CN101417787A - Borohydride hydrogen making system - Google Patents

Borohydride hydrogen making system Download PDF

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Publication number
CN101417787A
CN101417787A CNA2007102021816A CN200710202181A CN101417787A CN 101417787 A CN101417787 A CN 101417787A CN A2007102021816 A CNA2007102021816 A CN A2007102021816A CN 200710202181 A CN200710202181 A CN 200710202181A CN 101417787 A CN101417787 A CN 101417787A
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China
Prior art keywords
chamber
hydrogen
borohydride
making system
reaction
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Pending
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CNA2007102021816A
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Chinese (zh)
Inventor
肖钢
侯晓峰
王玉晓
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Hanergy Technology Co Ltd
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Hanergy Technology Co Ltd
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Priority to CNA2007102021816A priority Critical patent/CN101417787A/en
Publication of CN101417787A publication Critical patent/CN101417787A/en
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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
    • 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
    • Y02E60/50—Fuel cells

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Abstract

The invention discloses a hydrogen producing system by borohydride, which comprises a fuel chamber (2) used for storing a reaction liquid, a reaction chamber (4) used for placing catalysts and a waste material chamber (9), wherein, a reaction liquid inlet (11) is arranged at the fuel chamber (2), a waste material liquid outlet (1) is arranged at the waste material chamber (9), the fuel chamber (2) and the reaction chamber (4) are connected by a controlling valve(3), the upper end of the reaction chamber (4) is connected with the waste material chamber (9) by a connecting pipe (5) and a one-way valve (6), a gas-liquid separating chamber (7) is arranged at the upper part of the waste material chamber (9) and provided with a hydrogen outlet (8), an alkali removing device (10) is arranged between the gas-liquid separating chamber (7) and the hydrogen outlet (8), and absorption substances or organic acids are arranged in the alkali removing device (10). The invention is characterized by compact structure, simple operation, easy maintenance and the like, and can effectively inhibit damages of lye in the hydrogen to fuel battery piles.

Description

A kind of borohydride hydrogen making system
Technical field
The present invention relates to a kind of Preparation of Hydrogen device, relate to a kind of borohydride hydrogen making system concretely, belong to the fuel cell hydrogen source field.
Background technology
Hydrogen is a kind of clean fuel, because its can the hydrogen consumption device for example in fuel cell or the oil engine with oxygen reaction generate energy and water, in reaction, do not have other by product, therefore, use hydrogen to act as a fuel and effectively solved the environmental problem of following when using oil fuel.But, how safe and effective hydrogen gas storage is that the technician is in the problem of making great efforts to solve always, many hydrogen carriers comprise that hydrocarbon, metal hydride and chemical hydride all are regarded as storing hydrogen and supply system, for example alkalimetal hydride, composite alkali aluminum hydride and alkali metal borohydride.Wherein hydroborate is a kind of material of high storage hydrogen richness, can the catalytic hydrolysis release hydrogen as heavy body, High Purity Hydrogen source material, again can be directly by electrochemical means as the heavy body negative material, in typical heterogeneous catalytic system, hydroborate and water generates hydrogen and boratory stoichiometric reaction can be represented with following chemical reaction:
But that shortcoming is a weight is big, the storage hydrogen efficiency is low, even and at normal temperatures, hydroborate solution also can very fast hydrolysis fall half.Therefore, can in actual life, be applied, must hold it in the strong alkali solution at ordinary times in order to make hydroborate.Remaining hydroborate also all must remain in the strong alkali solution.It is a thermopositive reaction that hydroborate decomposes, every generation 1molH 2Emit the 75kJ heat, thereby make the temperature of reaction solution raise.Under higher temperature, the hydrogen of generation has more sodium hydroxide.If do not remove the sodium hydroxide in the hydrogen, then can damage the pile of fuel cell.
U.S. Pat 715033B2 discloses a kind of hydrogen generator system, it utilizes volume-exchange shell and the hydrogen separation chamber that produces the fuel material of hydrogen in order to storage reaction, this system comprises one or more permeable membranes, and it makes hydrogen to stop the aqueous solution to pass through this film by this film.Though this system has solved the alkali problem of removing of fuel cell to a certain extent, but because this film stops the aqueous solution to pass through, the hydrogen that makes is drying regime, before entering the pile of fuel cell, also need humidification, increased running cost, permeable membrane is dirty easily stifled in addition, needs periodic cleaning and replacing, is not easy to routine maintenance.
Summary of the invention
In order to solve the problems of the technologies described above, the invention provides a kind of compact construction, the simple to operate and novel borohydride hydrogen making system being convenient to safeguard, effectively suppressed the infringement of the alkali lye in the hydrogen to fuel cell pile.
Its concrete technical scheme is as follows: a kind of borohydride hydrogen making system, comprise the fuel chambers that is used for depot reaction liquid, be used to place the reaction chamber and the waste chamber of catalyzer, wherein fuel chambers is provided with the reaction solution import, waste chamber is provided with the outlet of waste material liquid, fuel chambers is connected by control valve with reaction chamber, the reaction chamber upper end is connected with waste chamber with check valve by pipe connecting, the top of waste chamber is provided with gas-liquid separation chamber, which is provided with hydrogen outlet, it is characterized in that: between gas-liquid separation chamber and hydrogen outlet, be provided with except that the alkali device, be provided with adsorbent or organic acid described removing in the alkali device.
Preferably, place organic acid described removing in the alkali device, the alkali because organic acid can neutralize in the hydrogen that generates, and moisture is retained in the hydrogen, and when hydrogen enters the pile of fuel cell, do not need humidification, saved production cost.
Described adsorbent can be one or several the mixture among absorbent cotton, molecular sieve, gac, discolour silica gel or FeCl3, the P2O5.
Described organic acid can be one or several the mixture in citric acid, acetate, toxilic acid, Succinic Acid or the oxysuccinic acid.
Described catalyzer can for any one can the catalytic decomposition borohydride hydrogen making catalyzer, for example can comprise one or more the mixture in Raney's nickel catalyst of fixed bed, fixed bed raney cobalt catalyst or the fixed bed raney nickel-cobalt catalyst.
The edge of described waste chamber is fixed on the whole device, and described waste chamber is made of elastic material, and described elastic material can be rubber, resilient sheet metal, high elastic rubber preferably, so, when not having waste liquid to enter, whole waste chamber swim in reaction solution above.Thereby make that the space of fuel chambers is bigger, saved volume, make whole device have bigger hydrogen-storage amount.
In order to guarantee that the reaction solution in the fuel chambers all flows in the reaction chamber, make sufficient reacting carry out, described reaction chamber can be arranged at the below of fuel chambers or be arranged on the side of fuel chambers, is positioned on the same horizontal plane with described fuel chambers.
Described control valve is used to regulate the hydroborate liquid flow rate that is flowed to reaction chamber by fuel chambers, to realize producing the adjusting of hydrogen speed.After control valve is opened, reaction solution in the fuel chambers flows into reaction chamber through control valve, the catalyzer that is fixed in solution and the reaction chamber contacts the back and produces hydrogen, hydrogen drives liquid and flows into waste chamber along pipe connecting through check valve, described check valve is used for controlling gas and the flow direction waste chamber in the reaction chamber, but the solution in the waste chamber then can not flow to reaction chamber by check valve.To the whereabouts, gas then makes progress liquid under the effect of gravity, finishes gas-liquid separation for the first time, and on reaction solution, hydrogen carries out the second time through gas-liquid separation chamber to be separated subsequently.In the indoor nickel foam that is provided with of described gas-liquid separation, be used for stopping the alkali lye of gas along with gas enters hydrogen outlet.
Before hydrogen enters hydrogen outlet, by the described alkali device that removes, further absorb the micro-alkali that contains in the hydrogen, become then and can flow out through hydrogen outlet for the pure hydrogen of Proton Exchange Membrane Fuel Cells use.
Reaction solution can be the alkaline solution of hydroborate, and described hydroborate can be borohydride salt (M (BH 4) n), three borohydride salt (MB 3H 8), decahydro ten borate (M 2B 10H 10), 13 hydrogen, ten borate (MB 10H 13), dodecahydrododecaborates (M 2B 12H 12), ten octahydros, 20 borate (M 2B 20H 18) in one or more mixture, wherein, M is one or several the mixture in the positively charged ion of basic metal, alkaline-earth metal or aluminium.
Described alkaline solution can be a kind of or wherein several mixture in sodium hydroxide, potassium hydroxide, hydrated barta, the lithium hydroxide solution.
Described alkaline concentration is 5-30wt%.
Compared with prior art, borohydride hydrogen making system disclosed in this invention has following advantage: 1. hydrogen generating system is a double-chamber unit, reaction solution is flowed through behind the catalyzer, no longer flow back to fuel chambers, but flow to waste chamber, thereby make that the reaction solution that at every turn enters reaction chamber all is fresh reaction solution, guaranteed constant hydrogen generating rate; Since waste chamber be to constitute by elastic material, when not having waste liquid to enter, whole waste chamber swim in reaction solution above, thereby make that the space of fuel chambers is bigger, saved volume, make whole device have bigger hydrogen-storage amount; 3. can regulate flow fuel to realize producing the adjusting of hydrogen speed by regulating liquid flow control valve; 4. compact construction can be realized controlled hydrogen production reaction effectively; 5. remove the alkali device in the system, simple in structure, can effectively remove the sodium hydroxide that contains in the hydrogen, obtain purified hydrogen, avoided infringement to fuel cell.
Description of drawings
Fig. 1 is the structural representation before the sodium borohydride hydrogen generating system reaction according to the preferred embodiment of the invention.
Fig. 2 is the reacted structural representation of sodium borohydride hydrogen generating system of another preferred embodiment according to the present invention.
Embodiment
Below by embodiment, and in conjunction with the accompanying drawings, technical scheme of the present invention is described in further detail.
Embodiment 1
As shown in Figure 1, a kind of borohydride hydrogen making system, comprise fuel chambers 2, the waste chamber 9 that reaction chamber 4 and rubber are made, fuel chambers 2 is provided with reaction solution import 11, waste chamber 9 is provided with waste material liquid outlet 1, fuel chambers 2 is connected by control valve 3 with reaction chamber 4, reaction chamber 4 is positioned at the side of fuel chambers 2, be positioned on the same horizontal plane with it, reaction chamber 4 upper ends are connected with waste chamber 9 with check valve 6 by pipe connecting 5, the edge of waste chamber 9 is fixed on the whole device, the top of waste chamber 9 is provided with gas-liquid separation chamber 7, which is provided with hydrogen outlet 8, between gas-liquid separation chamber and hydrogen outlet, be provided with, be provided with activated carbon and discolour silica gel described removing in the alkali device 10 except that alkali device 10, Raney's nickel catalyst of fixed bed is fixed in the reaction chamber 4, be provided with the alkaline solution of sodium borohydride in the fuel chambers 2, wherein alkaline solution is a sodium hydroxide solution, and concentration is 15wt%;
Fresh feed liquid enters fuel chambers 2 by import 11, after control valve 3 is opened, reaction solution in the fuel chambers 2 flows into reaction chamber 4 through control valve 3, solution contacts the back and produces hydrogen with Raney's nickel catalyst of fixed bed in the reaction chamber 4, hydrogen drives liquid and flows into waste chamber 9 along pipe connecting 5 through check valve 6, and to the whereabouts, gas then makes progress liquid under the effect of gravity, finish gas-liquid separation for the first time, waste material liquid is through outside the outlet 1 discharge system.Hydrogen carries out flash liberation again through the gas-liquid separation chamber 7 that is provided with nickel foam subsequently on reaction solution.
Before hydrogen enters hydrogen outlet 8, by removing alkali device 10, further absorb the micro-alkali that contains in the hydrogen, become then and can flow out through hydrogen outlet 8 for the pure hydrogen of Proton Exchange Membrane Fuel Cells use.
Embodiment 2
As shown in Figure 2, a kind of borohydride hydrogen making system, comprise fuel chambers 2, the waste chamber 9 that reaction chamber 4 and resilient blade are made, wherein reaction chamber 4 is positioned at the below of fuel chambers 2, is provided with acetate described removing in the alkali device 10, the fixed bed raney cobalt catalyst is fixed in the reaction chamber 4, be provided with the alkaline solution of three POTASSIUM BOROHYDRIDE in the fuel chambers 2, wherein alkaline solution is a potassium hydroxide solution, and concentration is 5wt%.All the other are with embodiment 1.
Embodiment 3
As shown in Figure 1, a kind of borohydride hydrogen making system comprises the waste chamber 9 that high elastic rubber is made, and fuel chambers 2 and reaction chamber 4 are provided with FeCl described removing in the alkali device 10 3, the fixed bed raney nickel-cobalt catalyst is fixed in the reaction chamber 4, is provided with the alkaline solution of decahydro ten lime borates and decahydro ten aluminum borates in the fuel chambers 2, and wherein alkaline solution is a barium hydroxide solution, and concentration is 26wt%.All the other are with embodiment 1.
Embodiment 4
As shown in Figure 1, a kind of borohydride hydrogen making system, comprise the waste chamber 9 that rubber is made, fuel chambers 2 and reaction chamber 4, be provided with toxilic acid, Succinic Acid and oxysuccinic acid described removing in the alkali device 10, the fixed bed raney cobalt catalyst is fixed in the reaction chamber 4, is provided with the alkaline solution of POTASSIUM BOROHYDRIDE, ten dihydros, ten hypoboric acid lithiums and ten octahydros, 20 aluminum borates in the fuel chambers 2, wherein alkaline solution is lithium hydroxide and potassium hydroxide solution, and concentration is 30wt%.All the other are with embodiment 1.
Embodiment 5
As shown in Figure 1, a kind of borohydride hydrogen making system comprises the waste chamber 9 that rubber is made, and fuel chambers 2 and reaction chamber 4 are provided with absorbent cotton, molecular sieve, P described removing in the alkali device 10 2O 5And gac, the fixed bed raney cobalt catalyst is fixed in the reaction chamber 4, is provided with the alkaline solution of POTASSIUM BOROHYDRIDE and ten dihydros, ten hypoboric acid lithiums in the fuel chambers 2, and wherein alkaline solution is lithium hydroxide, sodium hydroxide and barium hydroxide solution, and concentration is 20wt%.All the other are with embodiment 1.
Embodiment 6
As shown in Figure 1, a kind of borohydride hydrogen making system, comprise the waste chamber 9 that rubber is made, fuel chambers 2 and reaction chamber 4, be provided with citric acid and toxilic acid described removing in the alkali device 10, the fixed bed raney nickel-cobalt catalyst is fixed in the reaction chamber 4, is provided with the alkaline solution of ten dihydros, ten hypoboric acid aluminium in the fuel chambers 2, wherein alkaline solution is potassium hydroxide and barium hydroxide solution, and concentration is 18wt%.All the other are with embodiment 1.

Claims (11)

  1. [claim 1] a kind of borohydride hydrogen making system, comprise the fuel chambers (2) that is used for depot reaction liquid, be used to place the reaction chamber (4) and the waste chamber (1) of catalyzer, wherein fuel chambers (2) is provided with reaction solution import (11), waste chamber (9) is provided with waste material liquid outlet (1), fuel chambers (2) is connected by control valve (3) with reaction chamber (4), reaction chamber (4) upper end is connected with waste chamber (9) with check valve (6) by pipe connecting (5), gas-liquid separation chamber (7) is arranged at the top of waste chamber (9), which is provided with hydrogen outlet (8), it is characterized in that: between gas-liquid separation chamber (7) and hydrogen outlet (8), be provided with, be provided with adsorbent or organic acid described removing in the alkali device (10) except that alkali device (10)
  2. [claim 2] borohydride hydrogen making system according to claim 1, described adsorbent are absorbent cotton, molecular sieve, gac, discolour silica gel or FeCl 3, P 2O 5In one or several mixture.
  3. [claim 3] borohydride hydrogen making system according to claim 1, described organic acid are one or several the mixture in citric acid, acetate, toxilic acid, Succinic Acid or the oxysuccinic acid.
  4. [claim 4] borohydride hydrogen making system according to claim 1, described waste chamber (9) is made of elastic material, and described elastic material is rubber or resilient sheet metal.
  5. [claim 5] borohydride hydrogen making system according to claim 4, described elastic material are high elastic rubber.
  6. [claim 6] borohydride hydrogen making system according to claim 1, described gas-liquid separation chamber is provided with nickel foam in (7).
  7. [claim 7] borohydride hydrogen making system according to claim 1, described reaction chamber (4) can be arranged at the below of fuel chambers (2) or be arranged on the side of fuel chambers (2), are positioned on the same horizontal plane with described fuel chambers (2).
  8. [claim 8] borohydride hydrogen making system according to claim 1, described reaction solution are the alkaline solution of hydroborate.
  9. [claim 9] borohydride hydrogen making system according to claim 8, described hydroborate are borohydride salt (M (BH 4) n), three borohydride salt (MB 3H 8), decahydro ten borate (M 2B 10H 10), 13 hydrogen, ten borate (MB 10H 13), dodecahydrododecaborates (M 2B 12H 12), ten octahydros, 20 borate (M 2B 20H 18) in one or more mixture, wherein, M is one or several the mixture in the positively charged ion of basic metal, alkaline-earth metal or aluminium.
  10. [claim 10] borohydride hydrogen making system according to claim 8, described alkaline solution are a kind of or wherein several mixture in sodium hydroxide, potassium hydroxide, hydrated barta, the lithium hydroxide solution.
  11. [claim 11] according to Claim 8 or 10 described borohydride hydrogen making systems, described alkaline concentration is 5-30wt%.
CNA2007102021816A 2007-10-22 2007-10-22 Borohydride hydrogen making system Pending CN101417787A (en)

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Application Number Priority Date Filing Date Title
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103121663A (en) * 2011-11-18 2013-05-29 扬光绿能股份有限公司 Hydrogen generating equipment
CN108238587A (en) * 2016-12-27 2018-07-03 天津维金斯环保科技有限公司 A kind of hydrogen cleaning solid for sodium borohydride hydrogen manufacturing removes alkali device
CN109415205A (en) * 2017-04-22 2019-03-01 银河测试有限公司 Equipment for generating hydrogen
CN116514059A (en) * 2023-07-03 2023-08-01 四川卡文智氢新能源有限公司 Waste aluminum hydrogen production purification device and use method

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103121663A (en) * 2011-11-18 2013-05-29 扬光绿能股份有限公司 Hydrogen generating equipment
CN108238587A (en) * 2016-12-27 2018-07-03 天津维金斯环保科技有限公司 A kind of hydrogen cleaning solid for sodium borohydride hydrogen manufacturing removes alkali device
CN108238587B (en) * 2016-12-27 2021-08-13 天津维金斯环保科技有限公司 Hydrogen purification solid alkali remover for hydrogen production by sodium borohydride
CN109415205A (en) * 2017-04-22 2019-03-01 银河测试有限公司 Equipment for generating hydrogen
CN116514059A (en) * 2023-07-03 2023-08-01 四川卡文智氢新能源有限公司 Waste aluminum hydrogen production purification device and use method
CN116514059B (en) * 2023-07-03 2023-10-27 四川卡文智氢新能源有限公司 Waste aluminum hydrogen production purification device and use method

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Open date: 20090429