CN1022476C - Process for preparing high-pressure hyperpure hydrogen - Google Patents

Process for preparing high-pressure hyperpure hydrogen Download PDF

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Publication number
CN1022476C
CN1022476C CN90102922A CN90102922A CN1022476C CN 1022476 C CN1022476 C CN 1022476C CN 90102922 A CN90102922 A CN 90102922A CN 90102922 A CN90102922 A CN 90102922A CN 1022476 C CN1022476 C CN 1022476C
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hydrogen
metal hydride
compressor
pressure
terminal
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Expired - Fee Related
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CN90102922A
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CN1048833A (en
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陈长聘
王启东
吴京
方添水
敖鸣
叶舟
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Zhejiang University ZJU
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Zhejiang University ZJU
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
    • C01B3/56—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with solids; Regeneration of used solids
    • C01B3/58—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with solids; Regeneration of used solids including a catalytic reaction
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/0005—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes
    • C01B3/001—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes characterised by the uptaking medium; Treatment thereof
    • C01B3/0031—Intermetallic compounds; Metal alloys; Treatment thereof
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/32—Hydrogen storage

Abstract

The present invention relates to a method and a device for manufacturing high pressure super pure hydrogen which adopts two catalytic deoxidation drying purifiers 2 (2 ') and two metallic hydride terminal purifying compressors 3 (3 '). The device for manufacturing high pressure super pure hydrogen makes the industrial common hydrogen into the high pressure super pure hydrogen with the purity more than 99.9999 % and the 13-15mpa pressure. When the hydride is desorbed and pressurized, the metal hydride purifier 3 / 3 ' is heated by the water with 97 to 100 DEG C. The device for manufacturing high pressure super pure hydrogen has simple equipment, low investment, low cost, low energy consumption and convenient operation.

Description

Process for preparing high-pressure hyperpure hydrogen
The present invention relates to pack into the method and apparatus of pressurized vessel of a kind of hydrogen cleaning and pressurized gas.
Hydrogen is a kind of important industrial raw material, and its purity can branch purity be that 99% general hydrogen, purity are that 99.99% pure hydrogen, purity are that 99.999% High Purity Hydrogen and purity are 99.9999% ultra-pure hydrogen.Commercially available various High Pressure Hydrogen are all through the compression of mechanical commprssor or molding machine, and this compress mode exists energy consumption height, poor stability and produces defectives such as noise, leakage, oil pollution, and not to be suitable for compressing purity be 99.9999% ultra-pure hydrogen.
Metal hydride cleaner utilization Hydrogen Storage Alloys wherein is converted into metal hydride, and hydrogen-storage alloy-hydrogen is that decomposition pressure increases with the temperature rising, utilizes this specific character, just can produce the high High Pressure Hydrogen of purity to metal hydride heating desorption supercharging compression.
Preparation about ultra-pure hydrogen, Japanese Patent JP55-149104 provides four kinds of different hydrogen-storage alloys of a kind of employing to make four metal hydrides and purifies the use of compressor tandem, purify and compression through level Four, make purity and be 99.9999%, pressure is the middle pressure ultra-pure hydrogen of 5.9MPa.The defective of this technology is the equipment complexity, and the ultra-pure hydrogen pressure of producing is not high, does not reach the requirement of commercially available steel cylinder hydrogen pressure.
The object of the present invention is to provide the industrial general hydrogen of a kind of usefulness to make that purity is 99.9999%, pressure is the method for the manufacturing high pressure ultra-pure hydrogen of 13～15MPa.
Fig. 1 is a kind of layout of equipment of making high pressure ultra-pure hydrogen.
Fig. 2 is when the metal hydride terminal is purified compressor heating supercharging, metal hydride decomposition pressure one temperature relation figure.
As shown in Figure 1, the inventive system comprises bottled general hydrogen 1, catalytic deoxidation dry cleaner 2,2 ', metal hydride terminal purifying compression device 3,3 ', product hydrogen steel cylinder 4, valve K1～K6, K1 '～K6 ' and connecting pipe. Catalytic deoxidation dry cleaner 2,2 ' be arranged in juxtaposition wherein, metal hydride terminal purifying compression device 3,3 ' be arranged in juxtaposition, the desorb supercharging compression that the latter is hocketed in purifying the compression process and inhaled hydrogen and hydrogen.
Catalytic deoxidation dry cleaner 2,2 ' in dehydrogenation catalyst and adsorption desiccant are housed, the former is as palladium molecular sieve, palladium aluminum oxide, palladium carbon fiber etc., the latter such as molecular sieve, silica gel, activated carbon etc.
The metal hydride terminal purifies the heat exchanger that hydrogen-storage alloy is housed in the compressor and hydrogen-storage alloy is carried out water flowing cooling or heating usefulness.
This device is characterised in that: be provided with 2 catalytic deoxidation dry cleaners that are arranged in juxtaposition 2,2 ' and 2 metal hydride terminals of being arranged in juxtaposition purify compressors 3,3, wherein catalytic deoxidation dry cleaner 2,2 ' in palladium molecular sieve and molecular sieve are housed, the metal hydride terminal purifies compressor 3(3 ') in storage alloy material for hydrogen adopt Mm 0.95-XCa XCu0.05Ni 5-YAl y, X=0.05～0.25 wherein, y=0.05～0.15; Or employing Mm 0.95Cu 0.05Ni 5-XAl XZr y, X=0.05 in the formula～0.15, Y=0.05～0.20; Wherein the norium Mm trade mark is RECe-45.
A kind of method of making high pressure ultra-pure hydrogen, comprise with purity be 99%, the bottled general hydrogen of pressure 2.0～3.0MPa is raw material, purify compressor through metal hydride and inhale hydrogen purification and heating desorption supercharging compression, acquisition purity is 99.9999% ultra-pure hydrogen, inhaling the hydrogen purification stage, the Hydrogen Storage Alloys heat release is by the logical cold water cooling of heat exchanger, heating supercharging compression during desorb is driven away this metal hydride with the hydrogen behind the purifying earlier before the filling bottle and is purified foreign gas in compressor.
The invention is characterized in: general hydrogen is through 2/2 ' preliminary cleaning of a catalytic deoxidation dry cleaner, a metal hydride terminal purifies 3/3 ' terminal of compressor and inhales hydrogen purification and heating desorption supercharging compression, producing purity is 99.9999%, pressure is the high pressure ultra-pure hydrogen of 13～15MPa, wherein the metal hydride terminal purifies compressor 3,3 ' in hydrogen-storage alloy before inhaling hydrogen purification first, need to carry out activation treatment with 99.99% pure hydrogen, when hydrogen-storage alloy all is converted into metal hydride, open the hydrogen of valve K5/K5 ' after with preliminary cleaning drive away be free in the metal hydride terminal purify compressor 3/3 ' in foreign gas, then valve-off K4/K4 ', with the metal hydride terminal purify compressor 3/3 ' in the part ultra-pure hydrogen drive away residual impurity gas to metal hydride terminal and purify compressor 3/3 ' exit hydrogen purity and reach 99.9999% and end; At hydrogen-storage alloy desorb supercharging compression stage, adopt hot water that the metal hydride terminal is purified 97～100 ℃ of compressors 3/3 ' heating.
Catalytic deoxidation dry cleaner 2 and 2 ' hocketing purifies and regeneration, metal hydride terminal purification compressor 3/3 ' hocket and inhale hydrogen purification and heating desorption supercharging compression.
Be to improve the production efficiency of high pressure ultra-pure hydrogen, can adopt jumbo metal hydride terminal to purify compressor 3,3 ' each, perhaps the metal hydride terminal of a plurality of parallel connections purify compressor 3,3 '.
Fig. 2 is metal hydride decomposition pressure and Heating temperature graph of a relation.Among the figure:
A-adopts existing MmNi 5Hydride.
B-adopts Mm 0.95Cu 0.05Ni 4.95Al 0.05Zr 0.10Hydride.
C-adopts Mm 0.75Ca 0.2Cu 0.05Ni 4.95Al 0.05Hydride.
With prior art relatively, the present invention has the following advantages:
1. only need to purify compressor and purify compression, just can obtain purity and be 99.9999%, pressure is the high pressure ultra-pure hydrogen product of 13～15MPa through the preliminary cleaning of a catalytic deoxidation dry cleaner and a metal hydride terminal; Prior art just can reach purity 99.9999%, pressure≤9.81MPa(100kgf/cm through metal hydride cleaner stage purification and compression 2).
2. be used for driving away the foreign gas that the metal hydride terminal purifies compressor, the consumption of ultra-pure hydrogen is 5%; And Japanese Patent JP55-149104, its ultra-pure hydrogen consumption is 15%.
Embodiment 1:
The catalytic deoxidation dry cleaner adopts stainless steel vessel, interior dress 5kg palladium molecular sieve and 35kg5A molecular sieve; It is that 19 diameter of phi 38mm of a usefulness, long 1200mm stainless steel tube are welded into tubular heat exchanger, interior dress Mm that the metal hydride terminal purifies compressor 0.75Ca 0.20Cu 0.05Ni 4.95Al 0.05Hydrogen-storage alloy 70kg; The decoration form of production equipment as shown in Figure 1.
The metal hydride terminal purifies compressor after withstand voltage and seal test is qualified, imports 99.99% pure hydrogen and carries out activation treatment.
With general hydrogen is raw material, operates by the method for this explanation, per hour can produce purity and be 99.9999%, pressure is 15MPa high pressure ultra-pure hydrogen 10Nm 3
Embodiment 2:
Hydrogen-storage alloy adopts Mm 0.95Cu 0.05Ni 4.95Al 0.05Zr 0.10, all the other conditions are identical with embodiment 1, per hour produce purity and be 99.9999%, pressure is 13MPa high pressure ultra-pure hydrogen 10Nm 3

Claims (1)

1, a kind of method of making high pressure ultra-pure hydrogen, comprise that the general hydrogen so that purity is 99%, pressure is 2.0～3.0MPa is raw material, purify compressor through metal hydride and inhale hydrogen purification and heating desorption supercharging compression, obtain purity and be 99.9999%, pressure is the ultra-pure hydrogen of 13～15MPa, it is characterized in that:
A. general hydrogen is through the 2/2 ' preliminary cleaning of a catalytic deoxidation dry cleaner;
B. the hydrogen after the preliminary cleaning send into metal hydride terminal compressor 3/3 ', this metal hydride terminal compressor 3/3 ' in hydrogen-storage alloy adopt Mm 0.95-XCa xCu0.05Ni 5-YAl y, wherein Mm is a norium, x=0.05～0.25, y=0.05～0.15; Perhaps adopt Mm 0.95Cu 0.05Ni 5-xAl xZr y, X=0.05～0.15 wherein, Y=0.05～0.20;
C. when the metal hydride terminal purify compressor 3/3 ' in hydrogen-storage alloy when all being converted into metal hydride, open valve K5/K5 ' with the hydrogen after purifying drive away be free in the metal hydride terminal purify compressor 3/3 ' in foreign gas;
D. valve-off K4/K4 ' purifies compressor 3/3 ' middle part ultra-pure hydrogen expeling residual impurity gas with the metal hydride terminal and purifies compressor 3/3 ' exit hydrogen purity to the metal hydride terminal and only reach 99.9999%;
E. at hydrogen-storage alloy desorb supercharging compression stage, adopt hot water that the metal hydride terminal is purified 97 ℃～100 ℃ of compressors 3/3 ' heating, only reached 13～15MPa until charging container pressure.
CN90102922A 1990-08-19 1990-08-19 Process for preparing high-pressure hyperpure hydrogen Expired - Fee Related CN1022476C (en)

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Application Number Priority Date Filing Date Title
CN90102922A CN1022476C (en) 1990-08-19 1990-08-19 Process for preparing high-pressure hyperpure hydrogen

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Application Number Priority Date Filing Date Title
CN90102922A CN1022476C (en) 1990-08-19 1990-08-19 Process for preparing high-pressure hyperpure hydrogen

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CN1048833A CN1048833A (en) 1991-01-30
CN1022476C true CN1022476C (en) 1993-10-20

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101792910A (en) * 2010-04-15 2010-08-04 上海交通大学 Household solar energy and hydrogen energy system
CN103359688B (en) * 2013-07-10 2015-08-05 西安交通大学 Blue charcoal coke-oven gas is utilized to produce method and the system thereof of different purity grade hydrogen
CN104760933B (en) * 2014-07-08 2018-02-02 苏州宝晶新材料科技有限公司 A kind of ultra-pure hydrogen generator
CN105060248A (en) * 2015-07-17 2015-11-18 北京浩运金能科技有限公司 Hydrogen purification device
CN111320137A (en) * 2018-12-14 2020-06-23 国家能源投资集团有限责任公司 Method and system for separating and purifying hydrogen from mixed gas

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