CN101693199A - Catalyst for purifying hydrogen as well as preparation method and applications thereof - Google Patents
Catalyst for purifying hydrogen as well as preparation method and applications thereof Download PDFInfo
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- CN101693199A CN101693199A CN200910197057A CN200910197057A CN101693199A CN 101693199 A CN101693199 A CN 101693199A CN 200910197057 A CN200910197057 A CN 200910197057A CN 200910197057 A CN200910197057 A CN 200910197057A CN 101693199 A CN101693199 A CN 101693199A
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Abstract
The invention relates to a catalyst for purifying hydrogen as well as a preparation method and applications thereof. The preparation method comprises the following steps: weighting and proportioning palladium, aluminum and mixed rare earth with a ratio of (1-10):1(0.5-4) in parts by weight, then utilizing mixing-hot melting and activation treatment to obtain an alloy catalyst, or dissolving the mixture together with carriers in deionized water, dipping, drying and conducting activation treatment to obtain a supported metal catalyst. The obtained catalyst can treat industrial-grade hydrogen into high-purification or ultra-high purification hydrogen. Compared with the existing technology, the catalyst effectively lowers the usage of metal platinum, and has better economical benefits and wider ranges of reaction temperature and air pressure in purification, thus bringing convenience for purification technology.
Description
Technical field
The present invention relates to a kind of Preparation of catalysts method and application, especially relate to a kind of Catalysts and its preparation method and application that is used for purifying hydrogen.
Background technology
Growing along with science and technology, many industrial production, scientific research department all need to use highly purified hydrogen.In semi-conductor industry, integrated circuit production, non-ferrous metal metallurgy and processing, silicon steel, band steel, Precise Alloy, float glass, gas industry and liquid hydrogen are produced or the like the aspect, all need to use the high-purity hydrogen of purity 99.999% to 99.99999%.
But the hydrogen purity that present industrial various hydrogen production process is produced all can not satisfy above-mentioned requirements.For example, the hydrogen purity of producing by brine electrolysis is roughly about 99%; Purity by the fossil fuel reforming hydrogen manufacturing is about 95%; The hydrogen purity that methanol decomposition is produced is generally about 75%.Wherein the hydrogen purity of producing with brine electrolysis is the highest, but will obtain only reliable further purifying of more high-purity hydrogen.Therefore, the rough product of purified hydrogen is the emphasis that people study always.
Existing hydrogen purification method roughly has following several:
1) palladium barrier diffusion method: this is a kind of method that is used in early days separating with purifying hydrogen, its principle is to allow the palladium film of hydrogen by preparing in advance, owing to have only hydrogen to pass through from the palladium film, and other gases can't pass through from the palladium film, have so just reached the purpose that hydrogen and other gas are separated.It has been generally acknowledged that the material of palladium film is with palladium 77%, silver 23% is best proportioning.Use the hydrogen of this method purifying, its purity is the highest can to reach 99.999999%, and water content reaches dew point-70 ℃～-80 ℃.But the shortcoming of this method also is conspicuous.At first, the palladium film is a kind of expensive material, and works under higher catalytic temperature, and catalytic activity is descended, and the palladium film that pressurizes when excessive is also very easily impaired.These drawbacks limit the palladium embrane method as the method for purifying hydrogen in industrial large-scale application, thereby this method only limits to use in the laboratory.
2) select absorption method: when selecting the various impurity of absorption method in removing hydrogen, can be divided into low-temperature adsorption and pressure swing adsorption method again.Under the general condition, use Kiselgel A to be adsorbent, the low-temperature adsorption under liquid nitrogen temperature is the highest, and to produce purity be ultra-pure hydrogen of 99.99999%.Pressure swing adsorption method can be removed the impurity of various ingredients in theory under the condition of once-through operation, but the method influence factor is numerous, the controlled condition complexity.
3) absorption process: based on the absorption process of solution, be made up of absorption tower and regenerator, absorbing and regenerating all is to carry out under certain temperature and pressure.This subtraction unit is simple, but will produce a large amount of waste liquids in purge process, does not therefore more and more meet the requirement of environmental protection and Green Chemistry.
4) catalytic reaction method: this method is exactly to utilize various catalyst to remove oxygen impurities in the hydrogen etc.Generally the oxygen impurities in the hydrogen can be purified to the ppm level from a few percent, even the ppb level.The method catalytic efficiency height, the product purity height of gained is fit to industrial uninterrupted big flow ground purifying hydrogen.The metal that is generally used for catalysis has Ti, Mn, Fe, Pt, Pd, Rh, Cu and lanthanide series metal or the like.
Summary of the invention
Purpose of the present invention is exactly that a kind of good in economic efficiency, the Catalysts and its preparation method that is used for purifying hydrogen and application that can obtain ultra-high purity hydrogen is provided in order to overcome the defective that above-mentioned prior art exists.
Purpose of the present invention can be achieved through the following technical solutions:
A kind of catalyst that is used for purifying hydrogen is characterized in that, this catalyst comprises following component and weight portion:
Palladium 1-10;
Aluminium 1;
Mishmetal 0.5-4.
A kind of Preparation of catalysts method that is used for purifying hydrogen, it is characterized in that, this method may further comprise the steps: with Metal Palladium, metallic aluminium and mishmetal (1-10) by weight: 1: (0.5-4) weighing and burden, heat fused becomes alloy pig in vacuum arc furnace ignition again, then alloy pig is put into disintegrating machine and be processed into the 0.1-10mm metallic particles, at last metallic particles is placed tube furnace, feed hydrogen, the control temperature is 500-700 ℃, and activation processing 5-8h promptly gets alloy catalyst; Perhaps the nitrate of palladium, the nitrate of aluminium, the nitrate and the carrier of mishmetal are dissolved in the deionized water, behind the dipping 10-14h, with the mixed material that obtains at 120-150 ℃ of dry 8-12h, again in 400 ℃ of roasting 3-5h, at last mixed material is seated in the tube furnace, logical hydrogen promptly obtains the metal supported catalyst at 300-400 ℃ of activation 8-12h.
The particle diameter of described metallic particles is 0.1-20mm.
Described carrier comprises molecular sieve, aluminium oxide, diatomite or silica gel, and carrier granular is 0.1-20mm.
The content of metal of described metal supported catalyst is 0.1-40% (wt%), and the weight ratio of the palladium in the catalyst, aluminium, mishmetal is (1-10): 1: (0.5-4).
A kind of Application of Catalyst that is used for purifying hydrogen is characterized in that, technical grade hydrogen in 100-300 ℃ after above-mentioned alloy catalyst is handled, can obtain purity and be 99.999% high-purity hydrogen; The hydrogen of technical grade in 400 ℃ after above-mentioned alloy catalyst is handled, can obtain purity and be ultra-pure hydrogen of 99.99999%; The hydrogen of technical grade in 100-200 ℃ after above-mentioned metal supported catalyst is handled, can obtain purity and be 99.999% high-purity hydrogen.
Compared with prior art, the new material of the hydrogen purification that the present invention proposes itself does not absorb hydrogen, is desirable hydrogen purification material.Because this new material itself is the composite of three kinds of alloys, under the prerequisite that does not reduce purification performance, compared with the catalysis of simple use palladium, reduced the consumption of Metal Palladium effectively, so better economic benefit, reaction temperature when purifying and gas pressure limit broad, this has brought convenience for purifying process, can obtain 99.999% high-purity hydrogen and 99.99999% ultra-high purity hydrogen.
The specific embodiment
The present invention is described in detail below in conjunction with specific embodiment.
Embodiment 1
With palladium, aluminium and mishmetal is raw material, with 40kg palladium, 20kg aluminium and 40kg mishmetal weighing and burden, makes electrode, and heat fused becomes alloy pig in vacuum arc furnace ignition, then the alloy pig of making is put into the metallic particles that disintegrating machine is processed into 1-8mm.Subsequently, this metallic particles is put into tube furnace,, be the alloy catalyst that can be used for purifying hydrogen through the alloying pellet after the activation processing at 500 ℃ of logical hydrogen activation 6h.
The hydrogen outlet of electrolytic cell is switched to the tube furnace inlet that activated alloy catalyst is housed, feeding (contains oxygen 900ppm by the hydrogen crude product that brine electrolysis makes, dew point is-40 ℃), the control gas pressure intensity is at 0.5-1.0MPa, 200 ℃ of cleansing temps, through behind this alloy catalyst single-stage purifying, the gained hydrogen product is passed through gas chromatographic detection, purity is 99.999%, reaches the requirement of high-purity hydrogen; When cleansing temp was 400 ℃, through behind this alloy catalyst single-stage purifying, the gained hydrogen product was by gas chromatographic detection, and purity is 99.99999%, reaches the requirement of ultra-pure hydrogen.
Embodiment 2
With 122.2g two ammino palladium nitrate, 555.6g aluminum nitrate nonahydrate, 124.0g mixed rare earth nitrates hexahydrate, be dissolved in the 2000ml deionized water, to wherein adding the molecular sieve that the 10kg particle diameter is 1-5mm, dipping 12h is then at 120 ℃ of dry 16h then, 150 ℃ of dry 4h, behind 400 ℃ of roasting 4h, it is seated in the tube furnace, logical hydrogen is at 300 ℃ of activation 6h again, do not have steam to occur to the gas outlet in 400 ℃ of activation 4h again, continue again at 400 ℃ of reductase 12 h.Obtaining palladium, aluminium, mishmetal weight ratio is 3: 1: 1, and content of metal is 2% metal supported catalyst.
The hydrogen outlet of electrolytic cell is switched to the tube furnace inlet that activated metal supported catalyst is housed, feeding (contains oxygen 900ppm by the hydrogen crude product that brine electrolysis makes, dew point is-40 ℃), the control gas pressure intensity is at 0.5-1.0MPa, 100 ℃ of cleansing temps, through behind this alloy catalyst single-stage purifying, the gained hydrogen product is passed through gas chromatographic detection, purity is 99.999%, reaches the requirement of high-purity hydrogen
Embodiment 3
A kind of Preparation of catalysts method that is used for purifying hydrogen, this method may further comprise the steps: take by weighing 1kg Metal Palladium, 1kg metallic aluminium and 0.5kg mishmetal, mix, heat fused becomes alloy pig in vacuum arc furnace ignition again, then alloy pig is put into disintegrating machine and be processed into the 0.1-10mm metallic particles, at last metallic particles is placed tube furnace, feed hydrogen, the control temperature is 500 ℃, and activation processing 5h promptly gets alloy catalyst.
Technical grade hydrogen in 100-300 ℃ after above-mentioned alloy catalyst is handled, can obtain purity and be 99.999% high-purity hydrogen; In 400 ℃ after above-mentioned alloy catalyst is handled, can obtain purity and be ultra-pure hydrogen of 99.99999%.
Embodiment 4
A kind of Preparation of catalysts method that is used for purifying hydrogen, this method may further comprise the steps: take by weighing 10kg Metal Palladium, 1kg metallic aluminium and 4kg mishmetal, mix, heat fused becomes alloy pig in vacuum arc furnace ignition again, then alloy pig is put into disintegrating machine and be processed into the 0.1-10mm metallic particles, at last metallic particles is placed tube furnace, feed hydrogen, the control temperature is 700 ℃, and activation processing 8h promptly gets alloy catalyst
Technical grade hydrogen in 100-300 ℃ after above-mentioned alloy catalyst is handled, can obtain purity and be 99.999% high-purity hydrogen; In 400 ℃ after above-mentioned alloy catalyst is handled, can obtain purity and be ultra-pure hydrogen of 99.99999%.
Embodiment 5
With 1kg two ammino palladium nitrate, 1kg aluminum nitrate nonahydrate, 0.5kg being the aluminium oxide 100kg of 0.1-20mm, mixed rare earth nitrates hexahydrate and particle diameter be dissolved in the deionized water, behind the dipping 10h, with the mixed material that obtains at 120 ℃ of dry 8h, in 400 ℃ of roasting 3h, at last mixed material is seated in the tube furnace, logical hydrogen promptly obtains the metal supported catalyst at 300 ℃ of activation 8h again.The content of metal of the metal supported catalyst that obtains is 0.1% (wt%), and the weight ratio of the palladium in the catalyst, aluminium, mishmetal is 1: 1: 0.5.
The hydrogen of technical grade in 100-200 ℃ after above-mentioned metal supported catalyst is handled, can obtain purity and be 99.999% high-purity hydrogen.
Embodiment 6
With 10kg two ammino palladium nitrate, 1kg aluminum nitrate nonahydrate, 4kg mixed rare earth nitrates hexahydrate and particle diameter are that the diatomite 50kg of 0.1-20mm is dissolved in the deionized water, behind the dipping 14h, with the mixed material that obtains at 150 ℃ of dry 12h, in 400 ℃ of roasting 5h, at last mixed material is seated in the tube furnace, logical hydrogen promptly obtains the metal supported catalyst at 400 ℃ of reduction 12h again.The content of metal of the metal supported catalyst that obtains is 40% (wt%), and the weight ratio of the palladium in the catalyst, aluminium, mishmetal is 10: 1: 4.
The hydrogen of technical grade in 100-200 ℃ after above-mentioned metal supported catalyst is handled, can obtain purity and be 99.999% high-purity hydrogen.
Claims (6)
1. a catalyst that is used for purifying hydrogen is characterized in that, this catalyst comprises following component and weight portion:
Palladium 1-10;
Aluminium 1;
Mishmetal 0.5-4.
2. Preparation of catalysts method that is used for purifying hydrogen, it is characterized in that, this method may further comprise the steps: with Metal Palladium, metallic aluminium and mishmetal (1-10) by weight: 1: (0.5-4) weighing and burden, heat fused becomes alloy pig in vacuum arc furnace ignition again, then alloy pig is put into disintegrating machine and be processed into the 0.1-10mm metallic particles, at last metallic particles is placed tube furnace, feed hydrogen, the control temperature is 500-700 ℃, and activation processing 5-8h promptly gets alloy catalyst; Perhaps the nitrate of palladium, the nitrate of aluminium, the nitrate and the carrier of mishmetal are dissolved in the deionized water, behind the dipping 10-14h, with the mixed material that obtains at 120-150 ℃ of dry 8-12h, again in 400 ℃ of roasting 3-5h, at last mixed material is seated in the tube furnace, logical hydrogen promptly obtains the metal supported catalyst at 300-400 ℃ of activation 8-12h.
3. a kind of Preparation of catalysts method that is used for purifying hydrogen according to claim 2 is characterized in that the particle diameter of described metallic particles is 0.1-20mm.
4. a kind of Preparation of catalysts method that is used for purifying hydrogen according to claim 2 is characterized in that described carrier comprises molecular sieve, aluminium oxide, diatomite or silica gel, and carrier granular is 0.1-20mm.
5. a kind of Preparation of catalysts method that is used for purifying hydrogen according to claim 2, it is characterized in that, the content of metal of described metal supported catalyst is 0.1-40% (wt%), and the weight ratio of the palladium in the catalyst, aluminium, mishmetal is (1-10): 1: (0.5-4).
6. an Application of Catalyst that is used for purifying hydrogen is characterized in that, technical grade hydrogen in 100-300 ℃ after above-mentioned alloy catalyst is handled, can obtain purity and be 99.999% high-purity hydrogen; The hydrogen of technical grade in 400 ℃ after above-mentioned alloy catalyst is handled, can obtain purity and be ultra-pure hydrogen of 99.99999%; The hydrogen of technical grade in 100-200 ℃ after above-mentioned metal supported catalyst is handled, can obtain purity and be 99.999% high-purity hydrogen.
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Cited By (1)
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| CN103071488A (en) * | 2013-01-09 | 2013-05-01 | 上海化工研究院 | High-purity hydrogen catalytic agent prepared by hydrogen catalytic deoxidation, as well as preparation method and application thereof |
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| DE3940758A1 (en) * | 1989-12-09 | 1991-06-13 | Degussa | METHOD FOR PURIFYING THE EXHAUST GAS FROM DIESEL ENGINES |
| CN1736589A (en) * | 2005-08-19 | 2006-02-22 | 张俊香 | Selective hydrogenation catalyst and its application condition |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103071488A (en) * | 2013-01-09 | 2013-05-01 | 上海化工研究院 | High-purity hydrogen catalytic agent prepared by hydrogen catalytic deoxidation, as well as preparation method and application thereof |
| CN103071488B (en) * | 2013-01-09 | 2015-04-01 | 上海化工研究院 | High-purity hydrogen catalytic agent prepared by hydrogen catalytic deoxidation, as well as preparation method and application thereof |
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Address after: 200062 Shanghai city Putuo District Yunling Road No. 345 Co-patentee after: QINGLEI SPECIAL GAS Co.,Ltd. SHANGHAI RESEARCH INSTITUTE OF CHEMICAL INDUSTRY Patentee after: SHANGHAI RESEARCH INSTITUTE OF CHEMICAL INDUSTRY Co.,Ltd. Address before: 200062 Shanghai city Putuo District Yunling Road No. 345 Co-patentee before: QINGLEI SPECIAL GAS Co.,Ltd. SHANGHAI RESEARCH INSTITUTE OF CHEMICAL INDUSTRY Patentee before: Shanghai Research Institute of Chemical Industry |
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Effective date of registration: 20171130 Address after: 200062 Shanghai city Putuo District Yunling Road No. 345 Patentee after: SHANGHAI RESEARCH INSTITUTE OF CHEMICAL INDUSTRY Co.,Ltd. Address before: 200062 Shanghai city Putuo District Yunling Road No. 345 Co-patentee before: QINGLEI SPECIAL GAS Co.,Ltd. SHANGHAI RESEARCH INSTITUTE OF CHEMICAL INDUSTRY Patentee before: SHANGHAI RESEARCH INSTITUTE OF CHEMICAL INDUSTRY Co.,Ltd. |