CN103861645A - Aluminium/water reaction controllable-hydrogen catalyst and preparation method thereof - Google Patents
Aluminium/water reaction controllable-hydrogen catalyst and preparation method thereof Download PDFInfo
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- CN103861645A CN103861645A CN201410145793.6A CN201410145793A CN103861645A CN 103861645 A CN103861645 A CN 103861645A CN 201410145793 A CN201410145793 A CN 201410145793A CN 103861645 A CN103861645 A CN 103861645A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention discloses an aluminium/water reaction controllable-hydrogen catalyst. The aluminium/water reaction controllable-hydrogen catalyst comprises the following materials in percent by weight: (a) 75%-85% of metal aluminium powder; (b) 5%-12% of mixture of bismuth chloride, sodium chloride and potassium chloride; (c) 5%-15% of mixture of metal calcium powder and metal zinc powder. A preparation method of the catalyst comprises the steps of: (1) fully stirring according to the proportion with 90% of aluminium powder and 10% of bismuth chloride, sodium chloride and potassium chloride, and mixing into an Al-BiCl3 base material; (2) fully stirring according to the proportion with 90% of Al-BiCl3 base material and 10% of metal calcium powder and metal zinc powder, and mixing into an Al-BiCl3 main material; (3) putting the Al-BiCl3 main material into a ball mill to carry out ball-milling for more than 5 hours so as to prepare a high-activity Al-BiCl3 composite material; (4) mixing and stirring the high-activity Al-BiCl3 composite material and polyacrylamide aqueous solution, preparing into blocks and then drying.
Description
Technical field
The present invention relates to a kind of aluminium/water and react controlled catalyst for preparing hydrogen, relate in particular to a kind of aluminium/water and react the accounting ratio of each formula material of controlled catalyst for preparing hydrogen.
Background technology
Aluminium is metallic element the richest in the earth's crust, and wide material sources are cheap, and density is low.The chemical phenomenon of the raw hydrogen of aluminium/water reaction, inspires the mankind by the anti-hydrogen producing technology of research and development aluminium/water, is green energy resource---and the extensive use of Hydrogen Energy provides method, and it is likely that the mankind solve and faces one of energy shortage and problem of environmental pollution active path.In China, about mechanism research and also deliver of application aspect of academic institution and expert's bound pair aluminium/water reaction hydrogen producing technology more.
(1) literary composition periodical " chemical progress " the 24th volume the 4th periodical is stepped on " aluminium/water reacts controlled hydrogen manufacturing " (middle figure classification number: TQ116.2 that (big vast refined Wang Ping is greatly worn in the 110016 Ma Guanglu village, Shenyang material science country of Metal Inst., Chinese Academy of Sciences (associating) Shenyang, laboratory) delivers; TM911.4 Document code: A article numbering: 1005-281X (2012) 04-0650-09), the achievement in research that this academic documents is explained tool directive significance is:
1, under mild temperature, the reaction of aluminium/water can spontaneously be carried out, but because there is one deck carrying out that (about 3-5nm) dense oxide (Al2O3) has stoped reaction as thin as a wafer on aluminium surface, the key of hydrogen manufacturing is to dissolve or suppresses this layer of intrinsic oxide-film or again generate this reaction mechanism of passivating film;
2, adopt mechanical ball-milling method, utilize oxide (MoO3, Bi2O3, CuO, MgO) plurality of inorganic salt (NaCl, KCl), for promoter, aluminium powder is carried out to surface active, can destroy aluminum shot surface film oxide, aluminium can be reacted with neutral water under mild temperature;
The speed of 3, aluminium/water reaction hydrogen production reaction depends primarily on the reaction condition such as temperature, the particle diameter of aluminium powder of reaction.
(2) (South China Science & Engineering University's chemistry is heat conduction reinforced and key lab of the process energy conservation Ministry of Education with chemical engineering institute in civilian periodical " power technology " publication, the bright Xie Dong of 510640 Liu of Guangzhou Guangdong come) " aluminium water reaction hydrogen producing technology Recent Progresses In The Development " (middle figure classification number: TM911 Document code: A article numbering: 1002-087X(2011) 01-0109-04) of delivering, this academic documents has been introduced the application progress of relevant aluminium water reaction hydrogen manufacturing both at home and abroad in Proton Exchange Membrane Fuel Cells, several promotions has been discussed and has been reacted the method that continues to carry out, shortens induction time.To our achievement in research of tool directive significance be:
1, by ball milling aluminium powder and oxide powder, it is mixed, mechanically destroyed the oxide layer on aluminium powder surface, thereby to have accelerated at pH be the generation of hydrogen in neutral water;
2, ball milling aluminium and water-soluble inorganic salt powder make its mixing, can produce certain destruction (wherein NaCl and KCl effect are best) to the oxide aluminium lamination on aluminium powder surface on the one hand, thereby activate reacting of aluminium and water, salt can prevent the reunion of metallic aluminium in mechanical milling process on the other hand, aluminium-salt mixture exists with powder particle, aluminium-salt ball milling product produces a large amount of unsalted surfaces and defect, and this also helps lend some impetus to the carrying out of reaction.
The application study of aluminium/water reaction hydrogen producing technology, focus mostly on and realized business-like Preliminary Applications in the research and development aspect fuel cells applications and on portable power source, technology application surface is very narrow, and this present situation is unfavorable for extensive popularization and the technology of aluminium/water reaction hydrogen producing technology universal.And commercial applications aspect aluminium/water reaction hydrogen generating system, key is a kind of instant efficient device for producing hydrogen of design, though more existing relevant design and inventions both at home and abroad at present, but because these published designs and invention exist system complex huge, exist reaction can not be continuously, clean inconvenience, large, high temperature resistant etc. the technological deficiency that need overcome consumes energy, practicality is not high, thereby does not all have a dissemination, is the technical barrier place of restriction aluminium/water reaction hydrogen producing technology application research and development.
In view of above-mentioned defect, being necessary to design a kind of improved aluminium/water reacts controlled catalyst for preparing hydrogen in fact.
Summary of the invention
Technical problem to be solved by this invention is: provide a kind of aluminium/water to react controlled catalyst for preparing hydrogen and manufacture method thereof.
For solving the problems of the technologies described above, technical scheme of the present invention is:
A kind of aluminium/water reacts controlled catalyst for preparing hydrogen, the composition that it comprises following mass percent:
(a) metallic aluminium powder of 75%～85% (weight);
(b) bismuth chloride of 5%～12% (weight), sodium chloride, potassium chloride mixture;
(c) metallic calcium powder of 5%-15% (weight), metal zinc mixture.
Aluminium/water reacts a manufacture method for controlled catalyst for preparing hydrogen, and it comprises the steps:
(1) press aluminium powder 90%, the ratio of bismuth chloride, sodium chloride, potassium chloride 10% fully stirs, and is mixed into Al-BiCl3 base-material;
(2) press Al-BiCl3 base-material 90%, the ratio of metallic calcium powder, metal zinc 10% fully stirs, and is mixed into Al-BiCl3 major ingredient;
(3) by Al-BiCl3 major ingredient, put ball mill into and carry out ball milling more than 5 hours, make high activity Al-BiCl3 composite.
(4) high activity Al-BiCl3 composite and polyacrylamide solution mix and blend are made to block post-drying.
Compared with prior art, high activity Al-BiCl3 composite-material formula tool of the present invention has the following advantages: raw material are non-scarcity material, ample supply of commodities on the market, the low easy buying of cost; Pollution-free, after reaction, accessory substance is chemically neutral, can repeatedly use, and the renewable metallic aluminium that is reduced into; The characteristics such as controlled hydrogen manufacturing as required, start-up time is short, reaction rate is fast, fuel conversion is high.
Detailed description of the invention
The present invention is further described to tie embodiment below.
High activity Al-BiCl3 composite of the present invention, be by aluminium from bismuth chloride according to different quality percentage composition mixing and ball milling, because bismuth chloride enbrittles and sharp edge, what in mechanical milling process, it can cut aluminium is less, this will improve the hydrolysis rate of aluminium greatly, and the displacement reaction of aluminium and bismuth chloride can occur simultaneously in this process, and pure aluminum displaces bismuth with elementary, between aluminium and bismuth, can form micro cell like this, accelerate the hydrolysis of aluminium.Due to the impact of these two factors, even if Al-BiCl3 composite hydrogen manufacturing material also has very strong hydrolytic hydrogen production performance at low temperatures, wherein the hydrogen output 1201ml/g conversion ratio of Al-10wt%BiCl3 reaches 98.20%, in addition, also carry out Ball-milling Time and different additive (NaCl and NaBH4) the impact test on Al-BiCl3 composite hydrogen manufacturing material activity, by the prolongation of Ball-milling Time, between aluminium and bismuth chloride, displacement is more abundant, improved bismuth dispersiveness simultaneously, reduce the average grain diameter of material, thereby improve the hydrogen manufacturing performance of composite.
Aluminium/water of the present invention reacts controlled catalyst for preparing hydrogen primary raw material: metallic aluminium powder, bismuth chloride, sodium chloride, potassium chloride, metallic calcium powder, metal zinc, polyacrylamide.Aluminium/water reacts controlled catalyst for preparing hydrogen, the composition that it comprises following mass percent: (a) metallic aluminium powder of 75%～85% (weight); (b) bismuth chloride of 5%～12% (weight), sodium chloride, potassium chloride mixture; (c) metallic calcium powder of 5%-15% (weight), metal zinc mixture.Preferably, the mass percent of described genus aluminium powder is 81%.
Preferably, the mass percent of described bismuth chloride, sodium chloride, potassium chloride mixture is 9%.Preferably, the mass percent of described bismuth chloride, sodium chloride, potassium chloride mixture is 9%.
Aluminium/water reacts a manufacture method for controlled catalyst for preparing hydrogen, and it comprises the steps:
(1) press aluminium powder 90%, the ratio of bismuth chloride, sodium chloride, potassium chloride 10% fully stirs, and is mixed into Al-BiCl3 base-material;
(2) press Al-BiCl3 base-material 90%, the ratio of metallic calcium powder, metal zinc 10% fully stirs, and is mixed into Al-BiCl3 major ingredient;
(3) by Al-BiCl3 major ingredient, put ball mill into and carry out ball milling more than 5 hours, make high activity Al-BiCl3 composite.
(4) high activity Al-BiCl3 composite and polyacrylamide solution mix and blend are made to block post-drying.
When use, this kind of block high activity Al-BiCl3 composite put into pressure vessel, by valve control, pressure vessel is introduced bubble and the water vapour of 120 DEG C of left and right of 0.4-0.5PaM pressure, make to form in pressure vessel the aluminium water reaction condition of HTHP, most of bubble and water vapour will cracking go out hydrogen with this understanding, after the water vapour of this kind after the catalysis of high activity Al-BiCl3 composite emitted, add methyl alcohol combustion-supporting with regard to incendivity, flame kernel temperature can reach 1200 DEG C again.
Aluminium/water of the present invention reacts controlled catalyst for preparing hydrogen, set up innovatively one and can directly apply to industry pot (kiln) stove, city for industry heating production links such as temperature, thermal power generation, finally realize the commercial applications of water hydrogen energy source, face the shortage of traditional fossil energy and problem of environmental pollution is made contributions for China solves, make the popularization of clean energy resource realize economic benefit and social benefit doulbe-sides' victory sustainable development.
The present invention is not limited to above-mentioned concrete embodiment, and those of ordinary skill in the art is from above-mentioned design, and without performing creative labour, all conversion of having done, within all dropping on protection scope of the present invention.
Claims (6)
1. aluminium/water reacts a controlled catalyst for preparing hydrogen, it is characterized in that the composition that it comprises following mass percent:
(a) metallic aluminium powder of 75%～85% (weight);
(b) bismuth chloride of 5%～12% (weight), sodium chloride, potassium chloride mixture;
(c) metallic calcium powder of 5%-15% (weight), metal zinc mixture.
2. aluminium/water as claimed in claim 1 reacts controlled catalyst for preparing hydrogen, it is characterized in that: the mass percent of described metallic aluminium powder is 81%.
3. aluminium/water as claimed in claim 2 reacts controlled catalyst for preparing hydrogen, it is characterized in that: the mass percent of described bismuth chloride, sodium chloride, potassium chloride mixture is 9%.
4. aluminium/water as claimed in claim 3 reacts controlled catalyst for preparing hydrogen, it is characterized in that: the mass percent of described metallic calcium powder, metal zinc mixture is 10%.
5. aluminium/water as claimed in claim 1 reacts a manufacture method for controlled catalyst for preparing hydrogen, it is characterized in that, it comprises the steps:
(1) press aluminium powder 90%, the ratio of bismuth chloride, sodium chloride, potassium chloride 10% fully stirs, and is mixed into Al-BiCl3 base-material;
(2) press Al-BiCl3 base-material 90%, the ratio of metallic calcium powder, metal zinc 10% fully stirs, and is mixed into Al-BiCl3 major ingredient;
(3) by Al-BiCl3 major ingredient, put ball mill into and carry out ball milling more than 5 hours, make high activity Al-BiCl3 composite.
(4) high activity Al-BiCl3 composite and polyacrylamide solution mix and blend are made to block post-drying.
6. aluminium/water as claimed in claim 5 reacts the manufacture method of controlled catalyst for preparing hydrogen, it is characterized in that: when use, block high activity Al-BiCl3 composite is put into pressure vessel.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104549521A (en) * | 2015-01-14 | 2015-04-29 | 彭军 | Hydrogen production catalyst and preparation method thereof |
| CN104925753A (en) * | 2015-06-25 | 2015-09-23 | 桂林电子科技大学 | Al-BiCl<3>-LiBH<4> aluminum-based composite hydrogen production material and method for manufacturing same |
| CN105036075A (en) * | 2015-06-25 | 2015-11-11 | 桂林电子科技大学 | Al-BiBr3 aluminum base composite hydrogen production material and preparation method thereof |
| CN105170164A (en) * | 2015-10-22 | 2015-12-23 | 耿烽 | Active composite catalyst for preparing hydrogen from steam, and preparation method of active composite catalyst |
| JP2017190275A (en) * | 2016-04-15 | 2017-10-19 | 株式会社Ｋｓｆ | Byproduct hydrogen generation device |
| CN109133000A (en) * | 2018-08-23 | 2019-01-04 | 杭州氢源素生物科技有限公司 | A kind of micro-nano composite hydrolysis hydrogen manufacturing material of aluminium base |
| CN111573620A (en) * | 2020-04-21 | 2020-08-25 | 天津大学 | Modularized hydrogen production method |
| CN111788148A (en) * | 2017-12-18 | 2020-10-16 | 爱霍德有限公司 | Composition for generating hydrogen |
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| JPH01228543A (en) * | 1988-03-09 | 1989-09-12 | Jgc Corp | Preparation of catalyst |
| CN101289163A (en) * | 2007-04-20 | 2008-10-22 | 中国科学院大连化学物理研究所 | Aluminum alloy for preparing hydrogen by hydrolytic decomposition and preparation thereof |
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2014
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| JPH01228543A (en) * | 1988-03-09 | 1989-09-12 | Jgc Corp | Preparation of catalyst |
| CN101289163A (en) * | 2007-04-20 | 2008-10-22 | 中国科学院大连化学物理研究所 | Aluminum alloy for preparing hydrogen by hydrolytic decomposition and preparation thereof |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104549521A (en) * | 2015-01-14 | 2015-04-29 | 彭军 | Hydrogen production catalyst and preparation method thereof |
| CN104925753A (en) * | 2015-06-25 | 2015-09-23 | 桂林电子科技大学 | Al-BiCl<3>-LiBH<4> aluminum-based composite hydrogen production material and method for manufacturing same |
| CN105036075A (en) * | 2015-06-25 | 2015-11-11 | 桂林电子科技大学 | Al-BiBr3 aluminum base composite hydrogen production material and preparation method thereof |
| CN105170164A (en) * | 2015-10-22 | 2015-12-23 | 耿烽 | Active composite catalyst for preparing hydrogen from steam, and preparation method of active composite catalyst |
| JP2017190275A (en) * | 2016-04-15 | 2017-10-19 | 株式会社Ｋｓｆ | Byproduct hydrogen generation device |
| CN111788148A (en) * | 2017-12-18 | 2020-10-16 | 爱霍德有限公司 | Composition for generating hydrogen |
| CN111788148B (en) * | 2017-12-18 | 2024-01-26 | 爱霍德有限公司 | Composition for generating hydrogen |
| CN109133000A (en) * | 2018-08-23 | 2019-01-04 | 杭州氢源素生物科技有限公司 | A kind of micro-nano composite hydrolysis hydrogen manufacturing material of aluminium base |
| CN111573620A (en) * | 2020-04-21 | 2020-08-25 | 天津大学 | Modularized hydrogen production method |
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