method or chemical analysis method.
  • the weight percentage of the modified metal oxide on the surface of the carrier composition is measured by the XPS method, and the measured surface layer thickness is in the range from the outer surface to a thickness of 5 nm from the outer surface.
  • the mass part of the modified metal oxide is 1.5-20%, preferably 2.5-17% or 5-15%, or 5-10%.
  • the carrier composition according to scheme 3 characterized in that the modified metal oxide comprises titanium oxide, wherein preferably, in the carrier composition, the mass parts of titanium dioxide is preferably 2-20 %, for example, 5 to 15%, or 5 to 10%, or 2.5 to 17%, and the mass fraction of zirconium dioxide is preferably 0 to 8%, such as 0-6% or 0-3% or 1 to 6%.
  • the carrier composition according to scheme 4 characterized in that, relative to the pure phase of TiO2, in the XPS spectrum of the carrier composition, the binding energy of Ti 2P3/2 orbital electrons is offset, and the binding energy is 458.8
  • the peak at eV shifts from 0.6-0.7 eV to 459.4-459.5 eV, and/or the peak at the Ti 2P1/2 orbital electron binding energy of 464.5 eV shifts from 0.8-0.9 eV to 465.3. ⁇ 465.4eV.
  • a preparation method of a carrier composition comprising the following steps:
  • the alumina matrix is in contact with the modified metal oxide precursor gas flow carried by the gas, and when the titanium tetrachloride reaches the preset loading amount, the gas flow of the modified metal oxide precursor gas flow is stopped to obtain the loading Alumina matrix of a modified metal oxide precursor, wherein the modified metal oxide precursor is a titanium oxide precursor and/or a zirconia precursor;
  • the alumina matrix supporting the modified metal oxide precursor is hydrolyzed and calcined to obtain a carrier composition.
  • the titanium oxide precursor is selected from one or more of titanium tetrachloride, ethyl titanate, isopropyl titanate, and titanium acetate.
  • the zirconium oxide precursor is selected from one or more of zirconium tetrachloride, zirconium ethoxide, zirconium methoxide, zirconium isopropoxide, and tetrabutyl zirconate, preferably zirconium tetrachloride And/or zirconium methoxide.
  • alumina matrix is one or more of ⁇ -alumina, ⁇ -alumina, and rho alumina ⁇ alumina.
  • the specific surface area of the alumina matrix is reduced by ⁇ 10%.
  • the gas is an anhydrous inert gas
  • the water content in the anhydrous inert gas does not exceed 10 ppm.
  • the content of the modified metal oxide precursor in the modified metal oxide precursor gas stream carried by the gas is 0.1-3 g/L, wherein the content of the modified metal oxide precursor is calculated as the metal oxide.
  • step (1) The preparation method of the carrier composition according to scheme 9, characterized in that, in step (1), the temperature of the gas is room temperature to 350°C, for example, room temperature to 300°C or 15 to 300°C.
  • the volume of the gas is based on the volume under standard conditions, and the volume of the alumina matrix is based on the bulk volume.
  • the gas flow contact; the fluidized state can be, for example, a bubbling bed, a turbulent bed, a fast bed or a transport bed.
  • the hydrolysis in step (2) is as follows: the alumina matrix supporting the modified metal oxide precursor is brought into contact with a gas containing water vapor .
  • the ratio of the gas containing water vapor in contact with the alumina matrix is 3 to 80:1, such as 5 to 30:1, preferably 10 ⁇ 25:1, the ratio of water vapor in the gas containing water vapor to the total gas volume is 0.1% to 100% by volume, preferably 3% to 100% by volume, more preferably 10% to 70% by volume ;
  • gases besides water vapor can be inert gas or air.
  • the hydrolysis time is, for example, 1 hour to 50 hours, preferably 2 hours to 30 hours.
  • the usual hydrolysis time is greater than or equal to the load time (the load time refers to the time for the alumina matrix to contact the modified metal oxide precursor gas stream carried by the gas).
  • a catalyst for the dehydrogenation of organic matter to produce hydrogen characterized in that it comprises a carrier containing alumina and a modified metal oxide and an active metal component, the modified metal oxide being titanium oxide and/or Zirconium oxide; the active metal component is an active metal oxide and/or an active metal element.
  • the active metal for example, one of the eighth subgroup metal, the seventh subgroup metal, the fifth subgroup metal, the sixth subgroup metal, the first subgroup metal, the rare earth element, the alkaline earth metal, and the fourth main group metal Or multiple
  • the active metal includes Pt and/or Ni, including or not including other elements.
  • the other elements are V, Cr, Mn, Fe, Co, Ni, Cu, Ag, Ce, W, Mo, Sn, Ca, Pt, Pd, Ru, Re, Rh, Ir, Os, Zn One or more of, P, In.
  • the carrier is the carrier composition according to any one of schemes 1-8 or the carrier composition prepared by the method according to any one of schemes 9-20.
  • a catalyst for the dehydrogenation of organic matter to produce hydrogen comprising a carrier and a supported active metal component, characterized in that the carrier is the carrier composition according to any one of Schemes 1 to 8 or is any of Schemes 9-20.
  • the active metal includes Pt, with or without other metals, the other metals may be noble metals or non-noble metals, and the other metals are Pd, Ru, Re, One or more of Rh, Ir, Os, Sn, V, Mo, Cr, Mn, Fe, Co, Ni, Cu, Ag, Ce, W, Cu, and Ca elements.
  • the catalyst according to claim 22 characterized in that, in the catalyst, the content of active metal is 0.1-20% by weight, for example, 0.1-15% by weight, the content of carrier is 85-99.9% by weight, and the content of Pt is 0.1-10% by weight.
  • the content of the active metal is calculated by the elementary substance of noble metal and oxide of the non-noble metal.
  • the catalyst according to scheme 22 characterized in that, the other metal is one or more of Pd, Ru, Re, Rh, Ir, and Os.
  • the catalyst according to claim 24 characterized in that the content of the active metal in the catalyst is 0.1-10% by weight, preferably 0.5-8% by weight; the content of the carrier is 90-99.9% by weight , Preferably 92 to 99.5% by weight.
  • the weight% is, for example, 0.1-2 or 0.2-1% by weight or 0.1-0.8% by weight
  • the content of the carrier is preferably 90-99.9% by weight, such as 96-99.6% by weight or 98-99.5% by weight or 98.5-99.3% by weight.
  • the catalyst according to item 28 characterized in that the content of Pt in the catalyst is 0.1-2% by weight, such as 0.5-1.5% by weight, and the content of other metals is 0-15% by weight, such as 1-10% by weight. Or 2-8% by weight or 3-7% by weight; the content of the carrier is preferably 85-99.9% by weight, for example, 90-99% by weight or 90-98% by weight or 92-97% by weight.
  • a catalyst for the dehydrogenation of organic matter to produce hydrogen comprising a carrier and a supported active metal component, characterized in that the carrier is the carrier composition according to any one of schemes 1-8 or according to any one of schemes 9-20
  • the carrier is the carrier composition according to any one of schemes 1-8 or according to any one of schemes 9-20
  • the active metal includes nickel, with or without other metals, and the other metals are Zn, Sn, Cu, Fe, Ag, P, In, Re, Mo, Co One or more of, Ca, W.
  • the catalyst according to claim 30 characterized in that, in the catalyst, the mass fraction of the active metal is 5%-30%, the mass fraction of the carrier is 70-95%; the mass fraction of the carrier is preferably 75-90% The active metal mass fraction is preferably 10%-25%.
  • the catalyst according to item 30 characterized in that the content of nickel in the catalyst is 5-25% by weight, calculated as oxide, preferably 6-20% by weight, such as 7-15% by weight or 7-12 Weight% or 8-11% by weight, the content of the other metal is 0-15% by weight, preferably 0-10% by weight, such as 0.5-8% by weight or 1-5% by weight.
  • the carrier is the carrier composition according to any one of aspects 1 to 8 or a carrier composition prepared according to the method according to any one of aspects 9 to 20.
  • step (2) is: placing the carrier impregnated with the active metal component precursor in an environment below -40°C Place for 1h-24h; then vacuum dry to remove water adsorbed on the carrier, and then calcinate to obtain a catalytic composition.
  • the catalyst preparation method according to scheme 32 characterized in that the calcination in step 2: the calcination temperature is 400-700°C, and the calcination time is preferably 0.5-12 hours.
  • a method of using the catalytic composition comprising: combining an organic hydrogen storage compound with the dehydrogenation catalyst described in any one of the schemes 21 to 32 or the dehydrogenation catalyst prepared according to the method described in any one of the schemes 33 to 36 Contact the step of performing dehydrogenation reaction to generate hydrogen.
  • the method according to scheme 37 characterized in that the dehydrogenation reaction temperature is 150-450°C, the weight hourly space velocity is 0.5-50 h-1, and the reaction pressure is 0.3-5 MPa, and the contact is in the presence or absence of hydrogen.
  • the hydrogen-to-oil ratio (the molar ratio of the hydrogen introduced into the dehydrogenation reactor to the organic hydrogen storage compound) is 0-10.
  • the organic hydrogen storage compound is a saturated or unsaturated hydrocarbon containing a cycloalkane ring
  • the organic hydrogen storage compound is cyclohexane, methyl ring Hexane, decahydronaphthalene, bicyclohexane, decahydrocarbazole, dodecahydroethylcarbazole, indoline, 4-aminopiperidine, piperidine-4-carboxyamine, perhydro-4,7- Felorin, 2-methyl-1,2,3,4-tetrahydroquinoline, 2,6-dimethyldecahydro-1,5-naphthyridine, 1,2-BN-cyclohexane, 3 -One or more of methyl-1,2-BN-cyclopentane.
  • a method for providing high-purity hydrogen comprising: contacting an organic liquid hydrogen storage raw material with a dehydrogenation catalyst to react to obtain a dehydrogenation reaction product containing hydrogen;
  • the hydrogen-containing alloy is heated to release hydrogen and obtain high-purity hydrogen.
  • the hydrogen-rich gas is a hydrogen-rich gas product or a hydrogen-containing gas obtained by further separation of the hydrogen-rich gas product, and the further separation method is for example: temperature-variable separation , Membrane separation, pressure swing adsorption separation or their combination.
  • the hydrogen storage alloy can be one or more kinds, and multiple hydrogen storage alloys can be used in a mixture, or in series or in parallel, or in series and parallel;
  • the contact pressure of the hydrogen-rich gas and the hydrogen storage alloy is 0.001-5Mpa, for example, 0.01-5Mpa or 0.03-4Mpa or 0.05-5Mpa or 0.08-2Mpa or 0.005-3Mpa or 0.1-1Mpa.
  • the contact pressure of the hydrogen storage alloy finally contacted is 0.05-5Mpa, preferably 0.1-1MPa.
  • the high equilibrium pressure hydrogen storage alloy has at least one temperature point between 150°C and 450°C, and the equilibrium pressure of hydrogen absorption is greater than or equal to 35Mpa; preferably, the hydrogen storage alloy in at least one container
  • the hydrogen storage alloy is a high equilibrium pressure hydrogen storage alloy.
  • the method according to scheme 1 characterized in that it further comprises the steps of allowing the hydrogen-containing alloy to release hydrogen, and the released hydrogen is contacted with different hydrogen storage alloys to form the hydrogen-containing alloy, and the process is repeated one or more times, at least the last time
  • the hydrogen storage alloy used in the repeated process is a hydrogen storage alloy with high equilibrium pressure.
  • the hydrogen storage alloy is a combination of a first hydrogen storage alloy and a second hydrogen storage alloy; wherein the first hydrogen storage alloy is magnesium-based A 2 B
  • the type hydrogen storage alloy is used for hydrogen-rich gas contact, the second hydrogen storage alloy is used to pressurize the first hydrogen storage hydrogen, and the second hydrogen storage alloy is a hydrogen storage alloy with a high equilibrium pressure.
  • the second hydrogen storage alloy is one or more of rare earth AB 5 type, zirconium titanium AB 2 type, and titanium AB type.
  • the hydrogen desorption temperature of the first hydrogen storage alloy is higher than the hydrogen absorption temperature of the second hydrogen storage alloy, and the temperature difference is preferably ⁇ 100°C, preferably 350°C ⁇ temperature difference ⁇ 150°C.
  • first hydrogen storage alloy and the second hydrogen storage alloy are in different hydrogen storage alloy storage tanks, and the first hydrogen storage alloy storage tank and the second hydrogen storage alloy storage tank There is a heat exchange system in the middle of the tank.
  • B V y1 Cr y2 Mn y3 Fe y4 Co y5 Ni y6 Cu y7 , y1+y2+y3+y4
  • the hydrogen absorption temperature of the hydrogen-rich gas in contact with the first hydrogen storage alloy is preferably 50-100°C, and the hydrogen partial pressure is preferably 0.001-0.03Mpa;
  • the hydrogen release temperature of the hydrogen alloy is preferably 200-350°C, and the hydrogen partial pressure of hydrogen is preferably 0.1-1Mpa;
  • the hydrogen absorption temperature of the second hydrogen storage alloy is preferably -30-100°C, and the hydrogen partial pressure of hydrogen absorption is preferably 0.1-1Mpa
  • the second hydrogen storage alloy desorption temperature is preferably 200-350°C, and the hydrogen desorption hydrogen partial pressure is preferably ⁇ 35Mpa.
  • the method according to scheme 1 characterized in that the temperature at which the hydrogen storage alloy releases hydrogen (the temperature at which the hydrogen storage alloy is heated, referred to as the hydrogen release temperature) is 150 to 450°C, and the pressure of the released hydrogen is ⁇ 35Mpa, for example, 35 to 100 MPa to obtain high-purity and high-pressure hydrogen, or the partial pressure of hydrogen to be released is 0.1 to 5Mpa to obtain high-purity hydrogen, wherein the hydrogen release temperature is higher than the hydrogen absorption temperature.
  • the hydrogen release temperature the temperature at which the hydrogen storage alloy releases hydrogen
  • the pressure of the released hydrogen is ⁇ 35Mpa, for example, 35 to 100 MPa to obtain high-purity and high-pressure hydrogen
  • the partial pressure of hydrogen to be released is 0.1 to 5Mpa to obtain high-purity hydrogen
  • the method is such as: after the hydrogen storage alloy reaches a predetermined adsorption capacity, stop the hydrogen storage
  • the alloy supplies hydrogen-rich gas, allows hydrogen to pass through the hydrogen-containing alloy, and takes out the organic gas in the hydrogen-containing alloy and (also called hydrogen-containing alloy storage container), and introduces it into the storage tank or uses the storage in other hydrogen storage alloy storage containers.
  • Hydrogen alloy absorption; among them, preferably, the purging hydrogen has a purity greater than 90% by weight, more preferably greater than 95% by weight, such as greater than 99% by weight.
  • reaction temperature of the contact reaction between the organic liquid hydrogen storage raw material and the dehydrogenation catalyst is 150-450°C, preferably 200-400°C, more preferably 300-350°C.
  • the dehydrogenation catalyst is a metal-supported catalyst, and the metal-supported catalyst includes a carrier and a supported active metal component; the carrier, the active
  • the metal preferably includes one or more of Group VIII metals; more preferably, the active metal component contains a first active metal and optionally a second active metal, and the first active metal is Pt, Pd, Ru, Rh, One or more of Ir, one or more of the second active metal Ni, Re, Sn, Mo, Cu, Fe, Ca, Co, W, and the second active metal is preferably Ni, One or more of Re and Sn; more preferably, the first active metal includes Pt;
  • the dehydrogenation catalyst includes a carrier and a supported active metal component.
  • the carrier is selected from one or more of aluminum oxide, silicon dioxide, titanium dioxide, zirconium oxide, activated carbon, and silicon aluminum materials
  • the active metal is selected from At least two metals of Ni, Zn, Sn, Cu, Fe, Ag, P, In, Re, Mo, Co, Ca, W, and more preferably two or more of Ni, Zn, Sn, Cu, or
  • the active metal includes Ni and one or more selected from Zn, Sn, Cu, Fe, Ag, P, In, Re, Mo, Co, Ca, and W.
  • the dehydrogenation catalyst includes a carrier and an active metal component
  • the carrier is a carrier composition
  • the carrier composition includes alumina and a modified metal.
  • the weight percentage of the modified metal oxide in the carrier composition, the titanium oxide is calculated as TiO 2 and the zirconium oxide is calculated as ZrO 2 .
  • the method according to item 34 characterized in that the weight of alumina in the carrier composition is 80-98.5 %, preferably 83-97.5% or 85-95% or 90-95%;
  • the mass part of the modified metal oxide is 1.5 to 20%, preferably 2.5 to 17% or 5 to 15%, or 5 to 10%.
  • the modified metal oxide comprises titanium oxide, wherein preferably, the mass fraction of titanium dioxide in the carrier composition is preferably 2-20%. 5 to 15% or 5 to 10% or 2.5 to 17%, the mass fraction of zirconium dioxide is preferably 0 to 8%, such as 0 to 6% or 0 to 3% or 1 to 6%.
  • the oxide matrix has a phase structure of at least one of ⁇ oxide, ⁇ -alumina, rho alumina or ⁇ alumina.
  • the dehydrogenation catalyst comprises a carrier comprising alumina and a modified metal oxide and an active metal component, and the modified metal oxide is titanium oxide And/or zirconium oxide; the active metal component is an oxide of an active metal and/or a simple substance of an active metal.
  • the active metal for example, one of the eighth subgroup metal, the seventh subgroup metal, the fifth subgroup metal, the sixth subgroup metal, the first subgroup metal, the rare earth element, the alkaline earth metal, and the fourth main group metal Or multiple
  • the active metal includes Pt and/or Ni, including or not including other elements; preferably, the other elements are V, Cr, Mn, Fe, Co, Ni, Cu, Ag One or more of, Ce, W, Mo, Sn, Ca, Pt, Pd, Ru, Re, Rh, Ir, Os, Zn, P, In.
  • the active metal includes Pt, with or without other metals, the other metals may be precious metals or non-precious metals, and the other metals are Pd, Ru One or more of, Re, Rh, Ir, Os, Sn, V, Mo, Cr, Mn, Fe, Co, Ni, Cu, Ag, Ce, W, Cu, Ca.
  • the method according to item 43 characterized in that the content of Pt in the catalyst is 0.1-2% by weight, such as 0.5-1.5% by weight, and the content of other metals is 0-15% by weight, such as 1-10% by weight. Or 2-8% by weight or 3-7% by weight; the content of the carrier is preferably 85-99.9% by weight, for example, 90-99% by weight or 90-98% by weight or 92-97% by weight.
  • the active metal includes nickel, with or without other metals, and the other metals are Zn, Sn, Cu, Fe, Ag, P, In, Re, One or more of Mo, Co, Ca, and W.
  • the active metal mass fraction is 5%-30%, the carrier mass fraction is 70-95%; the carrier mass fraction is preferably 75-90% The active metal mass fraction is preferably 10%-25%.
  • the method according to item 51 characterized in that the content of nickel in the catalyst is 5-25% by weight, calculated as oxide, preferably 6-20% by weight, for example, 7-15% by weight or 7-12 Weight% or 8-11% by weight, the content of the other metal is 0-15% by weight, preferably 0-10% by weight, such as 0.5-8% by weight or 1-5% by weight.
  • the organic liquid hydrogen storage raw material is a saturated/or unsaturated hydrocarbon containing a naphthenic ring, with or without heteroatoms
  • the heteroatom-containing organic hydrogen storage compound is An organic substance obtained by the substitution of a hydrocarbon containing a cycloalkane ring by a heteroatom, wherein the heteroatom substitution occurs on the cycloalkane ring.
  • the organic liquid hydrogen storage raw material is preferably a saturated or unsaturated hydrocarbon containing a cycloalkane ring without a heterocyclic atom. More preferably, it is a saturated or unsaturated hydrocarbon containing no heterocyclic atoms with the total number of aromatic rings and cycloalkane rings less than or equal to 2;
  • the organic hydrogen storage raw material is a saturated or unsaturated hydrocarbon containing no heterocyclic atoms with the total number of aromatic rings and naphthenic rings being less than or equal to 2; said saturated and unsaturated hydrocarbon containing cycloalkane rings without heteroatoms Including: one or more of cyclohexane, methylcyclohexane, decalin, and bicyclohexane; saturated or unsaturated hydrocarbons containing heteroatoms and cycloalkane rings include: nitrogen-containing heterocyclic compounds and Nitrogen/boron heterocyclic compounds, such as nitrogen-containing heterocyclic compounds including decahydrocarbazole, dodecahydroethylcarbazole, indoline, 4-aminopiperidine, piperidine-4-carboxyamine, perhydro- One or more of 4,7-phenanthroline, 2-methyl-1,2,3,4-tetrahydroquinoline, 2,6-dimethyldecahydro-1,5-naphth
  • An efficient distributed method for producing high-purity and high-pressure hydrogen comprising:
  • the liquid organic hydrogen storage raw material is subjected to a dehydrogenation reaction in the presence of a dehydrogenation catalyst to obtain a dehydrogenation reaction product including hydrogen;
  • the dehydrogenation reaction product is cooled and separated to obtain a hydrogen-rich stream and an organic liquid;
  • Hydrogen purging removes organic matter in the hydrogen storage alloy storage container; wherein the purity of the purging hydrogen is preferably greater than 90% by weight, more preferably greater than 95% by weight;
  • the hydrogen-containing alloy is heated to release hydrogen to obtain high-pressure hydrogen and the obtained high-pressure hydrogen is supplied to a hydrogen device or a high-pressure hydrogen storage tank for storage.
  • a system for providing high-purity and high-pressure hydrogen including:
  • Organic liquid hydrogen storage raw material storage and supply device used to store organic liquid hydrogen storage raw materials and provide organic liquid hydrogen storage raw materials to the dehydrogenation reactor;
  • Dehydrogenated liquid storage device for storing liquid products obtained after dehydrogenation of organic liquid hydrogen storage raw materials
  • Dehydrogenation reactor device for dehydrogenation reaction of organic liquid hydrogen storage raw materials under the action of dehydrogenation catalyst to obtain dehydrogenation reaction product including hydrogen;
  • Cooling separation device for separating dehydrogenation reaction products to obtain hydrogen-rich gas products and liquid products
  • a hydrogen storage-hydrogen supply device which includes a hydrogen storage alloy storage container and a hydrogen storage alloy heating system for contacting hydrogen-rich gas with the hydrogen storage alloy at low temperature and low pressure to absorb hydrogen, and heat dehydrogenation after adsorption saturation;
  • An optional purge device is used to remove organic matter in the hydrogen storage container
  • the hydrogen supply device supplies high-pressure hydrogen to the hydrogen device or the hydrogen storage tank.
  • the system according to item 57 characterized in that the system is integrated and built in a container, and used as a container-type hydrogen production system in a hydrogen refueling station, or directly built in a hydrogen refueling station for use.
  • the hydrogen storage-hydrogen supply device includes one or more hydrogen storage alloy storage containers, and multiple hydrogen storage alloy storage containers can be connected in parallel or in series or mixed in parallel and in series Join.
  • a mobile hydrogen supply system comprising a transportation vehicle and the system for providing high-purity hydrogen according to any one of solutions 57 to 60 installed on the transportation vehicle.
  • a distributed hydrogen supply device comprising the system for supplying high-purity hydrogen according to any one of schemes 57 to 60, optionally including a high-pressure hydrogen storage tank.
  • SB powder Sasol, Germany, with a solid content of 75% by weight.
  • P25 titanium dioxide: Degussa, Germany, with a solid content of 98% by weight.
  • Metal salt and metal salt were purchased from Sinopharm Chemical Reagent Beijing Co., Ltd.
  • Organic liquid hydrogen storage materials were purchased from Bailingwei Technology Co., Ltd.
  • the composition of the supported organic liquid dehydrogenation catalyst was determined by X-ray fluorescence method, and the dehydrogenation product of the organic liquid hydrogen storage raw material was obtained by chromatographic analysis. The purity of hydrogen is analyzed by gas chromatography.
  • the separation adopts a cooling medium to cool the separation.
  • the energy delivery medium is hot water or hot water vapor, and the water vapor is generated by a water vapor generator.
  • the percentage of the crystal phase modified metal oxide is measured by the following method:
  • a Philips XRG3100 generator equipped with a long and thin concentrated copper X-ray source driven by 40kV, 30mA, a Philips3020 digital goniometer, a Philips3710MPD control computer and a Kevex PSI Peltier cooled silicon detector were used to perform all X-ray diffraction measurements.
  • Use Philips APD4.1C version software to obtain diffraction patterns.
  • Use Material Data, Inc.. Riqas version 3.1C software (Qutokumpu HSC Chemistry for Windows; User Manual, Qutokumpo Resarch Oy, Pori, Finland (1999)) performs all rietveld calculations.
  • the XPS experiment was performed on an ESCALab250 X-ray photoelectron spectrometer from Thermo Fisher.
  • the excitation source is a monochromatic Al K ⁇ X-ray with an energy of 1486.6 eV and a power of 150W.
  • the transmission energy used for the narrow scan is 30 eV.
  • the base vacuum during analysis is about 6.5 ⁇ 10 -10 mbar.
  • the binding energy is corrected by the C1s peak (284.8eV) of the contaminated carbon.
  • the weight percentage of the modified metal oxide on the surface of the carrier composition is measured by measuring 10 sample particles and taking the average value.
  • the specific surface area and pore volume are determined by the static low-temperature adsorption capacity method (according to the method of GB/T5816-1995) using the ASAP2400 automatic adsorption instrument of Micromertics Instrument Company, USA.
  • the specific method is: Vacuum degassing at 250°C and 1.33Pa for 4 hours, contact with nitrogen as adsorbate at -196°C, static adsorption reaches adsorption equilibrium; calculated from the difference between the nitrogen inlet and the remaining in the gas phase after adsorption Determine the amount of nitrogen adsorbed by the adsorbent, and then use the BET formula to calculate the specific surface area and pore volume.
  • the SB powder is calcined at 500°C for 4 hours to obtain ⁇ -Al 2 O 3.
  • the ⁇ -Al 2 O 3 has a specific surface area of 176 m 2 /g and a pore volume of 0.48 mL/g.
  • the nitrogen was stopped passing through the titanium tetrachloride bath; the nitrogen (temperature was 25°C) was changed to 10L/
  • the flow rate of min passes through the deionized water placed in a constant temperature bath at 50°C and then enters the fluidized reactor from the bottom of the reactor, fluidizes for 4 hours, and hydrolyzes to obtain the hydrolyzed carrier.
  • the hydrolyzed carrier was calcined in an air atmosphere at 550° C. for 4 hours to obtain the final carrier, which was named carrier 1.
  • carrier composition and carrier properties are shown in Table 1; its X-ray diffraction (XRD) spectrum is shown in "1" in 1.
  • the preparation method of Carrier 2-8 is the same as the preparation method of Carrier 1 in Carrier Example 1. The difference lies in the time for nitrogen to carry titanium tetrachloride into the fluidized bed and the hydrolysis time for nitrogen to pass into deionized water.
  • the carrier preparation conditions, carrier composition and carrier properties are shown in Table 1.
  • the preparation method of the carrier 9-11 is the same as the preparation method of the carrier 1 in carrier example 1, except that the nitrogen gas first passes through the titanium tetrachloride, and then passes through the zirconium tetrachloride steam generator-the temperature is 300°C.
  • the carrier preparation conditions, carrier composition and carrier properties are shown in Table 1.
  • SB powder is calcined at 500°C for 4 hours to obtain ⁇ -Al 2 O 3 directly, and the carrier is named carrier C1.
  • the carrier composition and carrier properties are shown in Table 1.
  • the carrier was prepared with reference to the method of carrier example 1, the difference is that the ⁇ -Al 2 O 3 obtained by calcining the SB powder at 500° C. for 4 hours is physically mixed with TiO 2 and the carrier is named carrier C2.
  • the carrier composition and carrier properties are shown in Table 1; the X-ray diffraction (XRD) spectrum is shown in "2" in 1.
  • the vector was prepared referring to the vector comparative example 2, and the vector was named vector C3.
  • the carrier composition and carrier properties are shown in Table 1.
  • the carrier was prepared by referring to the method of carrier embodiment 6, the difference is that the carrier is ⁇ -Al 2 O 3 obtained by calcining SB powder for 4 hours at 500° C., and physically mixed with an aqueous solution of titanium tetrachloride, the carrier is named carrier C4.
  • the carrier composition and carrier properties are shown in Table 1.
  • SB powder is calcined at 500°C for 4 hours to obtain ⁇ -Al 2 O 3 , tetrabutyl titanate and deionized water are mixed and stirred for 30 minutes, and then impregnated into ⁇ -Al 2 O 3 by an equal volume immersion method. After drying, 550 The composite oxide carrier was obtained by baking at C for 4 hours.
  • the vector was named vector C5.
  • the carrier composition and carrier properties are shown in Table 1; its X-ray diffraction (XRD) spectrum is shown in "5" in 1.
  • the carrier was prepared according to the formula of carrier example 9, the difference is that the ⁇ -Al 2 O 3 obtained by calcining the SB powder at 500° C. for 4 hours is physically mixed with TiO 2 and ZrO 2 .
  • the vector was named vector C6.
  • the carrier composition and carrier properties are shown in Table 1.
  • the vector was prepared referring to the vector comparative example 6, and the vector was named vector C7.
  • the carrier composition and carrier properties are shown in Table 1.
  • the above-prepared catalyst was subjected to methylcyclohexane dehydrogenation reaction evaluation in a fixed bed reactor.
  • the dehydrogenation reaction was carried out on a fixed bed micro-reactor.
  • the evaluation conditions were: reaction temperature 350°C, reaction pressure (reactor inlet pressure) 1MPa, supplementary hydrogen flow rate 150mL/minH 2 , methylcyclohexane feed 2mL/min, catalyst loading amount 20g.
  • Example 2 In a similar manner to Example 1, mix chloroplatinic acid, nickel nitrate and water into 20mL dipping solution, take 19.7 g of carrier 1, slowly add the dipping solution to carrier 1, and stir while adding to make the dipping solution uniform
  • the impregnation temperature is 25°C
  • the impregnated solid is dried under nitrogen purge at 120°C for 3 hours, and then calcined in air; the calcining temperature is 600°C, and the air-to-agent ratio (air/solid The volume ratio) is 600:1, and the calcination time is 4 hours to obtain a catalyst.
  • the composition of the catalyst is listed in Table 2.
  • the above-prepared catalyst was subjected to methylcyclohexane dehydrogenation reaction evaluation in a fixed bed reactor.
  • the dehydrogenation reaction was carried out on a fixed bed micro-reactor.
  • the evaluation conditions were: reaction temperature 350°C, reaction pressure (reactor inlet pressure) 1MPa, supplementary hydrogen flow rate 150mL/minH 2 , methylcyclohexane feed 2.5mL/min, catalyst loading amount 20g.
  • the dehydrogenation reaction of methylcyclohexane was evaluated on the catalyst prepared above in a fixed bed reactor.
  • the dehydrogenation reaction was carried out on a fixed bed microreactor.
  • the evaluation conditions were: reaction temperature 400°C, reaction pressure (reactor inlet pressure) 1MPa, supplemental hydrogen flow rate 150mL/minH 2 , methylcyclohexane feed rate 1.0mL/min, catalyst loading rate 20g.
  • the catalyst was prepared by the impregnation method.
  • the catalyst formula is shown in Table 2.
  • the carrier is calculated on a dry basis (calcined at 800°C for 1 hour)
  • platinum (Pt) is calculated on a simple dry basis
  • palladium (Pd) is calculated on a simple dry basis
  • iridium (Ir) is calculated on a simple dry basis.
  • Rhenium (Re) is calculated on a dry basis, nickel (Ni) is calculated as NiO, tin (Sn) is calculated as SnO2, zinc (Zn) is calculated as ZnO, copper (Cu) is calculated as CuO, iron (Fe) is calculated as Fe2O3, silver (Ag) according to the count AgO, phosphorus (P) in accordance with the count in accordance with MnO 2 meter P2O5, manganese (Mn).
  • Example 1 According to the evaluation method of Example 1, 5 or 10, the prepared catalyst was evaluated.
  • the evaluation conditions were as follows: reaction pressure (reactor inlet pressure) 1MPa, catalyst loading volume 20g; reaction temperature, supplementary hydrogen flow rate, and methyl
  • reaction pressure reactor inlet pressure
  • catalyst loading volume 20g
  • reaction temperature reaction temperature
  • supplementary hydrogen flow rate reaction temperature
  • methyl reaction temperature
  • the catalysts of Examples 3, 6 and 11 were prepared according to the methods of Examples 2, 5 and 10 respectively. The difference is that the impregnated solid was frozen at -45°C for 10 hours, and then at -5°C, 0.1atm (absolute pressure) vacuum conditions Drying is then carried out as described above.
  • Example 2 According to the evaluation method of Example 1, the prepared catalyst was evaluated.
  • the evaluation conditions were as follows: reaction pressure (reactor inlet pressure) 1MPa, catalyst loading amount 20g; reaction temperature, supplementary hydrogen flow rate, and methylcyclohexane
  • the material quantity is listed in Table 2.
  • the dehydrogenation catalyst provided by the present invention can have higher conversion activity than dehydrogenation catalysts prepared by existing methods. Under the same reaction conditions, it has a higher hydrogen generation rate.
  • the method of freezing and vacuum drying improves the activity and selectivity of the catalyst and the hydrogen generation rate.
  • the preparation conditions include: under a background vacuum of 1 ⁇ 10 -4 Pa, the melting temperature and time are as shown in the table 3; under a background vacuum of 1 ⁇ 10 -4 Pa, the temperature is lowered to the annealing temperature at a rate of 10°C/min, and annealing is performed.
  • the annealing temperature and time are shown in Table 3; in the background vacuum of 1 ⁇ 10 -4 Cool down naturally to room temperature under Pa.
  • the obtained alloy is crushed and sieved to obtain metal powder of 70-200 mesh.
  • the powder is put into a hydrogen storage tank, and the hydrogen storage tank is heated to 300°C under a vacuum of 0.1 Pa for 4 hours to activate the alloy powder to obtain hydrogen storage. Alloys 1-13 and C1-C4.
  • the preparation conditions include: under a background vacuum of 1 ⁇ 10 -4 Pa, the melting temperature and time are as shown in the table 3; under a background vacuum of 1 ⁇ 10 -4 Pa, the temperature is lowered to the annealing temperature at a rate of 10°C/min, and annealing is performed.
  • the annealing temperature and time are shown in Table 3; in the background vacuum of 1 ⁇ 10 -4 Cool down naturally to room temperature under Pa.
  • the obtained alloy is crushed and sieved to obtain metal powder of 70-200 mesh.
  • the powder is put into a hydrogen storage tank, and the hydrogen storage tank is heated to 300°C under a vacuum of 0.1 Pa for 4 hours to activate the alloy powder to obtain hydrogen storage. Alloy 14-26 and C5-C10.
  • the preparation conditions include: under a background vacuum of 1 ⁇ 10 -4 Pa, the melting temperature and time are as shown in the table 3; under a background vacuum of 1 ⁇ 10 -4 Pa, the temperature is lowered to the annealing temperature at a rate of 10°C/min, and annealing is performed.
  • the annealing temperature and time are shown in Table 3; in the background vacuum of 1 ⁇ 10 -4 Cool down naturally to room temperature under Pa.
  • the obtained alloy is crushed and sieved to obtain metal powder of 70-200 mesh.
  • the powder is put into a hydrogen storage tank, and the hydrogen storage tank is heated to 300°C under a vacuum of 0.1 Pa for 4 hours to activate the alloy powder to obtain hydrogen storage. Alloy 27-40 and C11-C14.
  • the obtained alloy is crushed and sieved to obtain 70-200 mesh metal powder, and the powder is put into a hydrogen storage tank, and the hydrogen storage tank is heated to 50-300°C under a vacuum of 0.1 Pa for 1-10 hours to activate the alloy powder (The specific temperature and time of activation are shown in Table 3) to obtain hydrogen storage alloy 57-67 and C20-C24.
  • the hydrogen storage alloy provided by the present invention has good resistance to organic pollution, has better hydrogen absorption efficiency when the hydrogen contains organic matters, and has a higher hydrogen storage capacity, and high-pressure and high-purity hydrogen can be obtained.
  • Example 1 The following test methods are used to illustrate the effect of the dehydrogenation reaction of the catalyst of Example 1 and the organic liquid hydrogen storage material of Example 68 of the AB 5 type hydrogen storage alloy, separation and purification and pressurization.
  • the raw material oil was methylcyclohexane, and the methylcyclohexane dehydrogenation reaction was evaluated on a fixed bed microreactor.
  • the evaluation conditions were: reaction temperature 350°C, pressure 1MPa, supplementary hydrogen flow rate 150mL/minH 2 (standard condition), The methylcyclohexane was fed at 2 mL/min, and the catalyst loading was 20 grams. The specific parameters and results are shown below.
  • the dehydrogenation reaction product After being cooled, the dehydrogenation reaction product is separated in a separation tank placed in 20°C brine, the cooling temperature is controlled to 20°C, the liquid product is collected, and the gas product is introduced into the hydrogen storage alloy storage tank for hydrogen absorption. After the adsorption capacity of the hydrogen storage alloy reaches the set value, the hydrogen storage alloy storage tank is purged with hydrogen with a purity of 99% at the hydrogen absorption temperature for 30 minutes, and then the hydrogen storage alloy is heated to release the hydrogen.
  • the reaction product was analyzed by chromatography, and the conversion rate was calculated using the 10 minute product composition data.

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Abstract

一种用于有机储氢原料脱氢生成氢气的催化剂及该催化剂的载体以及其制备方法；该催化剂具有更高的活性，氢气选择性较高，该制备方法易于实施。

Description

有机储氢原料脱氢催化剂以及该催化剂的载体、储氢合金、和提供高纯度氢气的方法 技术领域
本发明涉及一种用于有机储氢原料脱氢生成氢气的催化剂及该催化剂的载体以及其制备方法；本发明还涉及一种储氢合金以及其制备方法；本发明还涉及一种提供高纯度氢气的方法、一种高效分布式制高纯高压氢气的方法、一种提供高纯高压氢气的系统、一种移动式供氢系统和一种分布式供氢装置。
背景技术
氢气作为可再生能源，不仅能效高，而且几乎不产生废弃物。发展氢气能源有望成为提高能效，降低石油消费，改善生态环境，保障能源安全的重要途径，可持续，高效率的规模制氢技术的开发，已成为氢能时代的迫切需求。
氢气在通常条件下以气态形式存在，且易燃，易爆，易扩散，使得人们在实际应用中要优先考虑氢的储存和运输中的安全，高效和无泄漏损失问题，这就给储存和运输带来很大的困难。因此，氢能利用需要解决氢气的储运问题。
氢气直接从生产场地通过高压气态运输到加氢站，运输成本较高，且长距离运输也存在一定的交通安全隐患；采用高压气态存储氢气，储氢罐成本高，占地面积大，也存在较大的安全隐患。
发明内容
本发明要解决的一个技术问题是提供一种用于有机储氢化合物脱氢制备氢气的催化剂以及该催化剂的载体。本发明要解决的另一个技术问题是提供一种用于含有机物氢气提纯方法的储氢合金及其制备方法。本发明要解决的另一个技术问题是提供一种提供高纯度氢气的方法、一种高效分布式制高纯高压氢气的方法、一种提供高纯高压氢气的系统、一种移动式供氢系统和一种分布式供氢装置。
为此，本发明提供以下技术方案：
1.一种提供高纯度氢气的方法，该方法包括：
(1)使有机液体储氢原料与脱氢催化剂接触反应，得到含有氢气的脱氢反应产物；
(2)将脱氢反应产物冷却，得到液体产物和富氢气体产物，收集液体产物；
(3)使富氢气体与储氢合金接触，得到含氢合金，收集未吸附的气体；
(3a)任选地，除去含氢合金储存容器中的有机物；
(4)加热含氢合金，释放氢气。
2.根据前述技术方案中任一项的提供高纯度氢气的方法，其特征在于，在(1)中：
有机液体储氢原料与脱氢催化剂接触反应的反应温度为150-450℃(例如，200-400℃，300-350℃)；
有机液体储氢原料与脱氢催化剂接触反应的重时空速0.5-50小时 -1(例如，1-45小时 -1，2-30小时 -1)；
有机液体储氢原料与脱氢催化剂接触反应的压力为0.03-5MPa(表压)(例如0.3-5MPa，0.1-3MPa，0.5-2MPa或0.2-1.6MPa)；
任选地，使有机液体储氢原料与氢气混合后与脱氢催化剂接触，氢烃比(氢气与有机液体储氢原料的摩尔比)为0-10(例如0-8)。
3.根据前述技术方案中任一项的提供高纯度氢气的方法，其特征在于，在(2)中，
将脱氢反应产物冷却的冷却温度低于液体产物中的有机物的沸点温度；优选的，低于其中的常温常压下为液态的沸点最低的有机物的沸点温度。
4.根据前述技术方案中任一项的提供高纯度氢气的方法，其特征在于，在(3)中，
所述的富氢气体为富氢气体产物或富氢气体产物经过进一步分离得到的含氢气的气体，所述的进一步分离的方法包括变温分离，膜分离，变压吸附分离或它们的组合；
所述的富氢气体中氢气的质量分数为≥80％(例如80-99％，优选为≥85％，更优选为≥90％)。
5.根据前述技术方案中任一项的提供高纯度氢气的方法，其特征在于，在(3)中，
所述的富氢气体与储氢合金的接触在一个或多个储氢合金储存容器中进行；
所述的储氢合金可以是一种或者多种，多种储氢合金可以混合使用，也可以串联使用或并联使用或串并联混合使用；
所述的富氢气体与储氢合金接触的压力为0.001-5MPa(例如，0.01-5MPa，0.03-4MPa，0.05-5MPa，0.08-2MPa，0.05-3MPa，0.1-1MPa)，当储氢合金储存容器为多个，且存在储氢容器串联的情况，按照富氢气体物流方向，最后接触储氢合金的接触压力(也称为吸氢压力)为0.05-5MPa(例如0.1-1MPa)；
所述的富氢气体与储氢合金接触的温度(也称为吸氢温度)为-70至100℃(例如，-50至90℃，-30至80℃)；
与储氢合金接触时，所述的富氢气体的温度低于有机液体储氢原料在常压下 的沸点温度。
6.根据前述技术方案中任一项的提供高纯度氢气的方法，其特征在于，在(3)中，
所述的储氢合金储存容器为一个或多个，其中按照接触氢气的顺序，最后与氢气接触的储氢合金储存容器中的储氢合金为具有高平衡压力的储氢合金，所述的具有高平衡压力的储氢合金为在温度为150-450℃之间至少存在一个温度点，氢气吸收的平衡压力大于等于35MPa；优选的，至少一个储氢合金储存容器中的储氢合金为具有高平衡压力的储氢合金。
7.根据前述技术方案中任一项的提供高纯度氢气的方法，其特征在于，进行步骤(3a)，其中除去含氢合金储存容器中的有机物采用吹扫的方法(例如使用氢气吹扫，其方法例如：储氢合金达到预定的吸附量以后，停止向储氢合金供应富氢气体，使氢气通过含氢合金，将含氢合金和含氢合金储存容器(也称储氢合金储存容器)中的有机气体带出，引入储罐储存或者使用其它储氢合金储存容器中的储氢合金吸收；其中优选的，吹扫用氢气的纯度大于90重量％，更优选大于95重量％，例如大于99重量％)。
8.根据前述技术方案中任一项的提供高纯度氢气的方法，其特征在于，在(4)中：
储氢合金释放的氢气的温度(即，加热储氢合金的温度，简称放氢温度)为150-450℃，释放的氢气的压力为≥35MPa(例如为35-100MPa)以得到高纯高压氢气，或者释放的氢气的分压为0.1-5MPa以得到高纯氢气，其中放氢温度高于吸氢温度。
9.根据前述技术方案中任一项的提供高纯度氢气的方法，其特征在于，还包括使含氢合金释放氢气，释放的氢气与不同的储氢合金接触形成含氢合金，该过程重复一次或多次，其中至少最后一次的重复过程所用的储氢合金为具有高平衡压力的储氢合金。
10.根据前述技术方案中任一项的提供高纯度氢气的方法，其特征在于，
所述的储氢合金为第一储氢合金与第二储氢合金联用；
第一储氢合金为镁系A 2B型储氢合金，用于富氢气体接触，
第二储氢合金用于将第一储氢氢气增压，第二储氢合金为具有高平衡压力的储氢合金，第二储氢合金为稀土系AB 5型，锆钛系AB 2型，钛系AB型储氢合金中的一种或者多种；
富氢气体先经过第一储氢合金，进行杂质分离；然后使第一储氢合金释放出的高纯氢气与第二储氢合金进行接触，然后使第二储氢合金在高压下释放氢气。
第一储氢合金放氢温度高于第二储氢合金吸氢温度，温差优选≥100℃(例如350℃≥温差≥150℃)；
第一储氢合金和第二储氢合金在不同的储氢合金储存罐中，且第一储氢合金储存罐和第二储氢合金储存罐中间有换热系统；
富氢气体与第一储氢合金接触的吸氢温度为20-150℃(例如50-100℃)，氢气分压为0.001-0.1MPa(0.001-0.03MPa)；
第一储氢合金释放氢气的温度(放氢温度)为150-450℃(例如200-350℃)，放氢的氢气分压为0.1-5MPa(例如0.1-1MPa)；
第二储氢合金吸收氢气的吸氢温度为-70至100℃(例如-30至100℃)，吸氢的氢气分压为0.1-5MPa(例如0.1-1MPa)，
第二储氢合金放氢温度为150-450℃(例如200-350℃)，放氢的氢气分压为≥35MPa(例如35-100MPa)。
11.根据前述技术方案中任一项的提供高纯度氢气的方法，其特征在于，
所述的有机液体储氢原料为分子中含有环的有机化合物，其任选地含有杂原子，所述的杂原子可以处于环上；
例如，含有环烷烃环的饱和或不饱和烃，如不含杂环原子的含有环烷烃环的饱和或不饱和烃，更具体地，芳环和环烷烃的环总数小于等于2的不含杂环原子的含有环烷烃环的饱和或不饱和烃，例如，环己烷，甲基环己烷，十氢萘，双环己烷；以及含杂原子的含有环烷烃环的饱和或不饱和烃，例如，含氮杂环化合物，以及含氮/硼杂环化合物，所述的含氮杂环化合物包括十氢咔唑，十二氢乙基咔唑，二氢吲哚，4-氨基哌啶，哌啶-4-羧胺，全氢-4，7-菲洛林，2-甲基-1，2，3，4-四氢喹啉，2，6-二甲基十氢-1，5-萘啶中的一种或者几种；所述的含氮/硼杂环化合物包括：1，2-硼杂氮杂-环己烷，3-甲基-1，2-硼杂氮杂-环戊烷中的一种或者多种。
12.根据前述技术方案中任一项的提供高纯度氢气的方法，其特征在于，
还包括将释放的氢气引入到氢气储罐以储存氢气；或者所得到的高纯高压氢气可以直接用于氢燃料电池车加注。
13.一种高效分布式制高纯高压氢气的方法，该方法包括：
在脱氢反应器中，将液体有机储氢原料在脱氢催化剂的存在下进行脱氢反应得到包括氢气的脱氢反应产物；
在冷却分离装置中，将脱氢反应产物冷却并分离，得到富氢物流和有机液体；
在储氢合金储存容器中，使富氢物流或提纯后的富氢物流与储氢合金接触，得到含氢合金；
氢气吹扫除去储氢合金储存容器中的有机物；其中，吹扫氢气的纯度优选大 于90重量％(例如大于95重量％，大于99重量％)；
将含氢合金加热释放氢气，得到高压氢气和将得到的高压氢气提供给用氢装置或高压氢气储存罐储存。
14.一种提供高纯高压氢气的系统，包括：
有机液体储氢原料储存和供应装置，用于储存有机液体储氢原料和向脱氢反应器提供有机液体储氢原料；
脱氢后液体储存装置，用于储存有机液体储氢原料脱氢后得到的液体产物；
脱氢反应器装置，用于将有机液体储氢原料在脱氢催化剂的作用下进行脱氢反应得到包括氢气的脱氢反应产物；
冷却分离装置，用于将脱氢反应产物分离得到富氢气体产物和液体产物；
储氢-供氢装置，其包括储氢合金储存容器，储氢合金加热系统，用于将富氢气体与储氢合金在低温低压下接触吸氢，吸附饱和后加热脱氢；
任选的吹扫装置用于除去储氢容器中的有机物；
氢气供应装置，将高压氢气提供给用氢装置或氢气储存罐；
优选地，所述的系统设置集成建造在集装箱内，作为集装箱式制氢系统置于加氢站使用，或直接建造在加氢站使用；
优选地，所述的储氢-供氢装置包括一个或多个储氢合金储存容器，多个储氢合金储存容器可以并联或串联或者并联和串联混合联接；
优选地，至少一个所述的储氢合金储存容器为耐高压容器和/或所述的氢气供应装置为耐高压的装置，例如其耐受压力为35MPa以上。
15.一种移动式供氢系统，包括运输车辆和设置在运输车辆上的根据前述技术方案中任一项的提供高纯高压氢气的系统。
16.一种分布式供氢装置，包括根据前述技术方案中任一项的提供高纯高压氢气的系统，并且任选地包括高压氢气贮存罐。
17.一种储氢合金或者根据前述技术方案中任一项的方法、系统或装置，其特征在于，所述的储氢合金为稀土系AB 5型，锆钛系AB 2型，钛系AB型，镁系A 2B型以及钒基固溶体型储氢合金中的一种或者多种，其中
所述的稀土系AB 5型储氢合金的分子表达式为：M mNi x1Co x2Mn x3Fe x4Al x5Sn x6，
4.5≤x1+x2+x3+x4+x5+x6≤5.5，
其中，M m为La y1Ce y2Nd y3Pr y4Y y5，
y1+y2+y3+y4+y5＝1，
其中，
0.4≤y1≤0.99(例如，0.4≤y1≤0.8)，0≤y2≤0.45(例如，0.1≤y2≤0.45)，0≤y3≤0.2 (例如，0≤y3≤0.2)，0≤y4≤0.05(例如，0≤y4≤0.05)，0.01≤y5≤0.1(例如，0.01≤y5≤0.05)，3≤x1≤5.45(例如，3≤x1≤4.9)，0≤x2≤1.5(例如，0.1≤x2≤1)，0≤x3≤0.8(例如，0.1≤x3≤0.6)，0≤x4≤0.8(例如，0.1≤x4≤0.6)，0≤x5≤0.75(例如，0.05≤x5≤0.5)，0≤x6≤0.2；(例如，0≤x6≤0.15)；
所述的锆钛系AB 2型储氢合金的的分子表达式为AB 2，其中
A＝Mg x1Ca x2Ti x3Zr x4Y x5La x6，x1+x2+x3+x4+x5+x6＝0.9-1.1，
B＝V y1Cr y2Mn y3Fe y4Co y5Ni y6Cu y7，y1+y2+y3+y4+y5+y6+y7＝1.9-2.1，
0≤x1≤0.54(例如，0.01≤x1≤0.3，0.01≤x1≤0.1)，0≤x2≤0.54(例如，0≤x2≤0.25)，0.5≤x3≤1.04(例如，0.6≤x3≤1)，0.05≤x4≤0.58(例如，0.1≤x4≤0.58)，0.01≤x5≤0.2(例如，0.01≤x5≤0.05)，0≤x6≤0.2(例如，0≤x6≤0.05)，0.05≤y1≤1.95(例如，0.05≤y1≤1.8)，0≤y2≤1.9(例如，0≤y2≤1.85)，0.05≤y3≤1.95(例如，0.1≤y3≤1.95)，0≤y4≤1.6(例如，0≤y4≤1.5)，0≤y5≤0.5(例如，0≤y5≤0.3)，0.1≤y6≤0.5(例如，0.1≤y6≤0.3)，0≤y7≤0.5(例如，0.1≤y7≤0.2)，
优选地，0.7≤x3：(x3+x4)≤0.95，
优选地，1.7≤y1+y2+y3+y4≤2；
所述的钛系AB型储氢合金的分子表达式为AB，其中
A＝Ti x1Zr x2Y x3La x4，x1+x2+x3+x4＝0.85-1.1，
B＝V y1Cr y2Mn y3Fe y4Co y5Ni y6Cu y7，y1+y2+y3+y4+y5+y6+y7＝0.95-1.05，
0≤x1≤1.09(例如，0.9≤x1≤1.05)，0≤x2≤1.09(例如，0≤x2≤0.5)，0.01≤x3≤0.2(例如，0.01≤x3≤0.05)，0≤x4≤0.2(例如，0≤x4≤0.05)，0.05≤y1≤0.5(例如，0.05≤y1≤0.2)，0≤y2≤0.8(例如，0≤y2≤0.2)，0≤y3≤0.8(例如，0.05≤y3≤0.4，或0.1≤y3≤0.4)，0.2≤y4≤1(例如，0.5≤y4≤0.9)，0≤y5≤0.35(例如，0≤y5≤0.1)，0≤y6≤0.45(例如，0≤y6≤0.2)，0≤y7≤0.3(例如，0≤y7≤0.2)，
优选地，x1和x2不同时为零；
所述的镁系A 2B型储氢合金的分子表达式为A 2B，其中
A＝Mg x1Ca x2Ti x3La x4Y x5，x1+x2+x3+x4+x5＝1.9-2.1，
B＝Cr y1Fe y2Co y3Ni y4Cu y5Mo y6；y1+y2+y3+y4+y5+y6＝0.9-1.1；
其中，
1.29≤x1≤2.09(例如，1.7≤x1≤2.05)，0≤x2≤0.5(例如，0≤x2≤0.2)，0≤x3≤0.8(例如，0≤x3≤0.5)，0≤x4≤0.5(例如，0≤x4≤0.2)，0.01≤x5≤0.2(例如，0.05≤x5≤0.1)，0≤y1≤0.3(例如，0≤y1≤0.2，0.05≤y1≤0.2)，0≤y2≤0.2(例如，0≤y2≤0.1)，0≤y3≤0.6(例如，0≤y3≤0.5)，0.2≤y4≤1.1(例如，0.7≤y4≤1.05)，0≤y5≤0.5(例如，0≤y5≤0.4)，0≤y6≤0.15(例如，0≤y6≤0.1)；
所述的钒基固溶体型储氢合金的分子表达式为A x1B x2，其中x1+x2＝1，
其中A＝Ti y1V y2Zr y3Nb y4Y y5La y6Ca y7，y1+y2+y3+y4+y5+y6+y7＝1，
B＝Mn z1Fe z2Co z3Ni z4，z1+z2+z3+z4＝1，
0.7≤x1≤0.95(例如，0.8≤x1≤0.95，0.9≤x1≤0.95)，0.05≤x2≤0.3(例如，0.05≤x2≤0.2，0.05≤x2≤0.1)，0.40≤y1≤0.9(例如，0.45≤y1≤0.9，0.5≤y1≤0.8)，0≤y2≤0.5(例如，0≤y2≤0.4)，0≤y3≤0.5(例如，0≤y3≤0.4)，0≤y4≤0.55(例如，0≤y4≤0.4)，0≤y5≤0.2(例如，0.01≤y5≤0.2，0.05≤y5≤0.2)，0≤y6≤0.1(例如，0≤y6≤0.05)，0≤y7≤0.1(例如，0≤y7≤0.05)，0≤z1≤1(例如，0.1≤z1≤1，0.2≤z1≤0.95)，0≤z2≤0.95(例如，0≤z2≤0.9)，0≤z3≤0.3(例如，0≤z3≤0.2)，0≤z4≤0.45(例如，0.05≤z4≤0.45，0.05≤z4≤0.3)，0.55≤z1+z2≤1(例如，0.7≤z1+z2≤1)。
18.根据前述技术方案中任一项的储氢合金、方法、系统或装置，其特征在于，所述的储氢合金选自以下：
La 0.61Ce 0.16Pr 0.04Nd 0.19 Ni 3.55Co 0.75Mn 0.4Al 0.3，(Ti 0.8V 0.2) 0.95(Fe 1) 0.05，(Ti 0.8Y 0.2) 0.95(Mn 0.95Ni 0.05) 0.05，(Ti 0.4V 0.4Y 0.2) 0.9(Fe 0.05Mn 0.95) 0.1，(Ti 0.4V 0.4Y 0.2) 0.9(Fe 0.05Mn 0.9Ni 0.05) 0.1，(Ti 0.7Nb 0.1Y 0.2) 0.9(Mn 1) 0.1，(Ti 0.7Nb 0.1Y 0.2) 0.9(Mn 0.7Ni 0.3) 0.1，(Ti 0.4Zr 0.4Y 0.2) 0.93(Fe 0.2Mn 0.7Co 0.1) 0.07，(Ti 0.4Zr 0.4Y 0.2) 0.93(Fe 0.2Mn 0.7Ni 0.1) 0.07，(Ti 0.4V 0.4Zr 0.2) 0.95(Fe 0.6Mn 0.2Co 0.1Ni 0.1) 0.05，(Ti 0.4V 0.35Zr 0.2Y 0.05) 0.95(Fe 0.6Mn 0.2Co 0.1Ni 0.1) 0.05，(Ti 0.88Y 0.1Ca 0.02) 0.95(Fe 0.3Mn 0.6Co 0.1) 0.05，(Ti 0.88Y 0.1Ca 0.02) 0.95(Fe 0.3Mn 0.6Ni 0.1) 0.05，(Ti 0.7Nb 0.1Y 0.2) 0.8(Mn 0.7Ni 0.3) 0.2，Ti 0.64Zr 0.45Y 0.01VMn 0.9Ni 0.1，Mg 0.01Ti 0.93Zr 0.15Y 0.01VMn 0.9Ni 0.1，Ti 0.55Zr 0.48Y 0.05La 0.02V 0.33Cr 0.05Mn 1.5Fe 0.09Ni 0.1，Ti 0.85Zr 0.18Y 0.05La 0.02V 0.23Cr 0.05Mn 1.5Fe 0.09Ni 0.1Cu 0.1，Ti 0.6Zr 0.4Y 0.05V 0.1Mn 1.8Ni 0.2，Mg 0.1Ti 0.7Zr 0.2Y 0.05V 0.1Mn 1.6Ni 0.2Cu 0.2，Ca 0.01Ti 0.9Zr 0.05Y 0.05V 1.2Mn 0.6Ni 0.3，Ca 0.01Ti 0.85Zr 0.05Y 0.05V 1.2Mn 0.6Ni 0.1Cu 0.2，TiZr 0.05Y 0.05V 0.1Cr 1.4Mn 0.2Co 0.1Ni 0.3，Mg 0.1Ti 0.8Zr 0.15Y 0.05V 0.1Cr 1.4Mn 0.2Co 0.1Ni 0.1Cu 0.2，Ti 0.5Zr 0.55Y 0.05V 1.79Mn 0.1Fe 0.01Ni 0.2，Ti 0.8Zr 0.25Y 0.05V 1.79Mn 0.1Fe 0.01Ni 0.1Cu 0.1，Mg 0.01Ti 0.63Zr 0.45Y 0.01VMn 0.9Ni 0.1，Mg 1.8Y 0.1Ni 1，Mg 1.8Y 0.1Cr 0.05Ni 1，Mg 1.5Ti 0.5Y 0.05Ni 1.1，Mg 1.5Ti 0.5Y 0.05Cr 0.1Ni 1，Mg 2Y 0.1Ni 0.6Cu 0.4，Mg 2Y 0.1Cr 0.05Ni 0.6Cu 0.4，Mg 1.92Y 0.08Ni 0.95Fe 0.05，Mg 1.92Y 0.08Cr 0.2Ni 0.75Fe 0.05，Mg 1.9Y 0.1Fe 0.1Ni 0.8Cu 0.1，Mg 1.9Y 0.1Cr 0.1Fe 0.1Ni 0.7Cu 0.1，Mg 1.9Y 0.1Ni 0.8Co 0.2，Mg 1.9Y 0.1Cr 0.1Ni 0.8Co 0.2，Mg 1.8Y 0.1La 0.1Ni 0.9Co 0.1，Mg 1.8Y 0.1La 0.1Cr 0.05Ni 0.9Co 0.1，Mg 1.7Ti 0.2Y 0.1Ni 0.7Co 0.32，Mg 1.7Ti 0.2Y 0.1Cr 0.05Ni 0.7Co 0.3，TiY 0.01V 0.1Fe 0.7Ni 0.2，TiY 0.01V 0.1Fe 0.7Mn 0.1Ni 0.1，TiY 0.02V 0.2Fe 0.8，TiY 0.02V 0.2Fe 0.7Mn 0.1，Ti 0.97Y 0.03V 0.05Cr 0.03Fe 0.9，Ti 0.97Y 0.03V 0.05Cr 0.03Fe 0.5Mn 0.4，Ti 0.9Y 0.04V 0.15Fe 0.9， Ti 0.9Y 0.04V 0.05Fe 0.9Mn 0.1，Ti 0.91Zr 0.05Y 0.04V 0.1Cr 0.2Fe 0.7，Ti 0.91Zr 0.05Y 0.04V 0.1Cr 0.2Fe 0.6Mn 0.1，Ti 0.95Y 0.05V 0.26Fe 0.7Cu 0.05，Ti 0.95Y 0.05V 0.05Fe 0.7Mn 0.21Cu 0.05，Ti 1.02Y 0.03V 0.05Fe 0.9Ni 0.1，Ti 1.02Y 0.03V 0.05Fe 0.8Mn 0.1Ni 0.1，La 0.5Ce 0.32Nd 0.15Pr 0.02Y 0.01Ni 4.4Fe 0.55Al 0.05，La 0.5Ce 0.32Nd 0.15Pr 0.02Y 0.01Ni 4.4Fe 0.6，La 0.8Ce 0.15Y 0.05Ni 4Mn 0.5Al 0.5，La 0.8Ce 0.15Y 0.05Ni 4.5Mn 0.5，La 0.45Ce 0.4Nd 0.1Pr 0.03Y 0.02Ni 4Co 0.8Al 0.2，La 0.45Ce 0.4Nd 0.1Pr 0.03Y 0.02Ni 4.2Co 0.8，La 0.75Ce 0.15Nd 0.05Pr 0.02Y 0.03Ni 4.7Al 0.1Fe 0.2，La 0.75Ce 0.15Nd 0.05Pr 0.02Y 0.03Ni 4.8Fe 0.2，La 0.8Ce 0.15Nd 0.03Y 0.02Ni 4.5Co 0.3Mn 0.1Al 0.1，La 0.8Ce 0.15Nd 0.03Y 0.02Ni 4.5Co 0.4Mn 0.1，La 0.97Y 0.03Ni 4Co 1。
19.根据前述技术方案中任一项的储氢合金、方法、系统或装置，其特征在于，所述的储氢合金选自以下：
(Ti 0.8Y 0.2) 0.95(Mn 0.95Ni 0.05) 0.05，(Ti 0.4V 0.4Y 0.2) 0.9(Fe 0.05Mn 0.9Ni 0.05) 0.1，(Ti 0.7Nb 0.1Y 0.2) 0.9(Mn 0.7Ni 0.3) 0.1，(Ti 0.4Zr 0.4Y 0.2) 0.93(Fe 0.2Mn 0.7Ni 0.1) 0.07，(Ti 0.4V 0.35Zr 0.2Y 0.05) 0.95(Fe 0.6Mn 0.2Co 0.1Ni 0.1) 0.05，(Ti 0.88Y 0.1Ca 0.02) 0.95(Fe 0.3Mn 0.6Ni 0.1) 0.05，Mg 0.01Ti 0.93Zr 0.15Y 0.01VMn 0.9Ni 0.1，Ti 0.85Zr 0.18Y 0.05La 0.02V 0.23Cr 0.05Mn 1.5Fe 0.09Ni 0.1Cu 0.1，Mg 0.1Ti 0.7Zr 0.2Y 0.05V 0.1Mn 1.6Ni 0.2Cu 0.2，Ca 0.01Ti 0.85Zr 0.05Y 0.05V 1.2Mn 0.6Ni 0.1Cu 0.2，Mg 0.1Ti 0.8Zr 0.15Y 0.05V 0.1Cr 1.4Mn 0.2Co 0.1Ni 0.1Cu 0.2，Ti 0.8Zr 0.25Y 0.05V 1.79Mn 0.1Fe 0.01Ni 0.1Cu 0.1，Mg 1.8Y 0.1Cr 0.05Ni 1，Mg 1.5Ti 0.5Y 0.05Cr 0.1Ni 1，Mg 2Y 0.1Cr 0.05Ni 0.6Cu 0.4，Mg 1.92Y 0.08Cr 0.2Ni 0.75Fe 0.05，Mg 1.9Y 0.1Cr 0.1Fe 0.1Ni 0.7Cu 0.1，Mg 1.9Y 0.1Cr 0.1Ni 0.8Co 0.2，Mg 1.8Y 0.1La 0.1Cr 0.05Ni 0.9Co 0.1，Mg 1.7Ti 0.2Y 0.1Cr 0.05Ni 0.7Co 0.3，TiY 0.01V 0.1Fe 0.7Mn 0.1Ni 0.1，TiY 0.02V 0.2Fe 0.7Mn 0.1，Ti 0.97Y 0.03V 0.05Cr 0.03Fe 0.5Mn 0.4，Ti 0.9Y 0.04V 0.05Fe 0.9Mn 0.1，Ti 0.91Zr 0.05Y 0.04V 0.1Cr 0.2Fe 0.6Mn 0.1，Ti 0.95Y 0.05V 0.05Fe 0.7Mn 0.21Cu 0.05，Ti 1.02Y 0.03V 0.05Fe 0.8Mn 0.1Ni 0.1，La 0.5Ce 0.32Nd 0.15Pr 0.02Y 0.01Ni 4.4Fe 0.55Al 0.05，La 0.8Ce 0.15Y 0.05Ni 4Mn 0.5Al 0.5，La 0.45Ce 0.4Nd 0.1Pr 0.03Y 0.02Ni 4Co 0.8Al 0.2，La 0.75Ce 0.15Nd 0.05Pr 0.02Y 0.03Ni 4.7Al 0.1Fe 0.2，La 0.8Ce 0.15Nd 0.03Y 0.02Ni 4.5Co 0.3Mn 0.1Al 0.1。
20.根据前述技术方案中任一项的储氢合金、方法、系统或装置，其特征在于，所述的储氢合金是通过下述方法制备的，其中所述的方法包括以下步骤：
(1)以达到储氢合金组成的方式称量各储氢合金原料进行混合；
(2)将步骤(1)混合得到的物质进行熔炼，然后进行退火；
其中，所述熔炼为电炉熔炼或者感应熔炼；
优选地，所述熔炼的条件包括：在真空或者惰性气氛下进行，温度为1200-3000℃，优选为1800-2200℃；
更优选地，在真空下进行，所述熔炼的压力为1×10 -5-1×10 -3帕(绝对压力)， 优选为0.5×10 -4-5×10 -4帕(绝对压力)；
更优选地，在惰性气氛下进行，所述熔炼的压力为0.5-1巴(例如0.6-1巴，0.7-1巴)(表压)，
其中，所述退火的条件包括：在真空或者惰性气氛(如氩气气氛)下进行，温度为500-900℃(例如700-1000℃)，时间为12-360小时；
任选地，该方法还包括将步骤(2)退火得到的物质降温后进行破碎处理以得到10-400目(例如20-400目)的产品，
任选地，该方法还包括将步骤(2)退火得到的物质进行活化处理；优选地，所述活化处理的条件包括：在真空下，温度为50-300℃，时间为1-10小时。
21.一种用于有机物脱氢催化剂的载体组合物，其特征在于，该载体组合物包括氧化铝和改性金属氧化物，所述的改性金属氧化物为钛氧化物和/或锆氧化物，其中，η＜0.3，优选地，η＝0；θ≥5，优选地，θ为5-40(例如5.4-34.3)；
η＝载体组合物中晶相改性金属氧化物的重量百分含量/载体组合物中改性金属氧化物的化学组成重量百分含量，
θ＝载体组合物表面上改性金属氧化物的重量百分含量/载体组合物中改性金属氧化物的化学组成重量百分含量，钛氧化物以TiO 2计，锆氧化物以ZrO 2计。
22.根据前述技术方案中任一项所述的用于有机物脱氢催化剂的载体组合物，其特征在于，所述的载体组合物中氧化铝质量分数为80-98.5％(例如83-97.5％，85-95％或90-95％)，改性金属氧化物的质量分数为1.5-20％(例如2.5-17％，5-15％，或5-10％)。
23.根据前述技术方案中任一项所述的用于有机物脱氢催化剂的载体组合物，其特征在于，所述的改性金属氧化物包括钛氧化物；所述的载体组合物中，二氧化钛的质量分数为2-20％(例如2.5-17％，5-15％或5-10％)，二氧化锆的质量分数为0-8％(例如0-6％，0-3％或1-6％)；优选地，所述的改性金属氧化物(例如二氧化钛)单层分散于氧化铝基质上。
24.根据前述技术方案中任一项所述的用于有机物脱氢催化剂的载体组合物，其特征在于，相对于TiO 2纯物相，所述的载体组合物XPS谱图中，Ti 2P 3/2轨道电子结合能为458.8eV处的峰向高结合能偏移0.6-0.7eV和/或Ti 2P 1/2轨道电子结合能为464.5eV处的峰向高结合能方向偏移0.8-0.9eV。
25.根据前述技术方案中任一项所述的用于有机物脱氢催化剂的载体组合物，其特征在于，所述的载体组合物具有γ-氧化铝，η-氧化铝，ρ-氧化铝或χ-氧化铝中至少一种的物相结构。
26.根据前述技术方案中任一项所述的用于有机物脱氢催化剂的载体组合 物，其特征在于，所述的载体组合物的比表面积为100-350m 2/g，所述的载体组合物的孔体积为0.3-1.3mL/g。
27.一种根据前述技术方案中任一项所述的用于有机物脱氢催化剂的载体组合物的制备方法，包括如下步骤：
(1)将氧化铝基质与气体携带的改性金属氧化物前驱体气流接触，得到负载改性金属氧化物前躯体的氧化铝基质，所述的改性金属氧化物前驱体为氧化钛前躯体和/或氧化锆前躯体；
(2)使负载改性金属氧化物前躯体的氧化铝基质水解，焙烧，得到载体组合物。
28.根据前述技术方案中任一项所述的载体组合物的制备方法，其特征在于，所述的氧化钛前躯体选自四氯化钛，钛酸(四)乙酯，钛酸四丁酯，钛酸(四)异丙酯，醋酸钛的一种或者多种(优选四氯化钛)；所述的氧化锆前躯体选自四氯化锆，乙醇锆，甲醇锆，异丙醇锆，锆酸四丁酯中的一种或多种(优选四氯化锆和/或甲醇锆)。
29.根据前述技术方案中任一项所述的载体组合物的制备方法，其特征在于，所述的氧化铝基质选自γ-氧化铝，η-氧化铝，ρ-氧化铝，χ-氧化铝，水合氧化铝中的一种或多种。
30.根据前述技术方案中任一项所述的载体组合物的制备方法，其特征在于，所述的氧化铝基质的比表面积为100-350m 2/g；优选地，所述的载体组合物的比表面积与所述的氧化铝基质的比表面积之比不低于90％。
31.根据前述技术方案中任一项所述的载体组合物的制备方法，其特征在于，所述的氧化铝基质的孔体积为0.3-1.3mL/g。
32.根据前述技术方案中任一项所述的载体组合物的制备方法，其特征在于，所述的气体为无水的非活性气体(例如氮气，氦气，氖气，氩气)，所述的无水的非活性气体中的水含量不超过10ppm；优选的，所述的气体携带的改性金属氧化物前驱体气流中改性金属氧化物前驱体的含量为0.1-3g/L(例如，0.2-2g/L)，其中改性金属氧化物前驱体含量以金属氧化物计。
33.根据前述技术方案中任一项所述的载体组合物的制备方法，其特征在于，步骤(1)中，所述的气体的温度为室温至350℃(例如为室温(室温是指15-40℃)至300℃，或15至300℃)。
34.根据前述技术方案中任一项所述的载体组合物的制备方法，其特征在于，步骤(1)中接触的压力为0.05-5atm(例如1-3atm)(表压)。
35.根据前述技术方案中任一项所述的载体组合物的制备方法，其特征在于， 所述的气体每分钟的体积流量与氧化铝基质体积的比值为3-80∶1(例如，5-30∶1，10-25∶1)；其中气体的体积以标准状况下的体积计，氧化铝基质的体积以堆积体积计。
36.根据前述技术方案中任一项所述的载体组合物的制备方法，其特征在于，所述的氧化铝基质在流化态下与气体携带的改性金属氧化物前驱体气流接触，或是在搅拌下与所述的气流接触；流化态例如可以是鼓泡床，湍动床，快速床或输送床。
37.根据前述技术方案中任一项所述的载体组合物的制备方法，其特征在于，步骤(2)所述的使负载改性金属氧化物前躯体的氧化铝基质水解，方法如下：使所述的负载改性金属氧化物前躯体的氧化铝基质与含水蒸气的气体接触。
38.根据前述技术方案中任一项所述的载体组合物的制备方法，其特征在于，步骤(2)所述的水解，所述的含水蒸气的气体与氧化铝基质接触的比值(标准状态下含水蒸气的气体与氧化铝基质堆积体积之比)为3-80∶1(例如5-30∶1，或10-25∶1)，所述的含水蒸气的气体中水蒸气占气体总体积的比例为0.1体积％-100体积％(例如3体积％-100体积％)；所述的含水蒸气的气体中水蒸汽以外的其它气体可以是惰性气体，氮气或空气。
39.根据前述技术方案中任一项所述的载体组合物的制备方法，其特征在于，步骤(2)所述的水解，水解时间为1小时至50小时，例如2小时至30小时。
40.根据前述技术方案中任一项所述的载体组合物的制备方法，其特征在于，对于所述的焙烧来说，焙烧温度为350℃-700℃，焙烧时间为0.5-12小时(焙烧气氛可以为不含氧气或含氧气的气氛。一种实施方式情况，所述的含氧气的气氛中氧气的含量可以为3-100％体积，例如为空气气氛或者氧气气氛)。
41.一种用于有机物脱氢制氢气的催化剂或者根据前述技术方案中任一项的储氢合金、方法、系统或装置，其特征在于所述的催化剂含有前述技术方案中任一项所述的用于有机物脱氢催化剂的载体组合物和活性组分。
42.根据前述技术方案中任一项所述的用于有机物脱氢制氢气的催化剂或者根据前述技术方案中任一项的储氢合金、方法、系统或装置，其中活性组分是以下(1)，(2)和(3)中的一种：
(1)贵金属组中的至少一种元素，优选地，活性组分是Pt以及任选地贵金属组中的除Pt以外的至少一种元素；
(2)Pt和第一金属组中的至少一种元素；
(3)Ni，第二金属组中的至少一种元素，和任选的磷；
其中
贵金属组是由选自Pt，Pd，Ru，Re，Rh，Ir，Os的元素构成的组；
第一金属组是由选自Sn，V，Mo，Cr，Mn，Fe，Co，Ni，Cu，Ag，Ce，W，Cu，Ca的元素构成的组；
第二金属组是由选自Zn，Sn，Cu，Fe，Ag，In，Re，Mo，Co，Ca，W的元素构成的组；
所述的催化剂中，载体的含量为70-99.9重量％；活性组分的含量为0.1-30重量％。
43.根据前述技术方案中任一项所述的用于有机物脱氢制氢气的催化剂或者根据前述技术方案中任一项的储氢合金、方法、系统或装置，其中活性组分是(1)贵金属组中的至少一种元素，所述的催化剂中，载体的含量为90-99.9重量％(例如92-99.4重量％，92-99.5重量％，95-99.4重量％，98-99.2重量％，98.5-99.5重量％)；活性组分的含量为0.1-10重量％(例如0.6-8重量％，0.5-8重量％，0.6-5重量％，0.8-2重量％或0.5-1.5重量％)；
优选地，活性组分是Pt以及任选地贵金属组中的除Pt以外的至少一种元素，其中Pt的含量为0.1-10重量％(例如0.1-2重量％，0.6-10重量％或0.6-0.8重量％)，贵金属组中的除Pt以外的至少一种元素的含量为0-9.9重量％(例如0.1-2重量％或0.1-0.8重量％)。
44.根据前述技术方案中任一项所述的用于有机物脱氢制氢气的催化剂或者根据前述技术方案中任一项的储氢合金、方法、系统或装置，其中活性组分是(2)Pt和第一金属组中的至少一种元素；
所述的催化剂中，载体的含量为；75-99.5重量％(例如75-99.4重量％，79.9-98.5重量％)，活性组分的含量为0.5-25重量％(例如0.6-25重量％，1.5-20.1重量％)；
在所述的活性组分中，以单质计的Pt的含量为0.01-10重量％(例如，0.2-8重量％，0.4-2重量％，0.3-0.6重量％，0.1-0.7重量％)；以氧化物计的第一金属组中的至少一种元素的含量为0.5-20重量％(例如0.5-15重量％或1-10重量％)；优选地，第一金属组中的至少一种元素为Ni或为Ni和选自第一金属组中的除Ni以外的至少一种元素的组合，其中Pt(以单质计)与Ni(以NiO计)的质量比为(0.01∶16)至(0.5∶0.1)。
45.根据前述技术方案中任一项所述的用于有机物脱氢制氢气的催化剂或者根据前述技术方案中任一项的储氢合金、方法、系统或装置，其中活性组分是(3)Ni，第二金属组中的至少一种元素，和任选的磷；
在所述的催化剂中，载体的含量为70-95重量％(例如，75-93重量％，或75-90重量％)，以氧化物计的活性组分的含量为5-30重量％(例如，7-25重量％)；
在所述的活性组分中，以NiO计的镍的含量为0.5-25重量％(例如，5-25重量％，6-20重量％，或6-11重量％)；以氧化物计的第二金属组中的至少一种元素的含量为0-15重量％(例如0-10重量％)；以P 2O 5计的磷的含量为0-15重量％。
46.一种催化剂的制备方法，其包括如下步骤根据前述技术方案中任一项所述的载体组合物的制备方法中的步骤(1)和(2)：
(1)将氧化铝基质与气体携带的改性金属氧化物前驱体气流接触，得到负载改性金属氧化物前躯体的氧化铝基质，所述的改性金属氧化物前驱体为氧化钛前躯体和/或氧化锆前躯体；
(2)使负载改性金属氧化物前躯体的氧化铝基质水解，焙烧，得到载体组合物；
其中所述的催化剂的制备方法还包括如下的步骤：
(3)用活性组分前驱体溶液浸渍所述的载体组合物，得到浸渍活性组分前驱体的载体；
(4)浸渍活性组分前驱体的载体干燥，焙烧；
优选地，活性组分是以下(1)，(2)和(3)中的一种：
(1)贵金属组中的至少一种元素，优选地，活性组分是Pt以及任选地贵金属组中的除Pt以外的至少一种元素；
(2)Pt和第一金属组中的至少一种元素；
(3)Ni，第二金属组中的至少一种元素，和任选的磷；
其中
贵金属组是由选自Pt，Pd，Ru，Re，Rh，Ir，Os的元素构成的组；
第一金属组是由选自Sn，V，Mo，Cr，Mn，Fe，Co，Ni，Cu，Ag，Ce，W，Cu，Ca的元素构成的组；
第二金属组是由选自Zn，Sn，Cu，Fe，Ag，In，Re，Mo，Co，Ca，W的元素构成的组。
47.根据前述技术方案中任一项所述的催化剂的制备方法，其特征在于，步骤(4)所述的焙烧，焙烧温度为400-700℃，焙烧时间为0.5-12小时。
48.根据前述技术方案中任一项所述的催化剂的制备方法，其特征在于，
活性组分前驱体是活性组分的可溶性盐(例如，金属硝酸盐，乙酸盐，金属氯化盐，金属碳酸盐，金属醋酸络合物，金属氢氧化物，金属草酸盐络合物，高 价金属酸，高价金属酸盐，金属配合物，铵盐中的一种或多种)。
49.根据前述技术方案中任一项所述的催化剂的制备方法，其特征在于，
将浸渍活性组分前驱体的载体于低于-40℃的环境中放置1小时至24小时；然后进行抽真空干燥，除去载体上吸附的水，然后焙烧，得到催化剂。
附图说明
图1为含氧化铝和钛氧化物的载体组合物的X射线衍射(XRD)谱图，其中“1”为本发明提供的载体组合物(氧化铝负载钛氧化物)的XRD谱图；“2”为浸渍法制备的氧化铝负载Ti氧化物载体组合物的XRD谱图；“3”为氧化铝与二氧化钛机械混合物的XRD谱图，在XRD曲线中，2θ＝25.37°，48.12°，53.97°，55.1°处是TiO 2(锐钛矿)衍射峰。
图2为X射线光电子能谱(XPS)谱图，其中1为纯TiO2的XPS谱图；其它曲线为本发明方法制备的不同TiO2含量的载体组合物(氧化铝负载钛氧化物)的XPS谱图，其中M-2、M-4、M-7和M-8分别为实施例载体2、4、7和8。由图2可见，本发明提供的载体组合物，Ti 2P 3/2轨道的电子结合能(简称结合能)在458.8eV处的峰向高结合能方向位移0.6-0.7eV，Ti 2P 1/2轨道的电子结合能在464.5eV处的峰向高结合能方向位移0.8-0.9eV，说明Ti跟氧化铝载体间有相互作用。
图3为本发明提供的一种提供高纯高压氢气的示意图，其中：1为有机液体存储罐，2为原料泵，3为换热器，4为脱氢反应器，5为换热器，6为储氢罐，7为单向阀，8为能量传递体系统，9为吹扫系统，10为储氢控制系统。
具体实施方案
本发明所述的压力均指表压，除非特别说明。
在本发明的一个方面中，本发明提供了一种用于有机物脱氢催化剂的载体组合物，该载体组合物包括氧化铝和改性金属氧化物，所述的改性金属氧化物为钛氧化物和/或锆氧化物，其中，η＜0.3，优选地，η＝0；θ≥5，优选地，θ为5-40(例如5.4-34.3)；
η＝载体组合物中晶相改性金属氧化物的重量百分含量/载体组合物中改性金属氧化物的化学组成重量百分含量，
θ＝载体组合物表面上改性金属氧化物的重量百分含量/载体组合物中改性金属氧化物的化学组成重量百分含量，钛氧化物以TiO 2计，锆氧化物以ZrO 2计。
优选的，所述的氧化铝和改性金属氧化物部分或全部形成载体组合物。在一种实施方式中，所述的改性金属氧化物负载在载体的表面。
根据本发明的载体组合物，所述的载体组合物中氧化铝质量分数为80-98.5％(例如83-97.5％，85-95％或90-95％)，改性金属氧化物的质量分数为1.5-20％(例如2.5-17％，5-15％，或5-10％)。
根据本发明的载体组合物，所述的改性金属氧化物包括钛氧化物；所述的载体组合物中，二氧化钛的质量分数为2-20％(例如2.5-17％，5-15％或5-10％)，二氧化锆的质量分数为0-8％(例如0-6％，0-3％或1-6％)；优选地，所述的改性金属氧化物(例如二氧化钛)单层分散于氧化铝基质上。
根据本发明的一种实施方案，如果通过XPS测量，在载体表面0-5nm厚的表面层中，所述的改性金属氧化物的含量高于90原子个数％，优选高于95原子个数％的话，就称为改性金属氧化物单层分散于氧化铝基质上。
根据本发明的载体组合物，相对于TiO 2纯物相，所述的载体组合物XPS谱图中，Ti 2P 3/2轨道电子结合能为458.8eV处的峰向高结合能偏移0.6-0.7eV和/或Ti 2P 1/2轨道电子结合能为464.5eV处的峰向高结合能方向偏移0.8-0.9eV。
根据本发明的载体组合物，所述的载体组合物具有γ-氧化铝，η-氧化铝，ρ-氧化铝或χ-氧化铝中至少一种的物相结构。
根据本发明的载体组合物，所述的载体组合物的比表面积为100-350m 2/g(例如，110-340m 2/g或130-250m 2/g或140-200m 2/g)，所述的载体组合物的孔体积为0.3-1.3mL/g(例如，0.32-1.0mL/g或0.35-0.6mL/g或0.35-0.8mL/g)。所述的载体组合物的比表面积与所述的氧化铝基质的比表面积之比不低于90％，即所述的载体组合物比表面积相比纯氧化铝(未引入改性元素改性的氧化铝)，减少的比例≤10％。
本发明提供的载体组合物可用于制备有机物脱氢制备氢气的催化剂，也可以用于烷烃类有机物氧化脱氢制备烯烃或含氧有机物催化剂。通常所述的催化剂包括本发明提供的载体组合物以及负载在该载体组合物上的活性金属组分，所述的活性金属组分为活性金属的氧化物和/或活性金属的单质。所述的活性金属例如第八副族金属，第七副族金属，第五副族金属，第六副族金属，第一副族金属，稀土元素，碱土金属，第四主族金属中的一种或多种。可以较使用现有载体和同样的活性金属制备的催化剂具有更高的脱氢活性和/或具有更高的选择性。
本发明提供的载体组合物，η值比较低，θ值比较高，可作为脱氢催化剂载体，尤其是用于含环烷烃环的有机液体储氢化合物脱氢制备氢气催化剂，可以改善催化剂的脱氢活性和/或选择性。
本发明提供的载体组合物制备方法，可以得到本发明提供的载体组合物，所得到的载体组合物η值比较低，θ值比较高，制备方法易于实施。
用本发明提供载体组合物制备的有机液体储氢化合物脱氢制备氢气的脱氢催化剂，具有更高的活性，氢气选择性较高。制备的氧化脱氢催化剂活性较高，具有更高的氧化选择性。
本发明提供的载体可以用于制备有机储氢化合物脱氢制备氢气催化剂，还可以用于其它涉氢反应催化剂或氧化催化剂作为载体，例如用于有机物氧化脱氢催化剂，不饱和烃加氢催化剂，有机物完全氧化催化剂或NO氧化催化剂。
在本发明的一个方面中，本发明提供了一种载体组合物的制备方法，包括如下步骤：(1)将氧化铝基质与气体携带的改性金属氧化物前驱体气流接触，得到负载改性金属氧化物前躯体的氧化铝基质，所述的改性金属氧化物前驱体为氧化钛前躯体和/或氧化锆前躯体；(2)使负载改性金属氧化物前躯体的氧化铝基质水解，焙烧，得到载体组合物。
根据本发明的载体组合物的制备方法，所述的改性金属氧化物前驱体优选为在室温至350℃能够气化形成气态金属氧化物前驱体的物质。所述的氧化钛前躯体选自四氯化钛，钛酸(四)乙酯，钛酸四丁酯，钛酸(四)异丙酯，醋酸钛的一种或者多种(优选四氯化钛)；所述的氧化锆前躯体选自四氯化锆，乙醇锆，甲醇锆，异丙醇锆，锆酸四丁酯中的一种或多种(优选四氯化锆和/或甲醇锆)。
根据本发明的载体组合物的制备方法，所述的氧化铝基质选自γ-氧化铝，η-氧化铝，ρ-氧化铝，χ-氧化铝，水合氧化铝(例如一水软铝石，一水硬铝石，拟薄水铝石，三水铝石(gibbsite)，拜铝石(bayerite)，诺水铝石(nordstrandite)，无定型氢氧化铝)中的一种或多种，优选地，所述的氧化铝基质平均粒径(直径)为5-100μm，例如为5-50μm。
根据本发明的载体组合物的制备方法，所述的氧化铝基质的比表面积为不低于100m 2/g(例如大于100且不超过380m 2/g，100-350m 2/g，125-335m 2/g)；优选地，所述的载体组合物的比表面积与所述的氧化铝基质的比表面积之比不低于90％，即所得到的载体组合物比表面积相比氧化铝基质比表面积，减少的比例≤10％。
根据本发明的载体组合物的制备方法，所述的氧化铝基质的孔体积为不低于0.3mL/g(例如大于0.3且不超过1.45mL/g，0.3-1.3mL/g，0.35-1.2mL/g，0.35-1.0或0.4-0.8mL/g)。
根据本发明的载体组合物的制备方法，所述的气体为无水的非活性气体(例如氮气，氦气，氖气，氩气)，所述的无水的非活性气体中的水含量不超过10ppm；优选的，所述的气体携带的改性金属氧化物前驱体气流中改性金属氧化物前驱体的含量为0.1-3g/L(例如，0.2-2g/L)，其中改性金属氧化物前驱体含量以金属氧 化物计。
根据本发明的载体组合物的制备方法，步骤(1)中，所述的气体的温度为室温至350℃(例如为室温(室温是指15-40℃)至300℃，或15至300℃)，接触的温度为15-350℃(例如15-300℃或15-100℃或15-200℃或18-60℃或15-40℃)。
根据本发明的载体组合物的制备方法，步骤(1)中接触的压力为0.05-5atm(例如1-3atm)(表压)。
根据本发明的载体组合物的制备方法，所述的气体每分钟的体积流量与氧化铝基质体积的比值为3-80∶1(例如，5-30∶1，10-25∶1)；其中气体的体积以标准状况下的体积计，氧化铝基质的体积以堆积体积计。
根据本发明的载体组合物的制备方法，所述的氧化铝基质在流化态下与气体携带的改性金属氧化物前驱体气流接触，或是在搅拌下与所述的气流接触；流化态例如可以是鼓泡床，湍动床，快速床或输送床。
在一种实施方式中，将氧化铝基质与气体携带的改性金属氧化物前驱体气流(也称为气流)接触，所述的氧化铝基质在固定床下与所述的气流接触，或在流化态下与所述的气体携带的改性金属氧化物前驱体气流接触，也可以是在搅拌下与所述的气流接触。所述的流化态下接触例如可以是以鼓泡床，湍动床，快速床或输送床的方式接触。所述的气体每分钟的体积流量与氧化铝基质的体积的比值为3-80∶1，例如5-30∶1，或10-25∶1。其中气体的体积为以标准状况下的体积计，氧化铝基质的体积以堆积体积计。在另一种实施方式中，所述的气流和氧化铝基质在流化床中接触，接触的体积空速为3-80∶1分钟 -1，例如5-30∶1分钟 -1或者10-25∶1分钟 -1，其中，所述的气流流动的体积流量以所述的气体在标准状况下的体积计，所述的氧化铝基质以堆积体积计，所述的流化床可以是散式流化床，鼓泡床或湍动床。
根据本发明的载体组合物的制备方法，步骤(2)所述的使负载改性金属氧化物前躯体的氧化铝基质水解，方法如下：使所述的负载改性金属氧化物前躯体的氧化铝基质与含水蒸气的气体接触。
根据本发明的载体组合物的制备方法，步骤(2)所述的水解，所述的含水蒸气的气体与氧化铝基质接触的比值(标准状态下含水蒸气的气体与氧化铝基质堆积体积之比)为3-80∶1(例如5-30∶1，或10-25∶1)，所述的含水蒸气的气体中水蒸气占气体总体积的比例为0.1体积％-100体积％(例如3体积％-100体积％，10体积％-70体积％)；所述的含水蒸气的气体中水蒸汽以外的其它气体可以是惰性气体，氮气或空气。
根据本发明的载体组合物的制备方法，步骤(2)所述的水解，水解时间为1 小时至50小时，例如2小时至30小时(通常，水解时间大于等于负载时间，负载时间是指氧化铝基质与气体携带的改性金属氧化物前驱体气流接触的时间)。
根据本发明的载体组合物的制备方法，焙烧气氛可以为不含氧气或含氧气的气氛。一种实施方式情况，所述的含氧气的气氛中氧气的含量可以为3-100％体积，例如为空气气氛或者氧气气氛。焙烧温度为350℃-700℃(如400-700℃)，焙烧时间为0.5-12小时(例如1-10小时，或2-9小时，或4-8小时)。
在本发明的一个方面中，本发明提供了一种用于有机物脱氢制氢气的催化剂，其含有本发明的用于有机物脱氢催化剂的载体组合物和活性组分。
本发明提供的催化剂中，活性组分可以以氧化物和/或活性金属单质的形式存在。
根据本发明的用于有机物脱氢制氢气的催化剂，活性组分是以下(1)，(2)和(3)中的一种：(1)贵金属组中的至少一种元素，优选地，活性组分是Pt以及任选地贵金属组中的除Pt以外的至少一种元素；(2)Pt和第一金属组中的至少一种元素；(3)Ni，第二金属组中的至少一种元素，和任选的磷；其中贵金属组是由选自Pt，Pd，Ru，Re，Rh，Ir，Os的元素构成的组；第一金属组是由选自Sn，V，Mo，Cr，Mn，Fe，Co，Ni，Cu，Ag，Ce，W，Cu，Ca的元素构成的组；第二金属组是由选自Zn，Sn，Cu，Fe，Ag，In，Re，Mo，Co，Ca，W的元素构成的组；所述的催化剂中，载体的含量为70-99.9重量％；活性组分的含量为0.1-30重量％。
根据本发明的用于有机物脱氢制氢气的催化剂，活性组分是(1)贵金属组中的至少一种元素，所述的催化剂中，载体的含量为90-99.9重量％(例如92-99.4重量％，92-99.5重量％，95-99.4重量％，98-99.2重量％，98.5-99.5重量％)；活性组分的含量为0.1-10重量％(例如0.6-8重量％，0.5-8重量％，0.6-5重量％，0.8-2重量％或0.5-1.5重量％)；优选地，活性组分是Pt以及任选地贵金属组中的除Pt以外的至少一种元素，其中Pt的含量为0.1-10重量％(例如0.1-2重量％，0.6-10重量％或0.6-0.8重量％)，贵金属组中的除Pt以外的至少一种元素的含量为0-9.9重量％(例如0.1-2重量％或0.1-0.8重量％)。
根据本发明的用于有机物脱氢制氢气的催化剂，活性组分是(2)Pt和第一金属组中的至少一种元素(例如Sn，Ni，Mn，Cu中的一种或多种)；所述的催化剂中，载体的含量为；75-99.5重量％(例如75-99.4重量％，79.9-98.5重量％)，活性组分的含量为0.5-25重量％(例如0.6-25重量％，1.5-20.1重量％)；在所述的活性组分中，以单质计的Pt的含量为0.01-10重量％(例如，0.2-8重量％，0.4-2重量％，0.3-0.6重量％，0.1-0.7重量％)；以氧化物计的第一金属组中的至少一种 元素的含量为0.5-20重量％(例如0.5-15重量％或1-10重量％)；优选地，第一金属组中的至少一种元素为Ni或为Ni和选自第一金属组中的除Ni以外的至少一种元素(例如Sn，Mn，和Cu，优选Cu)的组合，其中Pt(以单质计)与Ni(以NiO计)的质量比为(0.01∶16)至(0.5∶0.1)。优选地，所述的催化剂中Pt的含量为0.1-0.5重量％，以氧化物计Ni的含量为0.5-15重量％，例如1-10重量％，以氧化物计第一金属组中的除Ni以外的元素的含量为0-10重量％，例如1-6重量％。所述的活性组分更进一步优选为Pt，Ni和Cu。
根据本发明的用于有机物脱氢制氢气的催化剂，其中活性组分是(3)Ni，第二金属组中的至少一种元素(优选，Sn，Cu，Zn，Fe，Ag，更优选，Sn，Ag，Cu和Zn，进一步优选Sn，Zn和Cu，更进一步优选Sn和Zn)，和任选的磷。根据该优选的实施方式，可以具有较高的转化率和氢气生成速率，并且相对于其它活性金属可以具有较高的氢气选择性。在所述的催化剂中，载体的含量为70-95重量％(例如，75-93重量％，或75-90重量％)，以氧化物计的活性组分的含量为5-30重量％(例如，7-25重量％，10-25重量％，8-20重量％，或10-16重量％)；在所述的活性组分中，以NiO计的镍的含量为0.5-25重量％(例如，0.5-20重量％，5-25重量％，6-20重量％，5-15重量％，8-10重量％，或6-11重量％)；以氧化物计的第二金属组中的至少一种元素的含量为0-15重量％(例如0-10重量％，2-6重量％)；以P 2O 5计的磷的含量为0-15重量％(例如，0-8重量％，0-6重量％)。
根据本发明的用于有机物脱氢制氢气的催化剂，所述的催化剂比表面积为100-350m 2/g(例如120-330m 2/g)，所述的催化剂的孔体积为0.3-1.3mL/g(例如0.35-1.2mL/g)。
在本发明的一个方面中，本发明提供了一种本发明的用于有机物脱氢制氢气的催化剂的制备方法，其包括如下步骤：(1)将氧化铝基质与气体携带的改性金属氧化物前驱体气流接触，得到负载改性金属氧化物前躯体的氧化铝基质，所述的改性金属氧化物前驱体为氧化钛前躯体和/或氧化锆前躯体；(2)使负载改性金属氧化物前躯体的氧化铝基质水解，焙烧，得到载体组合物；(3)用活性组分前驱体溶液浸渍所述的载体组合物，得到浸渍活性组分前驱体的载体；(4)浸渍活性组分前驱体的载体干燥，焙烧；优选地，活性组分是以下(1)，(2)和(3)中的一种：(1)贵金属组中的至少一种元素，优选地，活性组分是Pt以及任选地贵金属组中的除Pt以外的至少一种元素；(2)Pt和第一金属组中的至少一种元素；(3)Ni，第二金属组中的至少一种元素，和任选的磷；其中贵金属组是由选自Pt，Pd，Ru，Re，Rh，Ir，Os的元素构成的组；第一金属组是由选自Sn，V，Mo，Cr，Mn，Fe，Co，Ni，Cu，Ag，Ce，W，Cu，Ca的元素构成的组； 第二金属组是由选自Zn，Sn，Cu，Fe，Ag，In，Re，Mo，Co，Ca，W的元素构成的组。
根据本发明的用于有机物脱氢制氢气的催化剂的制备方法，步骤(4)所述的焙烧，焙烧温度为400-700℃，焙烧时间为0.5-12小时。
在一种实施方式中，在用活性组分前驱体的溶液浸渍载体组合物时，通常包括所述的将活性金属组分前躯体溶解在水中，浸渍载体组合物，得到浸渍活性金属组分前驱体的载体。其中浸渍的方法可采用现有浸渍方法，例如可以是等体积浸渍，过量浸渍的方法。所述的水例如去离子水，蒸馏水或脱阳离子水中的一种或多种。也可以将金属前躯体溶解在水中，得到金属前躯体溶液；将金属前躯体溶液以共浸或分步浸渍的方法引入到载体上，浸渍可采用饱和浸渍或过饱和浸渍。当催化剂中含有两种以上金属活性时，所述的共浸渍为两种以上金属元素可以共同溶解在去离子水中，再将浸渍液浸渍到载体上，在进行干燥和焙烧。所述的分步浸渍为，将两种以上金属元素分别溶解在去离子水中；分别将金属浸渍液浸渍在载体上，每次浸渍后得到的载体均需进行干燥和焙烧，对引入金属的先后次序没有要求。例如，可以将Pt的前驱体和第一金属组中的一种元素的前驱体配成溶液，用来浸渍所述的载体组合物，也可以先浸渍Pt的前驱体，干燥后，浸渍第一金属组中的该元素的前驱体。例如，浸渍时浸渍液与载体的液/固体积比为0.3-5.0，优选0.6-4.0，浸渍温度为10-50℃，优选15-40℃。优选地，浸渍后于室温下静置2-10小时，将浸渍后的固体干燥后进行焙烧，焙烧温度优选400-700℃，焙烧时间优选0.5-12小时，例如1-10小时或2-9小时或4-8小时。焙烧的气氛没有特殊要求，例如可以在空气中进行焙烧，焙烧时的空气(标况)/催化剂体积比例如为400-1000∶1，焙烧时间优选4-8小时。
根据本发明的用于有机物脱氢制氢气的催化剂的制备方法，活性组分前驱体是活性组分的可溶性盐(例如，金属硝酸盐，乙酸盐，金属氯化盐，金属碳酸盐，金属醋酸络合物，金属氢氧化物，金属草酸盐络合物，高价金属酸，高价金属酸盐，金属配合物，铵盐中的一种或多种)。在一种实施方案中，所述的高价金属酸/高价金属酸盐例如是氯铂酸，氯铂酸铵，四氨合硝酸铂，四氨合氢氧化铂中的一种或多种。所述的磷的前驱体例如磷酸铵，磷酸二氢铵，磷酸氢二铵，磷酸，金属磷酸盐中的一种或多种。
根据本发明的用于有机物脱氢制氢气的催化剂的制备方法，将浸渍活性组分前驱体的载体于低于-40℃的环境中放置1小时至24小时；然后进行抽真空干燥，除去载体上吸附的水，然后焙烧，得到催化剂。
在本发明的一个方面中，本发明提供了一种储氢合金，所述的储氢合金为稀 土系AB 5型，锆钛系AB 2型，钛系AB型，镁系A 2B型以及钒基固溶体型储氢合金中的一种或者多种，其中
所述的稀土系AB 5型储氢合金的分子表达式为：M mNi x1Co x2Mn x3Fe x4Al x5Sn x6，
4.5≤x1+x2+x3+x4+x5+x6≤5.5，
其中，M m为La y1Ce y2Nd y3Pr y4Y y5，
y1+y2+y3+y4+y5＝1，
其中，
0.4≤y1≤0.99(例如，0.4≤y1≤0.8)，0≤y2≤0.45(例如，0.1≤y2≤0.45)，0≤y3≤0.2(例如，0≤y3≤0.2)，0≤y4≤0.05(例如，0≤y4≤0.05)，0.01≤y5≤0.1(例如，0.01≤y5≤0.05)，3≤x1≤5.45(例如，3≤x1≤4.9)，0≤x2≤1.5(例如，0.1≤x2≤1)，0≤x3≤0.8(例如，0.1≤x3≤0.6)，0≤x4≤0.8(例如，0.1≤x4≤0.6)，0≤x5≤0.75(例如，0.05≤x5≤0.5)，0≤x6≤0.2；(例如，0≤x6≤0.15)。
所述的锆钛系AB 2型储氢合金的的分子表达式为AB 2，其中
A＝Mg x1Ca x2Ti x3Zr x4Y x5La x6，x1+x2+x3+x4+x5+x6＝0.9-1.1，
B＝V y1Cr y2Mn y3Fe y4Co y5Ni y6Cu y7，y1+y2+y3+y4+y5+y6+y7＝1.9-2.1，
0≤x1≤0.54(例如，0.01≤x1≤0.3，0.01≤x1≤0.1)，0≤x2≤0.54(例如，0≤x2≤0.25)，0.5≤x3≤1.04(例如，0.6≤x3≤1)，0.05≤x4≤0.58(例如，0.1≤x4≤0.58)，0.01≤x5≤0.2(例如，0.01≤x5≤0.05)，0≤x6≤0.2(例如，0≤x6≤0.05)，0.05≤y1≤1.95(例如，0.05≤y1≤1.8)，0≤y2≤1.9(例如，0≤y2≤1.85)，0.05≤y3≤1.95(例如，0.1≤y3≤1.95)，0≤y4≤1.6(例如，0≤y4≤1.5)，0≤y5≤0.5(例如，0≤y5≤0.3)，0.1≤y6≤0.5(例如，0.1≤y6≤0.3)，0≤y7≤0.5(例如，0.1≤y7≤0.2)，优选地，0.7≤x3：(x3+x4)≤0.95；优选地，1.7≤y1+y2+y3+y4≤2。
所述的钛系AB型储氢合金的分子表达式为AB，其中
A＝Ti x1Zr x2Y x3La x4，x1+x2+x3+x4＝0.85-1.1，
B＝V y1Cr y2Mn y3Fe y4Co y5Ni y6Cu y7，y1+y2+y3+y4+y5+y6+y7＝0.95-1.05，
0≤x1≤1.09(例如，0.9≤x1≤1.05)，0≤x2≤1.09(例如，0≤x2≤0.5)，0.01≤x3≤0.2(例如，0.01≤x3≤0.05)，0≤x4≤0.2(例如，0≤x4≤0.05)，0.05≤y1≤0.5(例如，0.05≤y1≤0.2)，0≤y2≤0.8(例如，0≤y2≤0.2)，0≤y3≤0.8(例如，0.05≤y3≤0.4，或0.1≤y3≤0.4)，0.2≤y4≤1(例如，0.5≤y4≤0.9)，0≤y5≤0.35(例如，0≤y5≤0.1)，0≤y6≤0.45(例如，0≤y6≤0.2)，0≤y7≤0.3(例如，0≤y7≤0.2)，优选地，x1和x2不同时为零；
所述的镁系A 2B型储氢合金的分子表达式为A 2B，其中
A＝Mg x1Ca x2Ti x3La x4Y x5，x1+x2+x3+x4+x5＝1.9-2.1，
B＝Cr y1Fe y2Co y3Ni y4Cu y5Mo y6；y1+y2+y3+y4+y5+y6＝0.9-1.1；
其中，1.29≤x1≤2.09(例如，1.7≤x1≤2.05)，0≤x2≤0.5(例如，0≤x2≤0.2)，0≤x3≤0.8(例如，0≤x3≤0.5)，0≤x4≤0.5(例如，0≤x4≤0.2)，0.01≤x5≤0.2(例如，0.05≤x5≤0.1)，0≤y1≤0.3(例如，0≤y1≤0.2，0.05≤y1≤0.2)，0≤y2≤0.2(例如，0≤y2≤0.1)，0≤y3≤0.6(例如，0≤y3≤0.5)，0.2≤y4≤1.1(例如，0.7≤y4≤1.05)，0≤y5≤0.5(例如，0≤y5≤0.4)，0≤y6≤0.15(例如，0≤y6≤0.1)；
所述的钒基固溶体型储氢合金的分子表达式为A x1B x2，其中x1+x2＝1，
其中A＝Ti y1V y2Zr y3Nb y4Y y5La y6Ca y7，y1+y2+y3+y4+y5+y6+y7＝1，
B＝Mn z1Fe z2Co z3Ni z4，z1+z2+z3+z4＝1，
0.7≤x1≤0.95(例如，0.8≤x1≤0.95，0.9≤x1≤0.95)，0.05≤x2≤0.3(例如，0.05≤x2≤0.2，0.05≤x2≤0.1)，0.4≤y1≤0.9(例如，0.45≤y1≤0.9，0.5≤y1≤0.8)，0≤y2≤0.5(例如，0≤y2≤0.4)，0≤y3≤0.5(例如，0≤y3≤0.4)，0≤y4≤0.55(例如，0≤y4≤0.4)，0≤y5≤0.2(例如，0.01≤y5≤0.2，0.05≤y5≤0.2)，0≤y6≤0.1(例如，0≤y6≤0.05)，0≤y7≤0.1(例如，0≤y7≤0.05)，0≤z1≤1(例如，0.1≤z1≤1，0.2≤z1≤0.95)，0≤z2≤0.95(例如，0≤z2≤0.9)，0≤z3≤0.3(例如，0≤z3≤0.2)，0≤z4≤0.45(例如，0.05≤z4≤0.45，0.05≤z4≤0.3)，0.55≤z1+z2≤1(例如，0.7≤z1+z2≤1)。
在一种实施方案中，本发明的储氢合金选自：
La 0.61Ce 0.16Pr 0.04Nd 0.19 Ni 3.55Co 0.75Mn 0.4Al 0.3，(Ti 0.8V 0.2) 0.95(Fe 1) 0.05，(Ti 0.8Y 0.2) 0.95(Mn 0.95Ni 0.05) 0.05，(Ti 0.4V 0.4Y 0.2) 0.9(Fe 0.05Mn 0.95) 0.1，(Ti 0.4V 0.4Y 0.2) 0.9(Fe 0.05Mn 0.9Ni 0.05) 0.1，(Ti 0.7Nb 0.1Y 0.2) 0.9(Mn 1) 0.1，(Ti 0.7Nb 0.1Y 0.2) 0.9(Mn 0.7Ni 0.3) 0.1，(Ti 0.4Zr 0.4Y 0.2) 0.93(Fe 0.2Mn 0.7Co 0.1) 0.07，(Ti 0.4Zr 0.4Y 0.2) 0.93(Fe 0.2Mn 0.7Ni 0.1) 0.07，(Ti 0.4V 0.4Zr 0.2) 0.95(Fe 0.6Mn 0.2Co 0.1Ni 0.1) 0.05，(Ti 0.4V 0.35Zr 0.2Y 0.05) 0.95(Fe 0.6Mn 0.2Co 0.1Ni 0.1) 0.05，(Ti 0.88Y 0.1Ca 0.02) 0.95(Fe 0.3Mn 0.6Co 0.1) 0.05，(Ti 0.88Y 0.1Ca 0.02) 0.95(Fe 0.3Mn 0.6Ni 0.1) 0.05，(Ti 0.7Nb 0.1Y 0.2) 0.8(Mn 0.7Ni 0.3) 0.2，Ti 0.64Zr 0.45Y 0.01VMn 0.9Ni 0.1，Mg 0.01Ti 0.93Zr 0.15Y 0.01VMn 0.9Ni 0.1，Ti 0.55Zr 0.48Y 0.05La 0.02V 0.33Cr 0.05Mn 1.5Fe 0.09Ni 0.1，Ti 0.85Zr 0.18Y 0.05La 0.02V 0.23Cr 0.05Mn 1.5Fe 0.09Ni 0.1Cu 0.1，Ti 0.6Zr 0.4Y 0.05V 0.1Mn 1.8Ni 0.2，Mg 0.1Ti 0.7Zr 0.2Y 0.05V 0.1Mn 1.6Ni 0.2Cu 0.2，Ca 0.01Ti 0.9Zr 0.05Y 0.05V 1.2Mn 0.6Ni 0.3，Ca 0.01Ti 0.85Zr 0.05Y 0.05V 1.2Mn 0.6Ni 0.1Cu 0.2，TiZr 0.05Y 0.05V 0.1Cr 1.4Mn 0.2Co 0.1Ni 0.3，Mg 0.1Ti 0.8Zr 0.15Y 0.05V 0.1Cr 1.4Mn 0.2Co 0.1Ni 0.1Cu 0.2，Ti 0.5Zr 0.55Y 0.05V 1.79Mn 0.1Fe 0.01Ni 0.2，Ti 0.8Zr 0.25Y 0.05V 1.79Mn 0.1Fe 0.01Ni 0.1Cu 0.1，Mg 0.01Ti 0.63Zr 0.45Y 0.01VMn 0.9Ni 0.1，Mg 1.8Y 0.1Ni 1，Mg 1.8Y 0.1Cr 0.05Ni 1，Mg 1.5Ti 0.5Y 0.05Ni 1.1，Mg 1.5Ti 0.5Y 0.05Cr 0.1Ni 1，Mg 2Y 0.1Ni 0.6Cu 0.4，Mg 2Y 0.1Cr 0.05Ni 0.6Cu 0.4，Mg 1.92Y 0.08Ni 0.95Fe 0.05，Mg 1.92Y 0.08Cr 0.2Ni 0.75Fe 0.05，Mg 1.9Y 0.1Fe 0.1Ni 0.8Cu 0.1，Mg 1.9Y 0.1Cr 0.1Fe 0.1Ni 0.7Cu 0.1，Mg 1.9Y 0.1Ni 0.8Co 0.2， Mg 1.9Y 0.1Cr 0.1Ni 0.8Co 0.2，Mg 1.8Y 0.1La 0.1Ni 0.9Co 0.1，Mg 1.8Y 0.1La 0.1Cr 0.05Ni 0.9Co 0.1，Mg 1.7Ti 0.2Y 0.1Ni 0.7Co 0.32，Mg 1.7Ti 0.2Y 0.1Cr 0.05Ni 0.7Co 0.3，TiY 0.01V 0.1Fe 0.7Ni 0.2，TiY 0.01V 0.1Fe 0.7Mn 0.1Ni 0.1，TiY 0.02V 0.2Fe 0.8，TiY 0.02V 0.2Fe 0.7Mn 0.1，Ti 0.97Y 0.03V 0.05Cr 0.03Fe 0.9，Ti 0.97Y 0.03V 0.05Cr 0.03Fe 0.5Mn 0.4，Ti 0.9Y 0.04V 0.15Fe 0.9，Ti 0.9Y 0.04V 0.05Fe 0.9Mn 0.1，Ti 0.91Zr 0.05Y 0.04V 0.1Cr 0.2Fe 0.7，Ti 0.91Zr 0.05Y 0.04V 0.1Cr 0.2Fe 0.6Mn 0.1，Ti 0.95Y 0.05V 0.26Fe 0.7Cu 0.05，Ti 0.95Y 0.05V 0.05Fe 0.7Mn 0.21Cu 0.05，Ti 1.02Y 0.03V 0.05Fe 0.9Ni 0.1，Ti 1.02Y 0.03V 0.05Fe 0.8Mn 0.1Ni 0.1，La 0.5Ce 0.32Nd 0.15Pr 0.02Y 0.01Ni 4.4Fe 0.55Al 0.05，La 0.5Ce 0.32Nd 0.15Pr 0.02Y 0.01Ni 4.4Fe 0.6，La 0.8Ce 0.15Y 0.05Ni 4Mn 0.5Al 0.5，La 0.8Ce 0.15Y 0.05Ni 4.5Mn 0.5，La 0.45Ce 0.4Nd 0.1Pr 0.03Y 0.02Ni 4Co 0.8Al 0.2，La 0.45Ce 0.4Nd 0.1Pr 0.03Y 0.02Ni 4.2Co 0.8，La 0.75Ce 0.15Nd 0.05Pr 0.02Y 0.03Ni 4.7Al 0.1Fe 0.2，La 0.75Ce 0.15Nd 0.05Pr 0.02Y 0.03Ni 4.8Fe 0.2，La 0.8Ce 0.15Nd 0.03Y 0.02Ni 4.5Co 0.3Mn 0.1Al 0.1，La 0.8Ce 0.15Nd 0.03Y 0.02Ni 4.5Co 0.4Mn 0.1，La 0.97Y 0.03Ni 4Co 1。
在一种优选的实施方案中，本发明的储氢合金选自：
(Ti 0.8Y 0.2) 0.95(Mn 0.95Ni 0.05) 0.05，(Ti 0.4V 0.4Y 0.2) 0.9(Fe 0.05Mn 0.9Ni 0.05) 0.1，(Ti 0.7Nb 0.1Y 0.2) 0.9(Mn 0.7Ni 0.3) 0.1，(Ti 0.4Zr 0.4Y 0.2) 0.93(Fe 0.2Mn 0.7Ni 0.1) 0.07，(Ti 0.4V 0.35Zr 0.2Y 0.05) 0.95(Fe 0.6Mn 0.2Co 0.1Ni 0.1) 0.05，(Ti 0.88Y 0.1Ca 0.02) 0.95(Fe 0.3Mn 0.6Ni 0.1) 0.05，Mg 0.01Ti 0.93Zr 0.15Y 0.01VMn 0.9Ni 0.1，Ti 0.85Zr 0.18Y 0.05La 0.02V 0.23Cr 0.05Mn 1.5Fe 0.09Ni 0.1Cu 0.1，Mg 0.1Ti 0.7Zr 0.2Y 0.05V 0.1Mn 1.6Ni 0.2Cu 0.2，Ca 0.01Ti 0.85Zr 0.05Y 0.05V 1.2Mn 0.6Ni 0.1Cu 0.2，Mg 0.1Ti 0.8Zr 0.15Y 0.05V 0.1Cr 1.4Mn 0.2Co 0.1Ni 0.1Cu 0.2，Ti 0.8Zr 0.25Y 0.05V 1.79Mn 0.1Fe 0.01Ni 0.1Cu 0.1，Mg 1.8Y 0.1Cr 0.05Ni 1，Mg 1.5Ti 0.5Y 0.05Cr 0.1Ni 1，Mg 2Y 0.1Cr 0.05Ni 0.6Cu 0.4，Mg 1.92Y 0.08Cr 0.2Ni 0.75Fe 0.05，Mg 1.9Y 0.1Cr 0.1Fe 0.1Ni 0.7Cu 0.1，Mg 1.9Y 0.1Cr 0.1Ni 0.8Co 0.2，Mg 1.8Y 0.1La 0.1Cr 0.05Ni 0.9Co 0.1，Mg 1.7Ti 0.2Y 0.1Cr 0.05Ni 0.7Co 0.3，TiY 0.01V 0.1Fe 0.7Mn 0.1Ni 0.1，TiY 0.02V 0.2Fe 0.7Mn 0.1，Ti 0.97Y 0.03V 0.05Cr 0.03Fe 0.5Mn 0.4，Ti 0.9Y 0.04V 0.05Fe 0.9Mn 0.1，Ti 0.91Zr 0.05Y 0.04V 0.1Cr 0.2Fe 0.6Mn 0.1，Ti 0.95Y 0.05V 0.05Fe 0.7Mn 0.21Cu 0.05，Ti 1.02Y 0.03V 0.05Fe 0.8Mn 0.1Ni 0.1，La 0.5Ce 0.32Nd 0.15Pr 0.02Y 0.01Ni 4.4Fe 0.55Al 0.05，La 0.8Ce 0.15Y 0.05Ni 4Mn 0.5Al 0.5，La 0.45Ce 0.4Nd 0.1Pr 0.03Y 0.02Ni 4Co 0.8Al 0.2，La 0.75Ce 0.15Nd 0.05Pr 0.02Y 0.03Ni 4.7Al 0.1Fe 0.2，La 0.8Ce 0.15Nd 0.03Y 0.02Ni 4.5Co 0.3Mn 0.1Al 0.1。
在本发明的一个方面中，本发明提供了一种本发明的储氢合金的制备方法，其中所述的方法包括以下步骤：(1)以达到储氢合金组成的方式称量各储氢合金原料进行混合；(2)将步骤(1)混合得到的物质进行熔炼，然后进行退火；其中，所述熔炼为电炉熔炼或者感应熔炼；优选地，所述熔炼的条件包括：在真空或者惰性气氛下进行，温度为1200-3000℃，优选为1800-2200℃；更优选地，在 真空下进行，所述熔炼的压力为1×10 -5-1×10 -3帕(绝对压力)，优选为0.5×10 -4-5×10 -4帕(绝对压力)；更优选地，在惰性气氛下进行，所述熔炼的压力为0.5-1巴(例如0.6-1巴，0.7-1巴)(表压)；所述退火的条件包括：在真空或者惰性气氛(如氩气气氛)下进行，温度为500-900℃(例如700-1000℃)，时间为12-360小时；任选地，该方法还包括将步骤(2)退火得到的物质降温后进行破碎处理以得到10-400目(例如20-400目)的产品；并且任选地，该方法还包括将步骤(2)退火得到的物质进行活化处理，优选地，所述活化处理的条件包括：在真空下，温度为50-300℃，时间为1-10小时。
在本发明的一个方面中，本发明提供了一种提供高纯度氢气的方法，该方法包括：(1)使有机液体储氢原料与脱氢催化剂接触反应，得到含有氢气的脱氢反应产物；(2)将脱氢反应产物冷却，得到液体产物和富氢气体产物，收集液体产物；(3)使富氢气体与储氢合金接触，得到含氢合金，收集未吸附的气体；(3a)任选地，除去含氢合金储存容器中的有机物；(4)加热含氢合金，释放氢气。
根据本发明的提供高纯度氢气的方法，使用本发明的用于有机物脱氢制氢气的催化剂和/或本发明的储氢合金。
根据本发明的提供高纯度氢气的方法，在(1)中：有机液体储氢原料与脱氢催化剂接触反应的反应温度为150-450℃(例如，200-400℃，300-350℃)；有机液体储氢原料与脱氢催化剂接触反应的重时空速0.5-50小时 -1(例如，1-45小时 -1，2-30小时 -1)；有机液体储氢原料与脱氢催化剂接触反应的压力为0.03-5MPa(表压)(例如0.3-5MPa，0.1-3MPa，0.5-2MPa或0.2-1.6MPa)；任选地，使有机液体储氢原料与氢气混合后与脱氢催化剂接触，氢烃比(氢气与有机液体储氢原料的摩尔比)为0-10(例如0-8)。引入氢气有利于减少脱氢反应的焦炭生成。
根据本发明的提供高纯度氢气的方法，在(2)中，将脱氢反应产物冷却的冷却温度低于液体产物中的有机物的沸点温度；优选的，低于其中的常温常压下为液态的沸点最低的有机物的沸点温度。
根据本发明的提供高纯度氢气的方法，在(3)中，所述的富氢气体为富氢气体产物或富氢气体产物经过进一步分离得到的含氢气的气体，所述的进一步分离的方法包括变温分离，膜分离，变压吸附分离或它们的组合；所述的富氢气体中氢气的质量分数为≥80％(例如80-99％，优选为≥85％，更优选为≥90％)。通过冷却分离为一定氢气含量的富氢气体再进行储氢合金吸收，可以充分利用储氢合金吸收能力，改善储氢合金的吸收的效果。
根据本发明的提供高纯度氢气的方法，在(3)中，所述的富氢气体与储氢合金的接触在一个或多个储氢合金储存容器中进行；所述的储氢合金可以是一种 或者多种，多种储氢合金可以混合使用，也可以串联使用或并联使用或串并联混合使用；所述的富氢气体与储氢合金接触的压力为0.001-5MPa(例如，0.01-5MPa，0.03-4MPa，0.05-5MPa，0.08-2MPa，0.05-3MPa，0.1-1MPa)，当储氢合金储存容器为多个，且存在储氢容器串联的情况，按照富氢气体物流方向，最后接触储氢合金的接触压力(也称为吸氢压力)为0.05-5MPa(例如0.1-1MPa)；所述的富氢气体与储氢合金接触的温度(也称为吸氢温度)为-70至100℃(例如，-50至90℃，-30至80℃)；与储氢合金接触时，所述的富氢气体的温度低于有机液体储氢原料在常压下的沸点温度。
根据本发明的提供高纯度氢气的方法，在(3)中，所述的储氢合金储存容器为一个或多个，其中按照接触氢气的顺序，最后与氢气接触的储氢合金储存容器中的储氢合金为具有高平衡压力的储氢合金，所述的具有高平衡压力的储氢合金为在温度为150-450℃之间至少存在一个温度点，氢气吸收的平衡压力大于等于35MPa；优选的，至少一个储氢合金储存容器中的储氢合金为具有高平衡压力的储氢合金。通过具有高平衡压力的储氢合金可以获得高纯高压氢气，所得到的高纯高压氢气可以直接用于氢燃料电池车加注。
根据本发明的提供高纯度氢气的方法，进行步骤(3a)，其中除去含氢合金储存容器中的有机物采用吹扫的方法。例如使用氢气吹扫，其方法例如：储氢合金达到预定的吸附量以后，停止向储氢合金供应富氢气体，使氢气通过含氢合金，将含氢合金和含氢合金储存容器(也称储氢合金储存容器)中的有机气体带出，引入储罐储存或者使用其它储氢合金储存容器中的储氢合金吸收；其中优选的，吹扫用氢气的纯度大于90重量％，更优选大于95重量％，例如大于99重量％。
根据本发明的提供高纯度氢气的方法，在(4)中：储氢合金释放的氢气的温度(即，加热储氢合金的温度，简称放氢温度)为150-450℃，释放的氢气的压力为≥35MPa(例如为35-100MPa)以得到高纯高压氢气，或者释放的氢气的分压为0.1-5MPa以得到高纯氢气，其中放氢温度高于吸氢温度。
根据本发明的提供高纯度氢气的方法，还包括使含氢合金释放氢气，释放的氢气与不同的储氢合金接触形成含氢合金，该过程重复一次或多次，其中至少最后一次的重复过程所用的储氢合金为具有高平衡压力的储氢合金。
根据本发明的提供高纯度氢气的方法，所述的储氢合金为第一储氢合金与第二储氢合金联用；第一储氢合金为本发明所述的镁系A 2B型储氢合金，用于富氢气体接触，第二储氢合金用于将第一储氢氢气增压，第二储氢合金为具有高平衡压力的储氢合金，第二储氢合金为本发明所述的稀土系AB 5型，锆钛系AB 2型，钛系AB型储氢合金中的一种或者多种；富氢气体先经过第一储氢合金，进行杂 质分离；然后使第一储氢合金释放出的高纯氢气与第二储氢合金进行接触，然后使第二储氢合金在高压下释放氢气；第一储氢合金放氢温度高于第二储氢合金吸氢温度，温差优选≥100℃(例如350℃≥温差≥150℃)；第一储氢合金和第二储氢合金在不同的储氢合金储存罐中，且第一储氢合金储存罐和第二储氢合金储存罐中间有换热系统；富氢气体与第一储氢合金接触的吸氢温度为20-150℃(例如50-100℃)，氢气分压为0.001-0.1MPa(0.001-0.03MPa)；第一储氢合金释放氢气的温度(放氢温度)为150-450℃(例如200-350℃)，放氢的氢气分压为0.1-5MPa(例如0.1-1MPa)；第二储氢合金吸收氢气的吸氢温度为-70至100℃(例如-30至100℃)，吸氢的氢气分压为0.1-5MPa(例如0.1-1MPa)，第二储氢合金放氢温度为150-450℃(例如200-350℃)，放氢的氢气分压为≥35MPa(例如35-100MPa)。
根据本发明的提供高纯度氢气的方法，所述的有机液体储氢原料为分子中含有环的有机化合物，其任选地含有杂原子，所述的杂原子可以处于环上；例如，含有环烷烃环的饱和或不饱和烃，如不含杂环原子的含有环烷烃环的饱和或不饱和烃，更具体地，芳环和环烷烃的环总数小于等于2的不含杂环原子的含有环烷烃环的饱和或不饱和烃，例如，环己烷，甲基环己烷，十氢萘，双环己烷；以及含杂原子的含有环烷烃环的饱和或不饱和烃，例如，含氮杂环化合物，以及含氮/硼杂环化合物，所述的含氮杂环化合物包括十氢咔唑，十二氢乙基咔唑，二氢吲哚，4-氨基哌啶，哌啶-4-羧胺，全氢-4，7-菲洛林，2-甲基-1，2，3，4-四氢喹啉，2，6-二甲基十氢-1，5-萘啶中的一种或者几种；所述的含氮/硼杂环化合物包括：1，2-硼杂氮杂-环己烷，3-甲基-1，2-硼杂氮杂-环戊烷中的一种或者多种。
根据本发明的提供高纯度氢气的方法，还包括将释放的氢气引入到氢气储罐以储存氢气；或者所得到的高纯高压氢气可以直接用于氢燃料电池车加注。
在本发明的一个方面中，本发明提供了一种高效分布式制高纯高压氢气的方法，该方法包括：在脱氢反应器中，将液体有机储氢原料在脱氢催化剂的存在下进行脱氢反应得到包括氢气的脱氢反应产物；在冷却分离装置中，将脱氢反应产物冷却并分离，得到富氢物流和有机液体；在储氢合金储存容器中，使富氢物流或提纯后的富氢物流与储氢合金接触，得到含氢合金；氢气吹扫除去储氢合金储存容器中的有机物；其中，吹扫氢气的纯度优选大于90重量％(例如大于95重量％，大于99重量％)；将含氢合金加热释放氢气，得到高压氢气和将得到的高压氢气提供给用氢装置或高压氢气储存罐储存，例如得到的高压氢气可以直接用于氢燃料电池车加注。
在本发明的一个方面中，本发明提供了一种提供高纯高压氢气的系统，包括：有机液体储氢原料储存和供应装置，用于储存有机液体储氢原料和向脱氢反应器 提供有机液体储氢原料；脱氢后液体储存装置，用于储存有机液体储氢原料脱氢后得到的液体产物；脱氢反应器装置，用于将有机液体储氢原料在脱氢催化剂的作用下进行脱氢反应得到包括氢气的脱氢反应产物；冷却分离装置，用于将脱氢反应产物分离得到富氢气体产物和液体产物；储氢-供氢装置，其包括储氢合金储存容器，储氢合金加热系统，用于将富氢气体与储氢合金在低温低压下接触吸氢，吸附饱和后加热脱氢；任选的吹扫装置用于除去储氢容器中的有机物；氢气供应装置，将高压氢气提供给用氢装置或氢气储存罐；优选地，所述的系统设置集成建造在集装箱内，作为集装箱式制氢系统置于加氢站使用，或直接建造在加氢站使用；优选地，所述的储氢-供氢装置包括一个或多个储氢合金储存容器，多个储氢合金储存容器可以并联或串联或者并联和串联混合联接；优选地，至少一个所述的储氢合金储存容器为耐高压容器和/或所述的氢气供应装置为耐高压的装置，例如其耐受压力为35MPa以上。
如图3所示，本发明提供了一种提供高纯高压氢气的系统，其中：1为有机液体存储罐，2为原料泵，3为换热器，4为脱氢反应器，5为换热器，6为储氢罐，7为单向阀，8为能量传递体系统，9为吹扫系统，10为储氢控制系统，图3中所述的有机液体原料储存系统包括有机液体存储罐(1)和与有机液体脱氢反应器相连的原料泵(2)，所述的有机液体存储罐设置有有机液体原料入口和有机液体原料出口；所述的有机液体脱氢反应系统包括有机液体换热器(3)与脱氢反应器(4)，所述的有机液体换热器连接有机液体脱氢反应器出口和入口，用于反应器出口气体降温和原料预热；所述的反应器出口气体可以经过进一步换热降温(5)，降温后分离得到富氢物料，富氢物流可经过或者不经过膜分离装置和变压吸附装置之中一种或者几种；所述的提纯增压系统包括一组或者多组储氢罐(6)，且每组储氢罐与一组防止回流装置(7)连接储氢罐以并联方式连接到至少一条供氢管线上，至少包括一个能量递送系统(8)，用于向每个储氢罐中提供能量以便从固体储氢材料中解析氢气，至少包括一组真空泵(9)和吹扫系统，用于储氢罐中杂质气体的脱除，储氢罐出入口各与一个流量计连接，包括一个控制系统(10)，根据脱氢反应产氢量，控制整个每个储氢罐吸氢和放氢时间以及能量递送系统的启动时间。用储氢罐入口流量计计算储氢合金吸氢总量，当单个储氢罐储氢合金储氢量达到饱和吸氢总量80％以上时，关闭储氢罐富氢物流进气阀；吹扫系统开启，除去储氢罐中杂质，待吹扫管线中氢气纯度达到99％以上时，关闭吹扫系统；储氢罐同时吸氢总量应高于氢气产生速度的120％，储氢合金通过放氢阀连接到至少一条供氢管线上，供氢管线输送氢气到氢气存储装置，供氢管线上储氢合金放氢阀不能同时关闭和开启。
在本发明的一个方面中，本发明提供了一种移动式供氢系统，包括运输车辆和设置在运输车辆上的根据本发明的提供高纯高压氢气的系统。
在本发明的一个方面中，本发明提供了一种分布式供氢装置，包括根据本发明的提供高纯高压氢气的系统，并且任选地包括高压氢气贮存罐。
本发明提供的制备高纯度氢气的方法，可以高效地提供高纯度氢气，在使用具有高平衡压力的储氢合金的情况下可以提供高纯高压氢气。此外，本发明还可以具有以下有益技术效果中的至少一项，优选情况下具有其中的多项有益技术效果：
(1)本发明方法可以具有较高的有机液体储氢化合物脱氢效率。
(2)可以具有更高的有机液体储氢化合物脱氢转化率。
(3)可以具有更高的有机液体储氢化合物脱氢选择性。
(4)具有更高的储氢金属吸氢效率。
(5)在存在有机物的情况下储氢金属具有较好吸氢效率。
(6)通过有机物脱氢，冷却分离和储氢合金吸氢的耦合，可以取得提高有机物脱氢转化率的效果。
(7)有机原料脱氢和储氢合金吸氢可以更加高效的配合。
本发明提供的有机物脱氢制氢气的脱氢催化剂具有较高的脱氢活性、氢气选择性和/或氢气生成速率的优点。
本发明提供的有机物脱氢制氢气的脱氢催化剂，可以用非贵金属代替部分贵金属，可以减少贵金属的用量，并且保持较高的脱氢活性、氢气选择性和/或氢气生成速率。
本发明提供的催化剂可用于有机储氢化合物脱氢制备氢气，尤其是用于含有环例如含环烷烃环或含杂原子环的有机物脱氢制备氢气，具有较高的转化率，选择性和/或氢气生成速率。
根据本发明，所述的晶相改性金属氧化物百分含量可采用如下的方法测量：用X-射线衍射和相位滤波经修正的Rietveld模型，采用拟合的方法计算得到晶相改性金属氧化物的重量百分含量；相位滤波参见R.V.Siriwardane，J.A.Poston，G.Evans，Jr.Ind.Eng.Chem.Res.33(1994)，2810-2818，经修正的Rietveld模型见RIQAS rietveld Analysis，操作手册，Material Data，Inc.，Berkley，CA(1999)。
根据本发明，所述的改性金属氧化物的化学组成百分含量为所述的载体组合物中改性金属氧化物的总含量，改性金属氧化物的化学组成百分含量可采用X射线荧光法测定或化学分析的方法测定。
根据本发明，所述的载体组合物表面上改性金属氧化物的重量百分含量通过XPS方法测量，测量的表面层厚度为从外表面至距离外表面5nm厚度的范围内。
另外，本发明还提供了下述方案：
1.一种用于有机物脱氢制氢气催化剂的载体组合物，该载体组合物包括氧化铝和改性金属氧化物，所述的改性金属氧化物为钛氧化物和/或锆氧化物，其中所述的改性金属氧化物的η＜0.3，其中η＝载体组合物中晶相改性金属氧化物的重量百分含量/载体组合物中改性金属氧化物的化学组成重量百分含量，钛氧化物以TiO2计，锆氧化物以ZrO2计。
2.根据方案1所述的载体组合物，其特征在于，η＝0，优选的，所述的第一金属氧化物单层分散于氧化铝基质上。
3.根据方案1所述的载体组合物，其特征在于，所述载体组合物中氧化铝质量份数为80～98.5％，优选的为83～97.5％或85～95％或为90～95％；改性金属氧化物的质量份数为1.5～20％，优选为2.5～17％或5～15％，或为5～10％。
4.根据方案3所述的载体组合物，其特征在于，所述的改性金属氧化物包括钛氧化物，其中优选的，所述的载体组合物中，二氧化钛质量份数优选为2～20％例如5～15％或5～10％或2.5～17％，二氧化锆质量分数优选0～8％例如0-6％或0-3％或1～6％。
5.根据方案4所述的载体组合物，其特征在于，相对于TiO2纯物相，所述的载体组合物XPS谱图中，Ti 2P3/2轨道电子结合能存在偏移，结合能为458.8eV处的峰向高结合能偏移0.6-0.7eV至459.4-459.5eV，和/或Ti 2P1/2轨道电子结合能为464.5eV处的峰向高结合能方向偏移0.8-0.9eV至465.3～465.4eV。
6.根据方案1所述的载体组合物，其特征在于，所述的氧化物基质具有γ氧化物、η-氧化铝、ρ氧化铝或χ氧化铝至少一种的物相结构。
7.根据方案1所述的载体组合物，其特征在于，所述的载体组合物比表面积为100～350m2/g。
8.根据方案1所述的载体组合物，其特征在于，所述载体组合物的孔体积为0.3～1.3ml/g。
9.一种载体组合物的制备方法，包括如下步骤：
(1)将氧化铝基质与气体携带的改性金属氧化物前驱体气流接触，待四氯化钛达到预设负载量时，停止通入气体携带的改性金属氧化物前驱体气流，得到负载改性金属氧化物前躯体的氧化铝基质，所述的改性金属氧化物前驱体为氧化钛前躯体和/或氧化锆前躯体；
(2)使负载改性金属氧化物前躯体的氧化铝基质水解，焙烧，得到载体组合物。
10.根据方案9所述的载体组合物制备方法，其特征在于，所述氧化钛前躯体选自于四氯化钛、钛酸乙酯、钛酸异丙酯、醋酸钛的一种或者多种，优选四氯化钛；所述氧化锆前躯体选自四氯化锆、乙醇锆、甲醇锆、异丙醇锆、锆酸四丁酯中的一种或多种，优选四氯化锆和/或甲醇锆。
11.根据方案9所述的载体组合物制备方法，其特征在于，所述的氧化铝基质是γ-氧化铝、η-氧化铝、ρ氧化铝 χ氧化铝中的一种或多种。
12.根据方案9所述的载体组合物制备方法，其特征在于，所述氧化铝基质的比表面积100～350m2/g。其中，优选的，所得到的载体组合物比表面积相比
氧化铝基质比表面积，减少的比例≤10％。
13.根据方案9所述的载体组合物制备方法，其特征在于，所述氧化铝基质的孔体积为0.3～1.3ml/g。
14.根据方案9所述的载体组合物制备方法，其特征在于，所述的气体为无水的惰性气体，所述的无水的惰性气体中的水含量不超过10ppm。优选的，所述气体携带的改性金属氧化物前驱体气流中改性金属氧化物前驱体的含量为0.1～3g/L，其中改性金属氧化物前驱体含量以金属氧化物计。
15.根据方案9所述的载体组合物制备方法，其特征在于，步骤(1)中，所述气体的温度为室温～350℃，例如为室温～300℃或15～300℃。
16.根据方案9所述的载体组合物制备方法，其特征在于，步骤(1)中接触的压力为0.05～5atm例如1～3atm。
17.根据方案9所述的载体组合物制备方法，其特征在于，所述气体每分钟的体积流量与氧化铝基质体积的比值为3～80∶1例如为5～30∶1优选10～25∶1；其中气体的体积以标准状况下的体积计，氧化铝基质的体积以堆积体积计。
18.根据方案9所述的载体组合物制备方法，其特征在于，所述的氧化铝基质在流化态下与气体携带的改性金属氧化物前驱体气流接触，或是在搅拌下与所述气流接触；流化态例如可以是鼓泡床、湍动床、快速床或输送床。
19.根据方案9所述的载体组合物制备方法，其特征在于，步骤(2)所述水解，方法如下：使所述负载改性金属氧化物前躯体的氧化铝基质与含水蒸气的气体接触。一种实施方式，所述含水蒸气的气体与氧化铝基质接触的比值(标准状态下含水蒸气的气体与氧化铝基质堆积体积之比)为3～80∶1例如5～30∶1，优选10～25∶1，所述含水蒸气的气体中水蒸气占气体总体积的比例为0.1体 积％～100体积％，优选3体积％～100体积％，更优选的为10体积％～70体积％体积；水蒸汽以外的其它气体可以是惰性气体或空气。水解时间例如为1h～50h优选2h～30h。通常的水解时间大于等于负载时间(负载时间是指氧化铝基质与气体携带的改性金属氧化物前驱体气流接触的时间)。
20.根据方案9所述的载体组合物制备方法，其特征在于，所述焙烧，焙烧温度350℃～700℃，焙烧时间为0.5～12小时。
21.一种用于有机物脱氢制备氢气的催化剂，其特征在于，包括包含氧化铝和改性金属氧化物的载体以及活性金属组分，所述改性金属氧化物为钛氧化物和/或锆氧化物；所述的活性金属组分为活性金属的氧化物和/或活性金属的单质。所述活性金属例如第八副族金属、第七副族金属、第五副族金属、第六副族金属、第一副族金属、稀土元素、碱土金属、第四主族金属中的一种或多种；
优选的，所述的活性金属包括Pt和/或者Ni，包括或不包括含或者不含其它元素。优选的，所述的其它元素为V、Cr、Mn、Fe、Co、Ni、Cu、Ag、Ce、W、Mo、Sn、Ca、Pt、Pd、Ru、Re、Rh、Ir、Os、Zn、P、In中的一种或多种。优选的，所述的载体为方案1～8任一所述的载体组合物或方案9～20任一项所述方法制备的载体组合物。
22.一种有机物脱氢制备氢气的催化剂，包括载体和负载的活性金属组分，其特征在于，所述载体为方案1～8任一项所述的载体组合物或为方案9～20任一项所述方法制备的载体组合物，所述的活性金属包括Pt，含或者不含其它金属，所述的其它金属可以是贵金属也可以是非贵金属，所述其它金属为Pd、Ru、Re、Rh、Ir、Os、Sn、V、Mo、Cr、Mn、Fe、Co、Ni、Cu、Ag、Ce、W、Cu、Ca元素中的一种或多种。
23.根据方案22所述的催化剂，其特征在于，所述催化剂中，活性金属的含量为0.1-20重量％例如0.1～15重量％，载体的含量为85～99.9重量％，Pt的含量为0.1-10重量％。本发明催化剂组成中，活性金属的含量，贵金属以单质计，非贵金属以氧化物计。
24.根据方案22所述的催化剂，其特征在于，所述的其它金属为Pd、Ru、Re、Rh、Ir、Os中的一种或多种。
25.根据方案24所述的催化剂，其特征在于，所述催化剂中，所述活性金属的含量为0.1-10重量％，优选0.5～8重量％；所述载体的含量为90～99.9重量％，优选为92～99.5重量％。
26.根据方案25所述的催化剂，其特征在于，所述催化剂中，Pt含量为0.1～2重量％例如0.3～1.5重量％或0.5～1重量％，所述其它金属的含量为0～9.9重 量％例如0.1～2或0.2～1重量％或0.1～0.8重量％，所述载体的含量优选为90～99.9重量％例如96～99.6重量％或98～99.5重量％或98.5～99.3重量％。
27.根据方案22所述的催化剂，其特征在于，所述的其它金属为Sn、V、Mo、Cr、Mn、Fe、Co、Ni、Cu、Ag、Ce、W、Cu、Ca中的一种或多种。
28.根据方案27所述的催化剂，其特征在于，所述催化剂中，Pt含量为0.1～10重量％，所述其它金属的含量为0～15重量％。
29.根据方案28所述的催化剂，其特征在于，所述催化剂中，Pt含量为0.1～2重量％例如0.5～1.5重量％，其它金属的含量为0～15重量％例如1～10重量％或2～8重量％或3～7重量％；所述载体的含量优选为85～99.9重量％例如为90～99重量％或90～98重量％或92～97重量％。
30.一种有机物脱氢制备氢气的催化剂，包括载体和负载的活性金属组分，其特征在于，所述载体为方案1～8任一项所述的载体组合物或者按照方案9～20任一项所述方法制备的载体组合物，所述的活性金属包括镍，含或者不含其它金属，所述其它金属为Zn、Sn、Cu、Fe、Ag、P、In、Re、Mo、Co、Ca、W中的一种或者多种。
31.根据方案30所述的催化剂，其特征在于，所述催化剂中，所述活性金属质量分数为5％～30％，载体质量分数为70～95％；载体质量分数优选为75～90％，活性金属质量分数优选为10％～25％。
32.根据方案30所述的催化剂，其特征在于，所述催化剂中，镍的含量以氧化物计为5～25重量％，优选6～20重量％例如为7～15重量％或7～12重量％或8～11重量％，所述的其它金属的含量以氧化物计为0～15重量％优选0～10重量％例如为0.5～8重量％或1～5重量％。
33.方案21-32任一项所述催化剂的制备方法，包括：
(1)将活性金属组分前躯体溶解在水中，浸渍载体，得到浸渍活性金属组分前驱体的载体；
(2)浸渍活性金属组分前驱体的载体干燥、焙烧；
优选的，所述载体为方案1～8任一项所述的载体组合物或按照方案9～20任一项所述的方法制备的载体组合物。
34.根据方案33所述的催化剂制备方法，其特征在于，所述的活性金属包括非贵金属，步骤(2)为：将浸渍活性金属组分前驱体的载体于低于-40℃的环境中放置1h～24h；然后进行抽真空干燥，除去载体上吸附的水，然后焙烧，得到催化组合物。
35.根据方案33所述的催化剂制备方法，其特征在于，所述活性金属组分前躯体为：金属硝酸盐、金属氯化盐、乙酸盐、金属碳酸盐、金属醋酸络合物、金属氢氧化物、金属草酸盐络合物、高价金属酸盐中的一种或多种。
36.根据方案32所述的催化剂制备方法，其特征在于，步骤2所述焙烧：焙烧温度为400～700℃，焙烧时间优选0.5～12小时。
37.一种所述催化组合物的使用方法，包括：将有机储氢化合物与方案21～32任一项所述脱氢催化剂或者按照方案33～36任一项所述方法制备的脱氢催化剂接触进行脱氢反应生成氢气的步骤。
38.根据方案37所述的方法，其特征在于，脱氢反应温度为150～450℃，重时空速0.5～50h-1，反应压力0.3～5MPa，所述接触在临氢或者不临氢的条件下进行，氢油比(引入脱氢反应器的氢气和有机储氢化合物的摩尔比)为0～10。
39.根据方案37所述的方法，其特征在于，所述的有机储氢化合物为含环烷环的饱和或不饱和烃，例如，所述的有机储氢化合物为环己烷、甲基环己烷、十氢萘、双环己烷、十氢咔唑、十二氢乙基咔唑、二氢吲哚、4-氨基哌啶、哌啶-4-羧胺、全氢-4，7-菲洛林、2-甲基-1，2，3，4-四氢喹啉、2，6-二甲基十氢-1，5-萘啶、1，2-BN-环己烷、3-甲基-1，2-BN-环戊烷中的一种或者多种。
此外，本发明还进一步提供了下述方案：
1、一种提供高纯度氢气的方法，该方法包括：使有机液体储氢原料与脱氢催化剂接触反应，得到含有氢气的脱氢反应产物；
将脱氢反应产物冷却，得到液体产物和富氢气体产物，收集液体产物；
使富氢气体与储氢合金接触，得到含氢合金，收集未吸附的气体；
任选的，除去含氢合金储存容器中的有机物；
加热含氢合金，释放氢气，得到高纯氢气。
2、根据方案1所述的方法，其特征在于，所述的富氢气体为富氢气体产物或富氢气体产物经过进一步分离得到的含氢气的气体，所述进一步分离的方法例如：变温分离、膜分离、变压吸附分离或它们的组合。
3、根据方案1或2所述的方法，其特征在于，所述的富氢气体中氢气的质量分数大于等于80％例如80～99％，优选为≥85％，更优选为≥90％。
4、根据方案1所述的方法，其特征在于，所述富氢气体与储氢合金接触的温度为-70～100℃，优选-50～90℃更优选-30～80℃。
5、根据方案1所述的方法，其特征在于，脱氢反应产物冷却的温度低于有机物的沸点温度；优选的，低于其中的常温常压下为液态沸点最低的有机物的沸点温度。
6、根据方案1～5任一项所述的方法，其特征在于，与储氢合金接触时，所述富氢气体的温度低于有机液体储氢原料在常压下的沸点温度。
7、根据方案1所述的方法，其特征在于，所述的储氢合金可以是一种或者多种，多种储氢合金可以混合使用，也可以串联使用或并联使用或串并联混合使用；优选的所述的富氢气体与储氢合金接触压力为0.001～5Mpa例如为0.01～5Mpa或0.03～4Mpa或0.05～5Mpa或0.08～2Mpa或0.005～3Mpa或0.1～1Mpa。
8、根据方案1所述的方法，其特征在于，所述富氢气体与储氢合金接触在储氢合金储存容器中进行，储氢合金储存容器为一个或者多个；所述的富氢气体与储氢合金为接触压力为0.05～5Mpa优选0.1～1Mpa；
当储氢合金储存容器为多个，且存在储氢容器串联的情况，优选情况下，其中按照富氢气体物流方向，最后接触的储氢合金的接触压力为0.05～5Mpa优选0.1～1MPa。
9、根据方案1所述的方法，其特征在于，所述的储氢合金储存容器为一个或多个，其中按照接触氢气的顺序，最后与氢气接触的储氢合金容器中的储氢合金为具有高平衡压力的储氢合金，所述高平衡压力储氢合金为在温度为150～450℃之间至少存在一个温度点，氢气吸收的平衡压力大于等于35Mpa；优选的，至少一个容器中的储氢合金为高平衡压力储氢合金。
10、根据方案1所述的方法，其特征在于，还包括使含氢合金释放氢气、释放的氢气与不同的储氢合金接触形成含氢合金，该过程重复一次或多次，其中至少最后一次的重复过程所用的储氢合金为高平衡压力的储氢合金。
11、根据方案1～10任一项所述的方法，其特征在于，所述的储氢合金为稀土系AB 5型、锆钛系AB 2型、钛系AB型、镁系A 2B型合金以及钒基固溶体型中的一种或者多种。
12、根据方案11所述的方法，其特征在于，所述的稀土系AB 5型储氢合金，具体分子表达式为：M mNi x1Co x2Mn x3Fe x4Al x5Sn x6，其中，4.5≤x1+x2+x3+x4+x5+x6≤5.5，3≤x1≤5.5，优选3≤x1≤4.9，0≤x2≤1.5，优选0.1≤x2≤1，0≤x3≤0.8，优选0.1≤x3≤0.6，0≤x4≤0.8，优选0.1≤x4≤0.6，0≤x5≤0.75，优选0≤x5≤0.5，0≤x6≤0.2，优选0≤x6≤0.15；Mm为含La、Ce、Pr、Nd、Y的混合稀土金属，表达式为Mm＝La y1Ce y2Nd y3Pr y4Y y5，y1+y2+y3+y4+y5＝1，0.4≤y1≤1，优选0.4≤y1≤0.8，0≤y2≤0.45，优选0.1≤y2≤0.45，0≤y3≤0.2，0≤y4≤0.05，0≤y5≤0.05。
13、根据方案11所述的方法，其特征在于，所述的锆钛系AB 2型储氢合金，其中A＝Mg x1Ca x2Ti x3Zr x4Y x5La x6，x1+x2+x3+x4+x5+x6＝0.9-1.1，0≤x1≤1.1，优选0.90≤x1≤1.05，0≤x2≤0.7，优选0≤x2≤0.25，0≤x3≤1.05，优选0.8≤x3≤1， 0≤x4≤1.05，优选0.85≤x4≤1，0≤x5≤0.2，优选0≤x5≤0.05，0≤x6≤0.2，优选0≤x6≤0.05，且x3/(x3+x4)≥0.7或者x3/(x3+x4)≤0.3；B＝V y1Cr y2Mn y3Fe y4Co y5Ni y6Cu y7，y1+y2+y3+y4+y5+y6+y7＝1.9-2.1，0≤y1≤2.1，优选0≤y1≤1.8，0≤y2≤2.1，优选0≤y2≤1.85，0≤y3≤2.1，优选0≤y3≤2.05，0≤y4≤1.6，优选0≤y4≤1.5，0≤y5≤0.5，优选0≤y5≤0.3，0≤y6≤0.5，优选0≤y6≤0.3，0≤y7≤0.5，优选0≤y7≤0.2，且1.7≤y1+y2+y3+y4≤2.1。
14、根据方案11所述的方法，其特征在于，所述的AB型储氢合金，其中A＝Ti x1Zr x2Y x3La x4，x1+x2+x3+x4＝0.85-1.1，0≤x1≤1.1，优选0.90≤x1≤1.05，0≤x2≤1.1，优选0≤x2≤0.5，0≤x3≤0.2，优选0≤x3≤0.05，0≤x4≤0.2，优选0≤x4≤0.05；B＝V y1Cr y2Mn y3Fe y4Co y5Ni y6Cu y7，y1+y2+y3+y4＝0.95-1.05，0≤y1≤0.5，优选0≤y1≤0.2，0≤y2≤0.8，优选0≤y2≤0.2，0≤y3≤0.8，优选0.05≤y3≤0.3，0＜y4≤1.05，优选0.7≤y4≤1.05，0≤y5≤0.35，优选0≤y5≤0.10，0≤y6≤0.45，优选0≤y6≤0.20，0≤y7≤0.3，优选0≤y7≤0.2。
15、根据方案11所述的方法，其特征在于，所述的钒基固溶体型储氢合金，具体分子表达式为：A x1B x2，x1+x2＝1，0.85≤x1≤0.95，优选0.90≤x1≤0.95，0.05≤x2≤0.15，优选0.05≤x2≤0.10；其中A＝Ti y1V y2Zr y3Nb y4Y y5La y6Ca y7，y1+y2+y3+y4+y5+y6+y7＝1，0≤y1≤0.9，优选0≤y1≤0.8，0≤y2≤0.95，优选0≤y2≤0.95，0≤y3≤0.90，优选0≤y3≤0.8，0≤y4≤0.55，优选0≤y4≤0.4，0≤y5≤0.2，优选0.25≤y5≤0.05，0≤y6≤0.1，优选0≤y6≤0.05，0≤y7≤0.1，优选0≤y7≤0.05；B＝Mn z1Fe z2Co z3Ni z4，z1+z2+z3+z4＝1，0≤z1≤1，优选0≤z1≤0.95，0≤z2≤0.95，优选0≤z2≤0.95，0.7≤z1+z2≤1.0，0≤z3≤0.3，优选0≤z3≤0.2，0≤z4≤0.45，优选0≤z4≤0.3。
16、根据方案1或11所述的方法，其特征在于，所述的储氢合金为第一储氢合金与第二储氢合金联用；其中，第一储氢合金为镁系A 2B型储氢合金用于富氢气体接触，第二储氢合金用于将第一储氢氢气增压，第二储氢合金为具有高平衡压力的储氢合金。
17、根据方案16所述的方法，其特征在于，第二储氢合金为稀土系AB 5型、锆钛系AB 2型、钛系AB型中的一种或者多种。
18、根据方案1或16所述的方法，其特征在于，富氢气体先经过第一储氢合金，进行杂质分离；然后使第一储氢合金释放出的高纯氢气与第二储氢合金进行接触，然后使第二储氢合金在高压下释放氢气。
19、根据方案16所述的方法，其特征在于，第一储氢合金放氢温度高于第二储氢合金吸氢温度，温差优选≥100℃，优选350℃≥温差≥150℃。
20、根据方案16所述的方法，其特征在于，第一储氢合金和第二储氢合金在不同的储氢合金储存罐中，且第一储氢合金储存罐和第二储氢合金储存罐中间有换热系统。
21、根据方案16或17所述的方法，其特征在于，所述A 2B型第一储氢合金，其具体分子表达式为：A＝Mg x1Ca x2Ti x3La x4Y x5，x1+x2+x3＝1.9-2.1，1.5≤x1≤2.1，优选1.70≤x1≤2.05，0≤x2≤0.5，优选0≤x2≤0.2，0≤x3≤0.8，优选0≤x3≤0.50；B＝Cr y1Fe y2Co y3Ni y4Cu y5Mo y6，y1+y2+y3+y4+y5+y6＝0.9-1.1，0≤y1≤0.30，优选0≤y1≤0.2，0≤y2≤0.20，优选0≤x2≤0.10，0≤y3≤1.1，优选0≤y3≤1，0≤y4≤1.1，优选0≤y4≤1.05，0≤y5≤0.4，0≤y6≤0.15，优选0≤y6≤0.10；
所述AB5型第二储氢合金，具体分子表达式为：M mNi x1Co x2Mn x3Fe x4Al x5Sn x6，其中，4.5≤x1+x2+x3+x4+x5+x6≤5.5，3≤x1≤5.5，优选3≤x1≤4.9，0≤x2≤1.5，优选0.1≤x2≤1，0≤x3≤0.8，优选0.1≤x3≤0.6，0≤x4≤0.8，优选0.1≤x4≤0.6，0≤x5≤0.75，优选0≤x5≤0.5，0≤x6≤0.2，优选0≤x6≤0.15；Mm为含La、Ce、Pr、Nd、Y的混合稀土金属，表达式为Mm＝La y1Ce y2Nd y3Pr y4Y y5，y1+y2+y3+y4+y5＝1，0.4≤y1≤1，优选0.4≤y1≤0.8，0≤y2≤0.45，优选0.1≤y2≤0.45，0≤y3≤0.2，0≤y4≤0.05，0≤y5≤0.05；
所述的锆钛系AB 2型合金第二储氢合金中，A＝Mg x1Ca x2Ti x3Zr x4Y x5La x6，x1+x2+x3+x4+x5+x6＝0.9-1.1，0≤x1≤1.1，优选0.90≤x1≤1.05，0≤x2≤0.7，优选0≤x2≤0.25，0≤x3≤1.05，优选0.8≤x3≤1，0≤x4≤1.05，优选0.85≤x4≤1，0≤x5≤0.2，优选0≤x5≤0.05，0≤x6≤0.2，优选0≤x6≤0.05，且x3/(x3+x4)≥0.7或者x3/(x3+x4)≤0.3；B＝V y1Cr y2Mn y3Fe y4Co y5Ni y6Cu y7，y1+y2+y3+y4+y5+y6+y7＝1.9-2.1，0≤y1≤2.1，优选0≤y1≤1.8，0≤y2≤2.1，优选0≤y2≤1.85，0≤y3≤2.1，优选0≤y3≤2.05，0≤y4≤1.6，优选0≤y4≤1.5，0≤y5≤0.5，优选0≤y5≤0.3，0≤y6≤0.5，优选0≤y6≤0.3，0≤y7≤0.5，优选0≤y7≤0.2，且1.7≤y1+y2+y3+y4≤2.1；
所述的钛系AB型合金第二储氢合金，其中A＝Ti x1Zr x2Y x3La x4，x1+x2+x3+x4＝0.85-1.1，0≤x1≤1.1，优选0.90≤x1≤1.05，0≤x2≤1.1，优选0≤x2≤0.5，0≤x3≤0.2，优选0≤x3≤0.05，0≤x4≤0.2，优选0≤x4≤0.05；B＝V y1Cr y2Mn y3Fe y4Co y5Ni y6Cu y7，y1+y2+y3+y4＝0.95-1.05，0≤y1≤0.5，优选0≤y1≤0.2，0≤y2≤0.8，优选0≤y2≤0.2，0≤y3≤0.8，优选0.05≤y3≤0.3，0＜y4≤1.05，优选0.7≤y4≤1.05，0≤y5≤0.35，优选0≤y5≤0.10，0≤y6≤0.45，优选0≤y6≤0.20，0≤y7≤0.3，优选0≤y7≤0.2。
22、根据方案16所述的方法，其特征在于，富氢气体与第一储氢合金接触温度为20～150℃，氢气分压为0.001～0.1Mpa；第一储氢合金释放氢气的温度(放 氢温度)为150～450℃，放氢的氢气分压为0.1～5Mpa。
23、根据方案16或22所述的方法，其特征在于，第二储氢合金吸氢温度为-70～100℃，吸氢的氢气分压为0.1～5Mpa，第二储氢合金放氢温度为150～450℃，放氢的氢分压≥35Mpa例如35～100MPa。
24、根据方案16和22所述的方法，其特征在于，富氢气体与第一储氢合金接触的吸氢温度优选为50～100℃，氢气分压优选为0.001～0.03Mpa；第一储氢合金放氢温度优选为200～350℃，放氢氢气分压优选为0.1～1Mpa；第二储氢合金吸收氢气的吸氢温度优选为-30～100℃，吸氢的氢气分压优选为0.1～1Mpa，第二储氢合金放氢温度优选为200～350℃，放氢氢分压优选为≥35Mpa。
25、根据方案1所述的方法，其特征在于，储氢合金释放氢气的温度(储氢合金加热的温度，简称放氢温度)为150～450℃，释放的氢气的压力为≥35Mpa例如为35～100MPa以得到高纯高压氢气，或者放氢的氢气分压为0.1～5Mpa以得到高纯氢气，其中放氢温度高于吸氢温度。
26、根据方案1所述的方法，其特征在于，除去含氢合金中的有机物采用吹扫的方法例如使用氢气吹扫，其方法例如：储氢合金达到预定的吸附量以后，停止向储氢合金供应富氢气体，使氢气通过含氢合金，将含氢合金和(也称为含氢合金储存容器)中的有机气体带出，引入储罐储存或者使用其它储氢合金储存容器中的储氢合金吸收；其中优选的，吹扫用氢气的纯度大于90重量％更优选大于95重量％例如大于99重量％。
27、根据方案1所述的方法，其特征在于，有机液体储氢原料与脱氢催化剂接触反应的反应温度为150～450℃，优选200～400℃，更优选300～350℃。
28、根据方案1所述的方法，其特征在于，有机液体储氢原料与脱氢催化剂接触重时空速0.5～50h -1，优选1～45h -1更优选2～30h -1。
29、根据方案1所述的方法，其特征在于，有机液体储氢原料与脱氢催化剂接触反应的压力为0.03～5Mpa或0.3～5MPa，优选0.1～3Mpa例如0.5～2Mpa或0.2～1.6MPa。
30、根据方案1所述的方法，其特征在于，使有机液体储氢原料与氢气混合后与脱氢催化剂接触，氢烃比(氢气与有机液体储氢原料的摩尔比)为0～10。
31、根据方案1所述的方法，其特征在于，有机液体脱氢反应在临氢或者不临氢的状态下，有机液体脱氢反应温度为150～450℃，重时空速0.5～50h -1，反应压力0.3～5MPa，氢烃比为0～10摩尔比，优选的反应温度为200～400℃，重时空速1～30h -1，氢烃比为0～8摩尔比。
32、根据方案1所述的方法，其特征在于，所述的脱氢催化剂为金属负载 型催化剂，所述的金属负载型催化剂包括载体和负载的活性金属组分；所述载体，所述活性金属优选包括第VIII族金属中一种或者多种；更优选，活性金属组分含有第一活性金属和任选的第二活性金属，所述第一活性金属为Pt、Pd、Ru、Rh、Ir中的一种或多种，所述第二活性金属Ni、Re、Sn、Mo、Cu、Fe、Ca、Co、W中的一种或者多种，所述第二活性金属优选为Ni、Re、Sn中的一种或多种；更优选的，所述的第一活性金属包括Pt；
或者，
所述的脱氢催化剂包括载体和负载的活性金属组分，载体选自三氧化二铝、二氧化硅、二氧化钛、氧化锆、活性炭、硅铝材料中的一种或多种，活性金属选自Ni、Zn、Sn、Cu、Fe、Ag、P、In、Re、Mo、Co、Ca、W中的至少两种金属，进一步优选Ni、Zn、Sn、Cu中的两种或两种以上或者所述的活性金属包括Ni以及选自Zn、Sn、Cu、Fe、Ag、P、In、Re、Mo、Co、Ca、W中的一种或多种。
33、根据方案32所述的方法，其特征在于，所述的脱氢催化剂中载体质量分数为70～99.9％，金属组分的质量分数为0.1～30％。
34、根据方案1所述的方法，其特征在于，所述的脱氢催化剂包括载体和活性金属组分，所述的载体为一种载体组合物，该载体组合物包括氧化铝和改性金属氧化物，所述的改性金属氧化物为钛氧化物和/或锆氧化物，其中所述的改性金属氧化物的η＜0.3，其中η＝载体组合物中晶相改性金属氧化物的重量百分含量/载体组合物中改性金属氧化物的化学组成重量百分含量，钛氧化物以TiO 2计，锆氧化物以ZrO 2计。
35、根据方案34所述的方法，其特征在于，所述的载体组合物η＝0，优选的，所述的第一金属氧化物单层分散于氧化铝基质上。
36、根据方案34所述的方法，其特征在于，所述载体组合物中氧化铝质量份数为80～98.5％，优选的为83～97.5％或85～95％或为90～95％；改性金属氧化物的质量份数为1.5～20％，优选为2.5～17％或5～15％，或为5～10％。
37、根据方案34所述的方法，其特征在于，所述的改性金属氧化物包括钛氧化物，其中优选的，所述的载体组合物中，二氧化钛质量份数优选为2～20％例如5～15％或5～10％或2.5～17％，二氧化锆质量分数优选0～8％例如0-6％或0-3％或1～6％。
38、根据方案34所述的方法，其特征在于，相对于TiO 2纯物相，所述的载体组合物XPS谱图中，Ti 2P 3/2轨道电子结合能存在偏移，结合能为458.8eV处的峰向高结合能偏移0.6-0.7eV至459.4-459.5eV，和/或Ti 2P 1/2轨道电子结合能为464.5eV处的峰向高结合能方向偏移0.8-0.9eV至465.3～465.4eV。
39、根据方案34所述的方法，其特征在于，所述的氧化物基质具有γ氧化物、η-氧化铝、ρ氧化铝或χ氧化铝至少一种的物相结构。
40、根据方案34所述的方法，其特征在于，所述的载体组合物比表面积为100～350m 2/g。
41、根据方案34所述的方法，其特征在于，所述载体组合物的孔体积为0.3～1.3ml/g。
42、根据方案1或34所述的方法，其特征在于，所述脱氢催化剂包括包含氧化铝和改性金属氧化物的载体以及活性金属组分，所述改性金属氧化物为钛氧化物和/或锆氧化物；所述的活性金属组分为活性金属的氧化物和/或活性金属的单质。所述活性金属例如第八副族金属、第七副族金属、第五副族金属、第六副族金属、第一副族金属、稀土元素、碱土金属、第四主族金属中的一种或多种；
优选的，所述的活性金属包括Pt和/或者Ni，包括或不包括含或者不含其它元素；优选的，所述的其它元素为V、Cr、Mn、Fe、Co、Ni、Cu、Ag、Ce、W、Mo、Sn、Ca、Pt、Pd、Ru、Re、Rh、Ir、Os、Zn、P、In中的一种或多种。
43、根据方案42所述的方法，其特征在于，所述的活性金属包括Pt，含或者不含其它金属，所述的其它金属可以是贵金属也可以是非贵金属，所述其它金属为Pd、Ru、Re、Rh、Ir、Os、Sn、V、Mo、Cr、Mn、Fe、Co、Ni、Cu、Ag、Ce、W、Cu、Ca、中的一种或多种。
44、根据方案42所述的方法，其特征在于，所述脱氢催化剂中，活性金属的含量为0.1-20重量％例如0.1～15重量％，载体的含量为75～99.9重量％，Pt的含量为0.1-10重量％；本发明脱氢催化剂组成中，活性金属的含量，贵金属以单质计，非贵金属以氧化物计。
45、根据方案43所述的方法，其特征在于，所述的其它金属为Pd、Ru、Re、Rh、Ir、Os中的一种或多种。
46、根据方案43所述的方法，其特征在于，所述脱氢催化剂中，所述活性金属的含量为0.1-10重量％，优选0.5～8重量％；所述载体的含量为90～99.9重量％，优选为92～99.5重量％。
47、根据方案43所述的方法，其特征在于，所述催化剂中，Pt含量为0.1～2重量％例如0.3～1.5重量％或0.5～1重量％，所述其它金属的含量为0～9.9重量％例如0.1～2或0.2～1重量％或0.1～0.8重量％，所述载体的含量优选为90～99.9重量％例如96～99.6重量％或98～99.5重量％或98.5～99.3重量％。
48、根据方案43所述的方法，其特征在于，所述的其它金属元素为Sn、V、Mo、Cr、Mn、Fe、Co、Ni、Cu、Ag、Ce、W、Cu、Ca中的一种或多种。
49、根据方案43所述的方法，其特征在于，所述催化剂中，Pt含量为0.1～10重量％，所述其它金属的含量为0～15重量％。
50、根据方案43所述的方法，其特征在于，所述催化剂中，Pt含量为0.1～2重量％例如0.5～1.5重量％，其它金属的含量为0～15重量％例如1～10重量％或2～8重量％或3～7重量％；所述载体的含量优选为85～99.9重量％例如为90～99重量％或90～98重量％或92～97重量％。
51、根据方案34所述的方法，其特征在于，所述的活性金属包括镍，含或者不含其它金属，所述其它金属为Zn、Sn、Cu、Fe、Ag、P、In、Re、Mo、Co、Ca、W中的一种或者多种。
52、根据方案51所述的方法，其特征在于，所述催化剂中，所述活性金属质量分数为5％～30％，载体质量分数为70～95％；载体质量分数优选为75～90％，活性金属质量分数优选为10％～25％。
53、根据方案51所述的方法，其特征在于，所述催化剂中，镍的含量以氧化物计为5～25重量％，优选6～20重量％例如为7～15重量％或7～12重量％或8～11重量％，所述的其它金属的含量以氧化物计为0～15重量％优选0～10重量％例如为0.5～8重量％或1～5重量％。
54、根据方案1所述的方法，其特征在于，所述的有机液体储氢原料为含环烷环的饱和/或不饱和烃，含或不含杂原子，含杂原子有机储氢化合物为含环烷环的烃被杂原子取代得到的有机物，其中杂原子取代发生在环烷环上。其中，有机液体储氢原料优选不含杂环原子的含有环烷环的饱和或不饱和烃。更优选为芳环和环烷环总数小于等于2的不含杂环原子的饱和或不饱和烃；
更更优选，有机储氢原料为芳环和环烷环总数小于等于2的不含杂环原子的饱和或不饱和烃；所述的不含杂原子的含有环烷环的饱和与不饱和烃包括：环己烷、甲基环己烷、十氢萘、双环己烷中的一种或者多种；含杂原子的含有环烷环的饱和或不饱和烃包括：含氮杂环化合物和含氮/硼杂环化合物，例如为含氮杂环化合物包括十氢咔唑、十二氢乙基咔唑、二氢吲哚、4-氨基哌啶、哌啶-4-羧胺、全氢-4，7-菲洛林、2-甲基-1，2，3，4-四氢喹啉、2，6-二甲基十氢-1，5-萘啶中的一种或者几种；含氮/硼杂原子不饱和烃包括：1，2-BN-环己烷、3-甲基-1，2-BN-环戊烷中的一种或者多种。
55、根据方案1的方法，其特征在于，还包括将释放的氢气引入到氢气储罐以储存氢气；或者，所得到的高纯高压氢气可以直接用于氢燃料电池车加注。
56、一种高效分布式制高纯高压氢气的方法，该方法包括：
在脱氢反应器中，将液体有机储氢原料在脱氢催化剂的存在下进行脱氢反应 得到包括氢气的脱氢反应产物；
在冷却分离装置中，将脱氢反应产物冷却并分离，得到富氢物流和有机液体；
在储氢合金储存容器中，使富氢物流或提纯后的富氢物流与储氢合金接触，得到含氢合金；
氢气吹扫除去储氢合金储存容器中的有机物；其中，吹扫氢气的纯度优选大于90重量％更优选大于95重量％；
将含氢合金加热释放氢气，得到高压氢气和将得到的高压氢气提供给用氢装置或高压氢气储存罐储存。
57、一种提供高纯高压氢气的系统，包括：
有机液体储氢原料储存和供应装置，用于储存有机液体储氢原料和向脱氢反应器提供有机液体储氢原料；
脱氢后液体储存装置，用于储存有机液体储氢原料脱氢后得到的液体产物；
脱氢反应器装置，用于将有机液体储氢原料在脱氢催化剂的作用下进行脱氢反应得到包括氢气的脱氢反应产物；
冷却分离装置，用于将脱氢反应产物分离得到富氢气体产物和液体产物；
储氢-供氢装置，其包括储氢合金储存容器，储氢合金加热系统，用于将富氢气体与储氢合金在低温低压下接触吸氢，吸附饱和后加热脱氢；
任选的吹扫装置用于除去储氢容器中的有机物；
氢气供应装置，将高压氢气提供给用氢装置或氢气储存罐。
58、根据方案57所述的系统，其特征在于，所述系统设置集成建造在集装箱内，作为集装箱式制氢系统置于加氢站使用，或直接建造在加氢站使用。
59、根据方案57所述的系统，其特征在于，所述的储氢-供氢装置包括一个或多个储氢合金储存容器，多个储氢合金储存容器可以并联或串联或者并联和串联混合联接。
60、根据方案57～59任一项所述的系统，其特征在于，至少一个所述的储氢合金储存容器为耐高压容器和/或所述的氢气供应装置为耐高压的装置。优选的，其耐受压力为35Mpa以上。
61、一种移动式供氢系统，包括运输车辆和设置在运输车辆上的方案57～60任一项所述的提供高纯氢气的系统。
62、一种分布式供氢装置，包括方案57～60任一项所述的提供高纯氢气的系统，任选包括高压氢气贮存罐。
实施例
下面的实施例将对本发明予以进一步说明，但其不应被用于限制本发明。
原料和测试方法
SB粉：德国Sasol公司，固含量75重量％。
P25(二氧化钛)：德国Degussa公司，固含量98重量％。
金属酸盐和金属盐购买于国药集团化学试剂北京有限公司。
有机液体储氢原料购买于百灵威科技有限公司。
在各实施例和对比例中，负载型有机液体脱氢催化剂的组成均由X射线荧光法测定，有机液体储氢原料脱氢的产物由色谱分析得到。氢气纯度由气相色谱法分析得到。
本发明实施例和对比例的有机液体脱氢实验是在固定床反应器中进行的。
分离采用冷却介质冷却分离，储氢容器连接在分离系统后，能量递送介质为热水或者热水蒸气，水蒸气由水蒸气发生器产生。
在以下实施例中，在制备有机液体储氢原料的脱氢催化剂的载体中，所述的晶相改性金属氧化物百分含量采用如下的方法测量：
使用装配有以40kV，30mA驱动的长细聚集铜X-射线源的Philips XRG3100发生器，Philips3020数字测角仪，Philips3710MPD控制计算机和Kevex PSI Peltier冷却硅探测器进行所有的X-射线衍射测量。采用Kevex4601离子泵控制器，Kevex4608Peltier电源，Kevex4621检测器偏压，Kevex4561A脉冲处理器和Kevex4911-A单通道分析器操作Kevex检测器。使用Philips APD4.1C版软件获得衍射图案。使用Material Data，Inc.。Riqas 3.1C版软件(Qutokumpu HSC Chemistry for Windows；用户手册，Qutokumpo Resarch Oy，Pori，芬兰(1999))进行所有的rietveld计算。
在以下实施例中，XPS实验在Thermo Fisher公司的ESCALab250型X射线光电子能谱仪上进行。激发源为单色化Al K αX射线，能量为1486.6eV，功率为150W。窄扫描所用通透能为30eV。分析时的基础真空约为6.5×10 -10mbar。结合能用污染碳的C1s峰(284.8eV)校正。载体组合物表面上改性金属氧化物的重量百分含量通过测量10个样品颗粒，取平均值。
在以下实施例中，比表面积和孔体积采用美国Micromertics仪器公司的ASAP2400型自动吸附仪，通过静态低温吸附容量法测定(根据GB/T5816-1995的方法)，具体方法为：将待测物在250℃，1.33Pa下抽真空脱气4小时，在-196℃下使其与作为吸附质的氮气接触，静态吸附达到吸附平衡；由氮气进气量与吸附后残存于气相中的差值计算出吸附剂吸附氮气的量，然后用BET公式计算比表面积和孔体积。
制备有机液体储氢原料脱氢催化剂的载体
载体实施例1
将SB粉在500℃焙烧4小时得到γ-Al 2O 3，该γ-Al 2O 3的比表面积176m 2/g，孔体积为0.48mL/g。
取上述γ-Al 2O 3500g置于流化反应器(反应器的内径为10cm，高度为40cm)内，将四氯化钛置于20℃恒温浴槽中，氮气(温度是25℃)以10L/min的流速通四氯化钛再从流化反应器底部进入流化反应器，流化1小时后，停止将氮气通过四氯化钛浴槽；将氮气(温度是25℃)以10L/min的流速通过放置于50℃恒温浴槽中的去离子水再从反应器底部进入流化反应器，流化4小时，进行水解，得到水解后的载体。将水解后的载体在空气气氛，550℃焙烧4小时，得到最终的载体，命名为载体1。载体组成以及载体性质见表1；其X射线衍射(XRD)谱图见图1中的“1”。
载体实施例2-8
载体2-8的制备方法同载体实施例1中的载体1的制备方法，区别在于氮气携带四氯化钛进入流化床时间，和氮气通入去离子水的水解时间。载体的制备条件，载体组成以及载体性质见表1。
载体实施例9-11
载体9-11的制备方法同载体实施例1中的载体1的制备方法，区别在于氮气先通过四氯化钛，再通过四氯化锆蒸汽发生器——其温度为300℃。载体的制备条件，载体组成以及载体性质见表1。
载体对比例1
SB粉经过500℃焙烧4小时直接得到的γ-Al 2O 3，载体命名为载体C1。载体组成以及载体性质见表1。
载体对比例2
参考载体实施例1的方法制备载体，区别在于，SB粉经过500℃焙烧4小时得到的γ-Al 2O 3，和TiO 2物理混合，载体命名为载体C2。载体组成以及载体性质见表1；其X射线衍射(XRD)谱图见图1中的“2”。
载体对比例3
参考载体对比例2制备载体，载体命名为载体C3。载体组成以及载体性质见表1。
载体对比例4
参考载体实施例6的方法制备载体，区别在于载体为SB粉经过500℃焙烧4小时得到的γ-Al 2O 3，和四氯化钛的水溶液物理混合，载体命名为载体C4。载体组成以及载体性质见表1。
载体对比例5
SB粉经过500℃焙烧4小时得到的γ-Al 2O 3，钛酸四丁酯与去离子水混合搅拌30min，以等体积浸渍的方式浸渍到γ-Al 2O 3上，经过干燥，550℃焙烧4小时得到复合氧化物载体。载体命名为载体C5。载体组成以及载体性质见表1；其X射线衍射(XRD)谱图见图1中的“5”。
载体对比例6
按照载体实施例9的配方制备载体，区别在于，SB粉经过500℃焙烧4小时得到的γ-Al 2O 3，和TiO 2，ZrO 2物理混合。载体命名为载体C6。载体组成以及载体性质见表1。
载体对比例7
参考载体对比例6制备载体，载体命名为载体C7。载体组成以及载体性质见表1。
载体实施例1-11和载体对比例1-7制备的载体性质见表1。
制备和评价有机液体储氢原料脱氢催化剂
实施例1
取0.34克氯铂酸与水配成20mL浸渍液，取19.84克载体1，将浸渍液缓慢的加入到载体1中，一边加入一边搅拌，使浸渍液均匀负载在复合氧化物载体上，浸渍温度为25℃，浸渍后的固体在120℃氮气吹扫下干燥3小时，然后在空气中进行焙烧；焙烧温度600℃，焙烧时气剂比(空气/固体的体积比)为600∶1，焙烧时间为4小时，得到催化剂。催化剂的组成列于表2中。
在固定床反应器中对上述制备的催化剂进行甲基环己烷脱氢反应评价，脱氢反应在固定床微反上进行，评价条件为：反应温度350℃，反应压力(反应器进口压力)1MPa，补充氢气流速150mL/minH 2，甲基环己烷进料2mL/min，催化剂装填量20克。催化剂的评价结果列于表2中，其中转化率＝反应的甲基环己烷/总的甲基环己烷进料；选择性＝生成甲苯的甲基环己烷/反应的甲基环己烷。
实施例5
以类似于实施例1的方式，将氯铂酸和硝酸镍与水配成20mL浸渍液，取19.7克载体1，将浸渍液缓慢的加入到载体1中，一边加入一边搅拌，使浸渍液均匀负载在复合氧化物载体上，浸渍温度为25℃，浸渍后的固体在120℃氮气吹扫下干燥3小时，然后在空气中进行焙烧；焙烧温度600℃，焙烧时气剂比(空气/固体的体积比)为600∶1，焙烧时间为4小时，得到催化剂。催化剂的组成列于表2中。
在固定床反应器中对上述制备的催化剂进行甲基环己烷脱氢反应评价，脱氢 反应在固定床微反上进行，评价条件为：反应温度350℃，反应压力(反应器进口压力)1MPa，补充氢气流速150mL/minH 2，甲基环己烷进料2.5mL/min，催化剂装填量20克。催化剂的评价结果列于表2中，其中转化率＝反应的甲基环己烷/总的甲基环己烷进料；选择性＝生成甲苯的甲基环己烷/反应的甲基环己烷。
实施例10
取硝酸镍和氯化锡与水配成20mL浸渍液，取17.8克载体1，将浸渍液缓慢的加入到载体1中，一边加入一边搅拌，使浸渍液均匀负载在复合氧化物载体上，浸渍温度为25℃，浸渍后的固体在120℃氮气吹扫下干燥3小时，然后在空气中进行焙烧；焙烧温度600℃，焙烧时气剂比(空气/固体的体积比)为600∶1，焙烧时间为4小时，得到催化剂。催化剂的组成列于表2中。
在固定床反应器中对上述制备的催化剂进行甲基环己烷脱氢反应评价，脱氢反应在固定床微反上进行，评价条件为：反应温度400℃，反应压力(反应器进口压力)1MPa，补充氢气流量150mL/minH 2，甲基环己烷进料量1.0mL/min，催化剂装填量20克。催化剂的评价结果列于表2中，其中转化率＝反应的甲基环己烷/总的甲基环己烷进料；选择性＝生成甲苯的甲基环己烷/反应的甲基环己烷。
实施例2，4，7-9，12-39和对比例1-17
按照实施例1，5或10，采用浸渍的方法制备催化剂。催化剂配方见表2，其中载体按照干基(800℃焙烧1小时)计算，铂(Pt)按照单质干基计算，钯(Pd)按照单质干基计算，铱(Ir)按照单质干基计算，铼(Re)按照单质干基计算，镍(Ni)按照NiO计，锡(Sn)按照SnO2计，锌(Zn)按照ZnO计，铜(Cu)按照CuO计，铁(Fe)按照Fe2O3计，银(Ag)按照AgO计，磷(P)按照P2O5计，锰(Mn)按照MnO 2计。
按照实施例1，5或10的评价方法，对所制备的催化剂进行评价，评价条件为：反应压力(反应器进口压力)1MPa，催化剂装填量20克；反应温度，补充氢气流速，和甲基环己烷进料量列于表2中。
实施例3，6和11
分别按照实施例2，5和10的方法制备实施例3，6和11的催化剂，区别在于浸渍后的固体在-45℃冷冻10小时，然后于-5℃，0.1atm(绝压)真空条件下干燥，然后进行所述的焙烧。
按照实施例1的评价方法，对所制备的催化剂进行评价，评价条件为：反应压力(反应器进口压力)1MPa，催化剂装填量20克；反应温度，补充氢气流速，和甲基环己烷进料量列于表2中。
本发明提供的脱氢催化剂，可以较现有方法制备的脱氢催化剂具有更高的转 化活性。在同样的反应条件下，具有更高的氢气生成速率。采用冷冻，抽真空干燥的方法，催化剂的活性和选择性提高，氢气的生成速率提高。
制备和评价储氢合金
储氢合金实例1-13和C1-C4
按照合金成分称取金属共计约1000g，置于真空感应熔炼炉的水冷坩埚中，在真空下熔炼得到合金，制备条件包括：在背景真空1×10 -4Pa下进行，熔炼温度和时间如表3所示；在背景真空1×10 -4Pa下以10℃/min的速率降温至退火温度，进行退火，所述退火的温度、时间如表3所示；在背景真空1×10 -4Pa下自然冷却至室温。将得到的合金粉碎过筛，得到70-200目的金属粉末，将粉末装入储氢罐中，将储氢罐在0.1Pa真空下加热至300℃保温4小时对合金粉末进行活化，得到储氢合金1-13和C1-C4。
将1kg储氢合金置于储氢罐中，将20℃的含有机物氢气(甲烷含量为0.01体积％)作为模型化合物，通入储氢罐中，使得氢气与储氢合金进行反应形成含氢合金，待储氢合金储氢量达到理论容量的75％，停止通入含有机物氢气，并用纯度95％的氢气进行吹扫20分钟，然后对储氢罐进行加热，保持储氢合金在50MPa下进行持续放氢，氢气纯度采用气相色谱进行分析。氢气纯度、累计储氢量和储氢量衰减率列于表3中。累计储氢量是指三十次吸氢的总量。循环上述吸氢和放氢三十次后，测定储氢量的衰减率，所述衰减率＝(第一次吸放氢储氢量-第三十次吸放氢储氢量)/第一次吸放氢储氢量×100％。
储氢合金实例14-26和C5-C10
按照合金成分称取金属共计约1000g，置于真空感应熔炼炉的水冷坩埚中，在真空下熔炼得到合金，制备条件包括：在背景真空1×10 -4Pa下进行，熔炼温度和时间如表3所示；在背景真空1×10 -4Pa下以10℃/min的速率降温至退火温度，进行退火，所述退火的温度、时间如表3所示；在背景真空1×10 -4Pa下自然冷却至室温。将得到的合金粉碎过筛，得到70-200目的金属粉末，将粉末装入储氢罐中，将储氢罐在0.1Pa真空下加热至300℃保温4小时对合金粉末进行活化，得到储氢合金14-26和C5-C10。
将1kg储氢合金置于储氢罐中，将10℃的含有机物氢气(甲烷含量为0.05体积％)作为模型化合物，通入储氢罐中，使得氢气与储氢合金进行反应形成含氢合金，待储氢合金储氢量达到理论容量的75％，停止通入含有机物氢气，并用纯度98％以上的氢气进行吹扫20min，然后对储氢罐进行加热，保持储氢合金在35MPa下进行持续放氢，氢气纯度采用气相色谱进行分析。氢气纯度、累计储氢量和储氢量衰减率列于表3中。累计储氢量是指十次吸氢的总量。循环上述吸氢 和放氢10次后，测定储氢量的衰减率，所述衰减率＝(第一次吸放氢储氢量-第十次吸放氢储氢量)/第一次吸放氢储氢量×100％。
储氢合金实例27-40和C11-C14
按照合金成分称取金属共计约1000g，置于真空感应熔炼炉的水冷坩埚中，在真空下熔炼得到合金，制备条件包括：在背景真空1×10 -4Pa下进行，熔炼温度和时间如表3所示；在背景真空1×10 -4Pa下以10℃/min的速率降温至退火温度，进行退火，所述退火的温度、时间如表3所示；在背景真空1×10 -4Pa下自然冷却至室温。将得到的合金粉碎过筛，得到70-200目的金属粉末，将粉末装入储氢罐中，将储氢罐在0.1Pa真空下加热至300℃保温4小时对合金粉末进行活化，得到储氢合金27-40和C11-C14。
将1kg储氢合金置于储氢罐中，将20℃的含有机物氢气(甲烷含量为0.1体积％)作为模型化合物，以5MPa压力通入储氢罐中，使得氢气与储氢合金进行反应形成含氢合金，待储氢合金储氢量达到理论容量的75％，停止通入含有机物氢气，并用纯度95％的氢气进行吹扫20min，然后对储氢罐进行加热，保持储氢合金在20MPa下进行持续放氢，氢气纯度采用气相色谱进行分析。氢气纯度、累计储氢量和储氢量衰减率列于表3中。累计储氢量是指十次吸氢的总量。循环上述吸氢和放氢10次后，测定储氢量的衰减率，所述衰减率＝(第一次吸放氢储氢量-第十次吸放氢储氢量)/第一次吸放氢储氢量×100％。
储氢合金实例41-56和C15-C19
按照合金成分称取金属共计约1000g，置于电弧熔炼炉的水冷坩埚中，在氩气气氛下熔炼得到合金，具体制备过程：高纯Ar气氛(纯度99.999％)下，进行熔炼，熔炼的温度、压力和时间如表3所示；在背景真空1×10 -4Pa下以10℃/min的速率降温至退火温度650℃，在该温度下退火48小时。在真空下自然冷却至室温。将得到的合金粉碎过筛，得到70-200目的金属粉末，将粉末装入储氢罐中，将储氢罐在0.1Pa真空下加热至300℃保温4小时对合金粉末进行活化，得到储氢合金41-56和C15-C19。
将1kg储氢合金置于储氢罐中，将20℃的含有机物氢气(甲烷含量为0.1体积％)作为模型化合物，在压力2MPa通入储氢罐中，使得氢气与储氢合金进行反应形成含氢合金，待储氢合金储氢量达到理论容量的75％，停止通入含有机物氢气，在80℃下，用真空泵抽真空5min，然后对储氢罐进行加热，保持储氢合金在0.1MPa下进行持续放氢，氢气纯度采用气相色谱进行分析。氢气纯度、累计储氢量和储氢量衰减率列于表3中。累计储氢量是指十次吸氢的总量。循环上述吸氢和放氢10次后，测定储氢量的衰减率，所述衰减率＝(第一次吸放氢储氢 量-第十次吸放氢储氢量)/第一次吸放氢储氢量×100％。
储氢合金实例57-67和C20-C24
按照合金成分称取金属共计约1000g，置于电弧熔炼炉的水冷坩埚中，在氩气气氛下熔炼得到合金，具体制备过程：高纯Ar气氛(纯度99.999％)下，进行熔炼，熔炼的温度、压力和时间如表3所示；在Ar气氛下自然冷却至室温，然后转移至真空退火炉中进行真空退火，背景压力为1×10 -4Pa，所述退火的温度、时间如表3所示；自然冷却至室温。将得到的合金粉碎过筛，得到70-200目的金属粉末，将粉末装入储氢罐中，将储氢罐在0.1Pa真空下加热至50-300℃保温1-10小时对合金粉末进行活化(活化的具体温度和时间如表3所示)，得到储氢合金57-67和C20-C24。
将1kg储氢合金置于储氢罐中，将20℃的含有机物氢气(甲烷含量为0.1体积％)作为模型化合物，在压力2MPa通入储氢罐中，使得氢气与储氢合金进行反应形成含氢合金，待储氢合金储氢量达到理论容量的75％，停止通入含有机物氢气，并用纯度95％的氢气进行吹扫20min，然后对储氢罐进行加热，保持储氢合金在10MPa下进行持续放氢，氢气纯度采用气相色谱进行分析。氢气纯度列于表3中。循环上述吸氢和放氢10次后，测定累计储氢量和储氢量衰减率，列于表3中，所述衰减率＝(第一次吸放氢储氢量-第十次吸放氢储氢量)/第一次吸放氢储氢量×100％。累计储氢量是指十次吸氢量的总和。
本发明提供的储氢合金具有良好的抗有机物污染性能，在氢气中含有有机物的情况下具有较好的吸氢效率，并且具有较高的储氢量，可以获得高压高纯度氢气。
AB 5型储氢合金实例68：
MmNi 3.55Co 0.75Mn 0.4Al 0.3，其中Mm＝La 0.61Ce 0.16Pr 0.04Nd 0.19
按照合金成分称取金属共计约100g，置于电弧熔炼炉的水冷坩埚中，在氩气气氛下熔炼得到合金，制备条件：高纯Ar气氛(纯度99.999％)，压力0.9-1.0atm，电流80-200A，电压40V，熔炼时间10-60分钟，在Ar气氛下自然冷却至室温。转移到高真空退火炉中进行真空退火，背景压力1×10 -4Pa，退火温度800-950℃，退火时间24-168h，自然冷却至室温。将合金粉碎过筛，得到70-200目的金属粉末，将粉末装入储氢罐中，将储氢罐在0.1Pa真空下加热至200-400℃保温1-4小时对合金粉末进行活化。
通过下述测试方法，说明实施例1的催化剂和AB 5型储氢合金实例68的有机液体储氢原料脱氢反应，分离经提纯和增压的效果。
原料油为甲基环己烷，甲基环己烷脱氢反应在固定床微反上进行评价，评价 条件为：反应温度350℃，压力1MPa，补充氢气流速150mL/minH 2(标准状况)，甲基环己烷进料2mL/min，催化剂装填量20克，具体参数和结果如下所示。
脱氢反应产物经过冷却以后在放置于20℃盐水中的分离罐中分离，控制冷却的温度为20℃，收集液体产物，气体产物引入储氢合金储罐进行氢气的吸收。储氢合金吸附量达到设定值以后，用纯度为99％的氢气在吸氢温度下吹扫储氢合金储罐30分钟，然后加热储氢合金释放氢气。
其中，转化率＝反应的甲基环己烷/总的甲基环己烷进料
反应产物用色谱进行分析，用第10分钟产物组成数据计算转化率。
脱氢反应温度：350℃
脱氢反应压力：1MPa
有机液体脱氢转化率：98.50％
吸氢温度：20℃
吸氢氢分压：0.2MPa
放氢温度：200℃
放氢氢分压：35MPa
氢气纯度：99.99％
储氢量(200ml)：14.1g。
Figure PCTCN2020088740-appb-000001
Figure PCTCN2020088740-appb-000002
Figure PCTCN2020088740-appb-000003
Figure PCTCN2020088740-appb-000004
Figure PCTCN2020088740-appb-000005
Figure PCTCN2020088740-appb-000006
Figure PCTCN2020088740-appb-000007
Figure PCTCN2020088740-appb-000008

Claims (14)

  1. 一种用于有机物脱氢催化剂的载体组合物，该载体组合物包括氧化铝和改性金属氧化物，所述的改性金属氧化物为钛氧化物和/或锆氧化物，其中，η＜0.3，优选地，η＝0；θ≥5，优选地，θ为5-40(例如5.4-34.3)；
    η＝载体组合物中晶相改性金属氧化物的重量百分含量/载体组合物中改性金属氧化物的化学组成重量百分含量，
    θ＝载体组合物表面上改性金属氧化物的重量百分含量/载体组合物中改性金属氧化物的化学组成重量百分含量，钛氧化物以TiO 2计，锆氧化物以ZrO 2计。
  2. 根据前述权利要求中任一项所述的用于有机物脱氢催化剂的载体组合物，其特征在于，相对于TiO 2纯物相，所述的载体组合物XPS谱图中，Ti 2P 3/2轨道电子结合能为458.8eV处的峰向高结合能偏移0.6-0.7eV和/或Ti 2P 1/2轨道电子结合能为464.5eV处的峰向高结合能方向偏移0.8-0.9eV。
  3. 根据前述权利要求中任一项所述的用于有机物脱氢催化剂的载体组合物，其特征在于，所述的载体组合物中氧化铝质量分数为80-98.5％(例如83-97.5％，85-95％或90-95％)，改性金属氧化物的质量分数为1.5-20％(例如2.5-17％，5-15％，或5-10％)；
    所述的改性金属氧化物包括钛氧化物；所述的载体组合物中，二氧化钛的质量分数为2-20％(例如2.5-17％，5-15％或5-10％)，二氧化锆的质量分数为0-8％(例如0-6％，0-3％或1-6％)；优选地，所述的改性金属氧化物(例如二氧化钛)单层分散于氧化铝基质上；
    所述的载体组合物具有γ-氧化铝，η-氧化铝，ρ-氧化铝或χ-氧化铝中至少一种的物相结构；
    所述的载体组合物的比表面积为100-350m 2/g，所述的载体组合物的孔体积为0.3-1.3mL/g。
  4. 一种根据前述权利要求中任一项所述的用于有机物脱氢催化剂的载体组合物的制备方法，包括如下步骤：
    (1)将氧化铝基质与气体携带的改性金属氧化物前驱体气流接触，得到负载改性金属氧化物前躯体的氧化铝基质，所述的改性金属氧化物前驱体为氧化钛前躯体和/或氧化锆前躯体；
    (2)使负载改性金属氧化物前躯体的氧化铝基质水解，焙烧，得到载体组合物；所述的氧化钛前躯体选自四氯化钛，钛酸(四)乙酯，钛酸四丁酯，钛酸(四)异丙酯，醋酸钛的一种或者多种(优选四氯化钛)；所述的氧化锆前躯体选自四氯化锆，乙醇锆，甲醇锆，异丙醇锆，锆酸四丁酯中的一种或多种(优选四氯化锆和/或甲醇锆)；
    所述的氧化铝基质选自γ-氧化铝，η-氧化铝，ρ-氧化铝，χ-氧化铝，水合氧化铝中的一种或多种；
    所述的氧化铝基质的比表面积为100-350m 2/g；优选地，所述的载体组合物的比表面积与所述的氧化铝基质的比表面积之比不低于90％；
    所述的氧化铝基质的孔体积为0.3-1.3mL/g；
    所述的气体为无水的非活性气体(例如氮气，氦气，氖气，氩气)，所述的无水的非活性气体中的水含量不超过10ppm；优选的，所述的气体携带的改性金属氧化物前驱体气流中改性金属氧化物前驱体的含量为0.1-3g/L(例如，0.2-2g/L)，其中改性金属氧化物前驱体含量以金属氧化物计。
  5. 根据前述权利要求中任一项所述的载体组合物的制备方法，其特征在于，步骤(1)中，所述的气体的温度为室温至350℃(例如为室温(室温是指15-40℃)至300℃，或15至300℃)；
    步骤(1)中接触的压力为0.05-5atm(例如1-3atm)(表压)。
  6. 根据前述权利要求中任一项所述的载体组合物的制备方法，其特征在于，所述的气体每分钟的体积流量与氧化铝基质体积的比值为3-80∶1(例如，5-30∶1，10-25∶1)；其中气体的体积以标准状况下的体积计，氧化铝基质的体积以堆积体积计。
  7. 根据前述权利要求中任一项所述的载体组合物的制备方法，其特征在于，所述的氧化铝基质在流化态下与气体携带的改性金属氧化物前驱体气流接触，或是在搅拌下与所述的气流接触；流化态例如可以是鼓泡床，湍动床，快速床或输送床。
  8. 根据前述权利要求中任一项所述的载体组合物的制备方法，其特征在于，步骤(2)所述的使负载改性金属氧化物前躯体的氧化铝基质水解，方法如下：使所述的负载改性金属氧化物前躯体的氧化铝基质与含水蒸气的气体接触；
    步骤(2)所述的水解，所述的含水蒸气的气体与氧化铝基质接触的比值(标准 状态下含水蒸气的气体与氧化铝基质堆积体积之比)为3-80∶1(例如5-30∶1，或10-25∶1)，所述的含水蒸气的气体中水蒸气占气体总体积的比例为0.1体积％-100体积％(例如3体积％-100体积％)；所述的含水蒸气的气体中水蒸汽以外的其它气体可以是惰性气体，氮气或空气；
    步骤(2)所述的水解，水解时间为1小时至50小时，例如2小时至30小时；
  9. 根据前述权利要求中任一项所述的载体组合物的制备方法，其特征在于，对于所述的焙烧来说，焙烧温度为350℃-700℃，焙烧时间为0.5-12小时(焙烧气氛可以为不含氧气或含氧气的气氛。一种实施方式情况，所述的含氧气的气氛中氧气的含量可以为3-100％体积，例如为空气气氛或者氧气气氛)。
  10. 一种用于有机物脱氢制氢气的催化剂，其特征在于所述的催化剂含有前述权利要求中任一项所述的用于有机物脱氢催化剂的载体组合物和活性组分。
  11. 根据前述权利要求中任一项所述的用于有机物脱氢制氢气的催化剂，其中活性组分是以下(1)，(2)和(3)中的一种：
    (1)贵金属组中的至少一种元素，优选地，活性组分是Pt以及任选地贵金属组中的除Pt以外的至少一种元素；
    (2)Pt和第一金属组中的至少一种元素；
    (3)Ni，第二金属组中的至少一种元素，和任选的磷；
    其中
    贵金属组是由选自Pt，Pd，Ru，Re，Rh，Ir，Os的元素构成的组；
    第一金属组是由选自Sn，V，Mo，Cr，Mn，Fe，Co，Ni，Cu，Ag，Ce，W，Cu，Ca的元素构成的组；
    第二金属组是由选自Zn，Sn，Cu，Fe，Ag，In，Re，Mo，Co，Ca，W的元素构成的组；
    所述的催化剂中，载体的含量为70-99.9重量％；活性组分的含量为0.1-30重量％。
  12. 根据前述权利要求中任一项所述的用于有机物脱氢制氢气的催化剂，其中活性组分是(1)贵金属组中的至少一种元素，所述的催化剂中，载体的含量为90-99.9重量％(例如92-99.4重量％，92-99.5重量％，95-99.4重量％，98-99.2重量％，98.5-99.5重量％)；活性组分的含量为0.1-10重量％(例如0.6-8重量％，0.5-8重量％，0.6-5重量％，0.8-2重量％或0.5-1.5重量％)；
    优选地，活性组分是Pt以及任选地贵金属组中的除Pt以外的至少一种元素，其 中Pt的含量为0.1-10重量％(例如0.1-2重量％，0.6-10重量％或0.6-0.8重量％)，贵金属组中的除Pt以外的至少一种元素的含量为0-9.9重量％(例如0.1-2重量％或0.1-0.8重量％)；或者
    活性组分是(2)Pt和第一金属组中的至少一种元素；
    所述的催化剂中，载体的含量为；75-99.5重量％(例如75-99.4重量％，79.9-98.5重量％)，活性组分的含量为0.5-25重量％(例如0.6-25重量％，1.5-20.1重量％)；在所述的活性组分中，以单质计的Pt的含量为0.01-10重量％(例如，0.2-8重量％，0.4-2重量％，0.3-0.6重量％，0.1-0.7重量％)；以氧化物计的第一金属组中的至少一种元素的含量为0.5-20重量％(例如0.5-15重量％或1-10重量％)；优选地，第一金属组中的至少一种元素为Ni或为Ni和选自第一金属组中的除Ni以外的至少一种元素的组合，其中Pt(以单质计)与Ni(以NiO计)的质量比为(0.01∶16)至(0.5∶0.1)；或者
    活性组分是(3)Ni，第二金属组中的至少一种元素，和任选的磷；
    在所述的催化剂中，载体的含量为70-95重量％(例如，75-93重量％，或75-90重量％)，以氧化物计的活性组分的含量为5-30重量％(例如，7-25重量％)；
    在所述的活性组分中，以NiO计的镍的含量为0.5-25重量％(例如，5-25重量％，6-20重量％，或6-11重量％)；以氧化物计的第二金属组中的至少一种元素的含量为0-15重量％(例如0-10重量％)；以P 2O 5计的磷的含量为0-15重量％。
  13. 一种催化剂的制备方法，其包括如下步骤根据前述权利要求中任一项所述的载体组合物的制备方法中的步骤(1)和(2)：
    (1)将氧化铝基质与气体携带的改性金属氧化物前驱体气流接触，得到负载改性金属氧化物前躯体的氧化铝基质，所述的改性金属氧化物前驱体为氧化钛前躯体和/或氧化锆前躯体；
    (2)使负载改性金属氧化物前躯体的氧化铝基质水解，焙烧，得到载体组合物；其中所述的催化剂的制备方法还包括如下的步骤：
    (3)用活性组分前驱体溶液浸渍所述的载体组合物，得到浸渍活性组分前驱体的载体；
    (4)浸渍活性组分前驱体的载体干燥，焙烧；
    优选地，活性组分是以下(1)，(2)和(3)中的一种：
    (1)贵金属组中的至少一种元素，优选地，活性组分是Pt以及任选地贵金属组中的除Pt以外的至少一种元素；
    (2)Pt和第一金属组中的至少一种元素；
    (3)Ni，第二金属组中的至少一种元素，和任选的磷；
    其中
    贵金属组是由选自Pt，Pd，Ru，Re，Rh，Ir，Os的元素构成的组；
    第一金属组是由选自Sn，V，Mo，Cr，Mn，Fe，Co，Ni，Cu，Ag，Ce，W，Cu，Ca的元素构成的组；
    第二金属组是由选自Zn，Sn，Cu，Fe，Ag，In，Re，Mo，Co，Ca，W的元素构成的组；
    步骤(4)所述的焙烧，焙烧温度为400-700℃，焙烧时间为0.5-12小时；
    活性组分前驱体是活性组分的可溶性盐(例如，金属硝酸盐，乙酸盐，金属氯化盐，金属碳酸盐，金属醋酸络合物，金属氢氧化物，金属草酸盐络合物，高价金属酸，高价金属酸盐，金属配合物，铵盐中的一种或多种)。
  14. 根据前述权利要求中任一项所述的催化剂的制备方法，其特征在于，
    将浸渍活性组分前驱体的载体于低于-40℃的环境中放置1小时至24小时；然后进行抽真空干燥，除去载体上吸附的水，然后焙烧，得到催化剂。
PCT/CN2020/088740 2019-05-06 2020-05-06 有机储氢原料脱氢催化剂以及该催化剂的载体、储氢合金、和提供高纯度氢气的方法 WO2020224584A1 (zh)

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