CN102910582B - Aluminum alloy/hydroboron hydrolysis reaction-based miniature hydrogen production system and hydrogen production method - Google Patents
Aluminum alloy/hydroboron hydrolysis reaction-based miniature hydrogen production system and hydrogen production method Download PDFInfo
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- CN102910582B CN102910582B CN201210357701.1A CN201210357701A CN102910582B CN 102910582 B CN102910582 B CN 102910582B CN 201210357701 A CN201210357701 A CN 201210357701A CN 102910582 B CN102910582 B CN 102910582B
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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
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Abstract
The invention relates to an aluminum alloy/hydroboron hydrolysis reaction-based miniature hydrogen production system and a hydrogen production method thereof, belonging to the field of hydrogen preparation technique. The aluminum alloy/hydroboron hydrolysis reaction-based miniature hydrogen production system comprises a hydrogen production generator and a liquid storage tank, wherein the hydrogen production generator is coated by the liquid storage tank; an outlet at the bottom end of the liquid storage tank is connected with a hydrogen production generator liquid delivery pipe, a liquid delivery control valve, a stainless steel pipe and a reaction region; the top end of the liquid delivery pipe is connected with a hydrogen storage chamber; the hydrogen production generator is divided into a reaction chamber and the hydrogen storage chamber by a separation film; and two symmetrical circular truncated cones are arranged at the bottom of the reaction region. The hydrogen production method of the aluminum alloy/hydroboron hydrolysis reaction-based miniature hydrogen production system is characterized in that the hydroboron solution input velocity of the liquid delivery control valve is regulated to realize the start/stop of the hydrolysis reaction of the hydrogen production system, so as to stabilize the hydrogen pressure of the hydrogen production system. The aluminum alloy/hydroboron hydrolysis reaction-based miniature hydrogen production system and the hydrogen production method have the characteristics of being simple in structure, and safe and reliable, and suitable for supplying hydrogen for portable fuel cells or internal combustion engines.
Description
Technical field
The invention belongs to hydrogen production and storing technology, particularly relate to a kind of miniature hydrogen generating system hydrogen production process based on aluminium alloy/borohydride hydrolytic reaction.
Background technology
Along with becoming increasingly conspicuous of global environment and energy problem, vehicle energy saving and the research reducing noxious emission receive unprecedented attention.Calorific value 142.35kJ/g due to hydrogen is 2.8 times of gasoline, 4 times of coal, and the product of the burning of hydrogen and electrochemical reaction is water, therefore hydrogen be considered to following most potentiality, the energy carrier of low-carbon high-efficiency.As one of the best mode of hydrogen utilization, fuel cell achieves development at full speed in recent years.Fuel cell is the ideal power source of the vehicles such as automobile, also can be used as portable power supplies, small-sized movable field of power supplies provides power supply.And fuel cell will be widely used in these fields, be still faced with the select permeability of safe hydrogen storage method.There is the shortcomings such as storage hydrogen efficiency is low, complex process equipment as high-pressure hydrogen storing, alloy Chu Qing etc. in traditional hydrogen storage method, cannot meet the actual demand of fuel cell.
Miniature hydrogen generating system is the effective way solving fuel cell hydrogen source.The method mainly fuel as hydroborate, storage metal exist in hydrogen generating system, produce hydrogen supply fuel cell by hydrolysis reaction, realize hydrogen manufacturing at any time, hydrogen supply, solve the safety problem in the storage of hydrogen and transportation.Aluminium/hydroborate (NaBH
4and BH
3nH
3deng) system has that hydrogen content is high, pollution-free, reaction temperature and the advantage such as controlled, extensively by the concern of domestic and international scientific research personnel.Evgen [S.Evgeny, D.Victor, V.Arvind.Combustion of novel chemical mixtures for hydrogen generation.Int.J.HydrogenEnergy 2007,32:207-211] utilize nano aluminum/sodium borohydride system to work in coordination with hydrogen manufacturing, sodium borohydride hydrolysis dynamics is improved by the heat of aluminium hydrolysis release, when the mass ratio of nano aluminum/sodium borohydride is 1: 1, the hydrogen of 6.7wt% can be produced.Shenyang metal institute Wang Ping [H.B Dai, G.L Ma, P.Wang.Hydrogen generation from coupling reactions of sodiumborohydride and aluminum powder with aqueous solution of cobalt chloride.Catalysis Today2011,170:50-55] utilize aluminium/sodium borohydride/sodium hydroxide/cobalt chloride solution mixed system hydrogen manufacturing, optimum composition can realize the storage hydrogen number obtaining 5.4wt% at 2-3 minute, transformation efficiency reaches 91%.
But in actual applications, the amount of heat that aluminium/borohydride hydrolytic produces and insoluble substance, cause hydrolysate to lump and stick to aluminum alloy surface, prevent reaction continue carry out.
Summary of the invention
In order to overcome above-mentioned the deficiencies in the prior art, the present invention aims to provide a kind of miniature hydrogen generating system hydrogen production process meeting aluminium alloy/borohydride hydrolytic reaction, this system has the features such as hydrogen purity that is with low cost, preparation is high, reactant hydrolysis is complete, hydrolysis rate is controlled, is applicable to portable hydrogen.
To achieve these goals, the technical solution used in the present invention is:
Based on a miniature hydrogen generating system for aluminium alloy/hydroborate system hydrolysis reaction, comprise hydrogen generator, container for storing liquid, infusion pump and liquid-transport pipe-line; Hydrogen generator is hollow cylindrical body, comprises tank body and lid; Tank body comprises reaction chamber and hydrogen storage chamber; The peripheral coated rectangular parallelepiped container for storing liquid of hydrogen generator; The spacing of container for storing liquid inwall and hydrogen generator outer wall is 5 ~ 30cm; Hydrogen generator is higher than container for storing liquid 5 ~ 10cm; Container for storing liquid top arranges import, and bottom arranges outlet, and bottom end outlet connects hydrogen generator import tubing through tubing, infusion pump, tubing; Hydrogen generator import tubing and hydrogen generator tank body contour; Hydrogen generator import tubing end sealing, has a pore from 0 ~ 0.5cm place, top, connects hydrogen generator hydrogen storage chamber; A control valve of infusing is had from 1 ~ 4cm place, hydrogen generator import tubing top; Transfusion control valve is that two equivalent triangles cones are connected, and transfusion control valve upper and lower arranges upright open triangles cone and handstand open triangles cone respectively, and the shape of all pyrometric cones is identical with volume; The upright open triangles cone on transfusion control valve top and the handstand open triangles cone spacing of transfusion control valve bottom are 1 ~ 3cm, distance has an aperture and enters hydrogen generator reaction zone through stainless steel tube therebetween, stainless steel tube is downward-sloping with level be 5 ~ 15 ° around hydrogen generator inwall, and be welded on hydrogen generator inwall; The watering mouth that the distribution of stainless steel tube bottom even is circular, tiny; Directly over stainless steel tube, 0.5 ~ 2cm arranges gas-liquid separation membrane; Tank body is divided into reaction chamber and hydrogen storage chamber by separatory membrane; Hydrogen storage chamber's inner diameter is less than reaction chamber wall diameter 1 ~ 3cm, and between hydrogen storage chamber's inwall and reaction chamber wall, around equally distributed 4 root posts of hydrogen storage chamber's welding; Column penetrates separatory membrane, and the diameter of column is between 0.1 ~ 0.3cm, and height is between 0.5 ~ 1.5cm; Separatory membrane can move freely on column; Immediately below stainless steel tube, 10 ~ 30cm is symmetrical arranged 2 opening up round platforms; Have production well, connecting gas transmission pipe in the middle of lid, gas transmission pipe end connects air pressure valve; Circular hole is uniformly distributed, through polytetrafluoro pad, flange fixing seal around tank body and lid.
The hydrogen production process of described miniature hydrogen generating system, is characterized in that: aluminium alloy bars, aluminium alloy block are placed on the round platform of hydrogen generator reaction zone in advance; Hydroborate alkaline solution is stored in container for storing liquid in advance by the import of container for storing liquid top; Start infusion pump, hydroborate alkaline solution, through tubing, infusion pump, hydrogen generator import tubing, transfusion control valve and stainless steel tube, is sprayed onto hydrogen generator reaction zone aluminum alloy surface; Reaction produces hydrogen, and hydrogen, through separatory membrane, enters hydrogen storage chamber; When hydrogen storage chamber's hydrogen pressure increases gradually, promote transfusion control valve triangles cone, progressively withstand the fluid inlet of transfusion control valve, stop hydroborate alkaline solution to enter; When hydrogen storage chamber's hydrogen pressure reduces, hydroborate alkaline solution pushes transfusion control valve triangles cone open, through stainless steel tube, is sprayed onto the aluminum alloy surface reaction hydrogen manufacturing of hydrogen generator reaction zone.
Compared with existing hydrogen production process, the advantage that the present invention has and positively effect: 1) practicality is wide; The present invention is applicable to aluminium alloy/borohydride hydrolytic hydrogen production, comprises aluminium alloy and borohydride hydrolytic hydrogen production; Also other hydrogen manufacturing material aluminium/basic hydrolysis hydrogen manufacturing, alkaline earth metal hydride hydrolytic hydrogen production, alkalimetal hydride hydrolytic hydrogen production is applicable to.2) speed of reaction is easy to control, reaction efficiency is high; The hydrogen pressure that hydrogen generating system can produce according to hydrolysis reaction, the input rate of regulation and control hydroborate alkali lye and input, the hydrolysis reaction of regulator control system; In addition, Installed System Memory, at certain hydrogen pressure, also ensure that hydrogen stable output; Adopt the method that aluminium alloy is unsettled, hydroborate alkaline solution sprays, ensure that aluminium alloy is exposed in sodium borohydride alkaline solution always, therefore, this hydrogen production process has the high feature of reaction efficiency.3) the present invention has the feature of cheapness, environmental protection; Hydrogen manufacturing material aluminium alloy/borohydride hydrolytic product recovery capable of circulation, environmental friendliness is pollution-free; In addition, because hydrolysis reaction is controlled, the hydrogen pressure of hydrogen generating system maintains lower level, and hydrogen generating system can adopt cheapness, light material to make.4) the present invention is particularly suitable for the hydrogen supply of portable fuel battery or combustion machine.
Accompanying drawing illustrates:
Fig. 1 is structural representation of the present invention.
In figure, 1-gas valve, 2-hydrogen storage chamber, 3-column; 4-separatory membrane; 5-stainless steel tube; 6-fluid reservoir; 7-annulus pillar; 8-hydrogen generator import tubing; The import of 9-fluid reservoir; 10-infusion pump; 11-infuses control valve; 12-pore.
Embodiment
The following examples can make the present invention of those skilled in the art's comprehend, but do not limit the present invention in any way.
Embodiment 1
As shown in Figure 1, the present invention includes hydrogen generator, container for storing liquid, infusion pump and liquid-transport pipe-line; Hydrogen generator comprises tank body and lid; Tank body comprises reaction chamber and hydrogen storage chamber; Container for storing liquid top arranges import, and bottom arranges outlet, and bottom end outlet connects hydrogen generator import tubing through tubing, infusion pump, tubing; Hydrogen generator import tubing end sealing, has a pore from 0 ~ 0.5cm place, top, connects hydrogen generator hydrogen storage chamber; A control valve of infusing is had from 1 ~ 4cm place, hydrogen generator import tubing top; Transfusion control valve is that two equivalent triangles cones are connected, and transfusion control valve upper and lower arranges upright open triangles cone and handstand open triangles cone respectively; The upright open triangles cone on transfusion control valve top and the handstand open triangles cone middle of transfusion control valve bottom have an aperture to be connected stainless steel tube to enter hydrogen generator reaction zone, stainless steel tube is downward-sloping with level be 5 ~ 15 ° around hydrogen generator inwall, and be welded on hydrogen generator inwall; The watering mouth that the distribution of stainless steel tube bottom even is circular, tiny; Directly over stainless steel tube, gas-liquid separation membrane is set; Separatory membrane is reaction chamber, is hydrogen storage chamber under separatory membrane; Between hydrogen storage chamber's inwall and reaction chamber wall, around equally distributed 4 root posts of hydrogen storage chamber's welding; Column penetrates separatory membrane, and separatory membrane is moved freely thereon; 2 opening up round platforms are symmetrical arranged immediately below stainless steel tube; Have production well, connecting gas transmission pipe in the middle of lid, gas transmission pipe end connects air pressure valve; Circular hole is uniformly distributed, through polytetrafluoro pad, flange fixing seal around tank body and lid.
During work, first aluminium alloy bars, aluminium alloy block are placed on the round platform of hydrogen generator reaction zone in advance; Hydroborate alkaline solution is stored in container for storing liquid in advance by the import of container for storing liquid top; Start infusion pump, hydroborate alkaline solution through tubing, infusion pump, hydrogen generator import tubing, transfusion control valve, and is sprayed onto hydrogen generator reaction zone aluminum alloy surface by stainless steel tube; Aluminium alloy and hydroborate alkaline solution react and produce hydrogen, and hydrogen, through separatory membrane, enters hydrogen storage chamber; And hydroborate alkaline solution is taken advantage of a situation along aluminum alloy surface and stayed, thus ensure that fully contacting and reaction of aluminium alloy and hydroborate alkaline solution.Remaining a small amount of unreacted hydroborate alkaline solution and aluminium alloy also can bottom reaction zone contact reacts.When hydrogen storage chamber's hydrogen pressure increases gradually, hydrogen pressure promotes transfusion control valve triangles cone downwards, progressively withstand the fluid inlet of transfusion control valve, reduce hydroborate alkaline solution and enter, thus reduce the carrying out of the aluminium alloy/borohydride hydrolytic reaction of hydrogen generator reaction zone; Just because of the hydrogen pressure of hydrogen storage chamber, thus ensure that the steady output of hydrogen in hydrogen generating system; When hydrogen storage chamber's hydrogen pressure reduces, hydroborate alkaline solution pushes again transfusion control valve triangles cone gradually open, and through stainless steel tube, be sprayed onto the aluminum alloy surface reaction hydrogen manufacturing of hydrogen generator reaction zone, hydrolysis reaction carries out again.
Claims (1)
1., based on a miniature hydrogen generating system hydrogen production process for aluminium alloy/hydroborate system hydrolysis reaction, it is characterized in that: miniature hydrogen generating system comprises hydrogen generator, container for storing liquid, infusion pump and liquid-transport pipe-line; Hydrogen generator is hollow cylindrical body, comprises tank body and lid; Tank body comprises reaction chamber and hydrogen storage chamber; The peripheral coated rectangular parallelepiped container for storing liquid of hydrogen generator; The spacing of container for storing liquid inwall and hydrogen generator outer wall is 5 ~ 30cm; Hydrogen generator is higher than container for storing liquid 5 ~ 10cm; Container for storing liquid top arranges import, and bottom arranges outlet, and bottom end outlet connects hydrogen generator import tubing through tubing, infusion pump, tubing; Hydrogen generator import tubing and hydrogen generator tank body contour; Hydrogen generator import tubing end sealing, has a pore from 0 ~ 0.5cm place, top, connects hydrogen generator hydrogen storage chamber; A control valve of infusing is had from 1 ~ 4cm place, hydrogen generator import tubing top; Transfusion control valve is that two equivalent triangles cones are connected, and transfusion control valve upper and lower arranges upright open triangles cone and handstand open triangles cone respectively, and the shape of all pyrometric cones is identical with volume; The upright open triangles cone on transfusion control valve top and the handstand open triangles cone spacing of transfusion control valve bottom are 1 ~ 3cm, distance has an aperture and enters hydrogen generator reaction zone through stainless steel tube therebetween, stainless steel tube is downward-sloping with level be 5 ~ 15 ° around hydrogen generator inwall, and be welded on hydrogen generator inwall; The watering mouth that the distribution of stainless steel tube bottom even is circular, tiny; Directly over stainless steel tube, 0.5 ~ 2cm arranges gas-liquid separation membrane; Tank body is divided into reaction chamber and hydrogen storage chamber by separatory membrane; Hydrogen storage chamber's inner diameter is less than reaction chamber wall diameter 1 ~ 3cm, and between hydrogen storage chamber's inwall and reaction chamber wall, around equally distributed 4 root posts of hydrogen storage chamber's welding; Column penetrates separatory membrane, and the diameter of column is between 0.1 ~ 0.3cm, and height is between 0.5 ~ 1.5cm; Separatory membrane can move freely on column; Immediately below stainless steel tube, 10 ~ 30cm is symmetrical arranged 2 opening up round platforms; Have production well, connecting gas transmission pipe in the middle of lid, gas transmission pipe end connects air pressure valve; Circular hole is uniformly distributed, through polytetrafluoro pad, flange fixing seal around tank body and lid; Aluminium alloy bars, aluminium alloy block are placed on the round platform of hydrogen generator reaction zone in advance; Hydroborate alkaline solution is stored in container for storing liquid in advance by the import of container for storing liquid top; Start infusion pump, hydroborate alkaline solution, through tubing, infusion pump, hydrogen generator import tubing, transfusion control valve and stainless steel tube, is sprayed onto hydrogen generator reaction zone aluminum alloy surface; Reaction produces hydrogen, and hydrogen, through separatory membrane, enters hydrogen storage chamber; When hydrogen storage chamber's hydrogen pressure increases gradually, promote transfusion control valve triangles cone, progressively withstand the fluid inlet of transfusion control valve, stop hydroborate alkaline solution to enter; When hydrogen storage chamber's hydrogen pressure reduces, hydroborate alkaline solution pushes transfusion control valve triangles cone open, through stainless steel tube, is sprayed onto the aluminum alloy surface reaction hydrogen manufacturing of hydrogen generator reaction zone.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210357701.1A CN102910582B (en) | 2012-09-20 | 2012-09-20 | Aluminum alloy/hydroboron hydrolysis reaction-based miniature hydrogen production system and hydrogen production method |
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| CN201210357701.1A CN102910582B (en) | 2012-09-20 | 2012-09-20 | Aluminum alloy/hydroboron hydrolysis reaction-based miniature hydrogen production system and hydrogen production method |
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| CN102910582B true CN102910582B (en) | 2015-02-18 |
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| CN105366639B (en) * | 2015-12-10 | 2017-11-03 | 湖北工业大学 | A kind of Portable Automatic control aluminum-water reaction hydrogen producer |
| CN108483395B (en) * | 2018-04-20 | 2020-11-03 | 四川大学 | Hydrogen production and storage integrated device |
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| US20070036711A1 (en) * | 2005-08-11 | 2007-02-15 | Ardica Technologies Inc. | Hydrogen generator |
| CN101973520B (en) * | 2010-09-27 | 2012-05-30 | 中国计量学院 | Portable hydrogen generator based on aluminium hydrolysis reaction and control method |
| SG182885A1 (en) * | 2011-02-01 | 2012-08-30 | Horizon Fuel Cell Technologies Pte Ltd | Hydrogen generator and method of operating it |
| CN102167285A (en) * | 2011-03-02 | 2011-08-31 | 上海师范大学 | Portable, safe and controllable hydrolysis hydrogen-producing device |
| CN202864905U (en) * | 2012-09-20 | 2013-04-10 | 中国计量学院 | Aluminum alloy/hydroboron hydrolysis-based miniature hydrogen production system |
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Granted publication date: 20150218 Termination date: 20160920 |