CN101434378A - Hydrogen production device by borohydride - Google Patents

Hydrogen production device by borohydride Download PDF

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Publication number
CN101434378A
CN101434378A CNA2007102025022A CN200710202502A CN101434378A CN 101434378 A CN101434378 A CN 101434378A CN A2007102025022 A CNA2007102025022 A CN A2007102025022A CN 200710202502 A CN200710202502 A CN 200710202502A CN 101434378 A CN101434378 A CN 101434378A
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molecular sieve
hydrogen
hydrogen production
production device
fuel container
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CNA2007102025022A
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Chinese (zh)
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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 CNA2007102025022A priority Critical patent/CN101434378A/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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  • Hydrogen, Water And Hydrids (AREA)

Abstract

The invention relates to a hydrogen production device by hydroboron, which comprises a fuel container (1) and an inner-tube reactor (3) arranged in the fuel container (1), wherein, the fuel container comprises a shell (4) on which a demountable gas-liquid separation part (5) is arranged; the inner-tube reactor (3) is provided with an opening at the upper end, the lower end thereof is communicated with the interior of the fuel container (1); and the top part of the gas-liquid separation part (5) is provided with a gas outlet (6). The hydrogen production device has the advantages of compact structure, low cost, simple operation, being capable of providing clean hydrogen and the like, and pertains to the field of hydrogen gas generators providing hydrogen for fuel cells.

Description

A kind of hydrogen production device by borohydride
Technical field
The present invention relates to a kind of Preparation of Hydrogen device, relate to a kind of hydrogen production device by borohydride specifically.
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:
Figure A200710202502D00031
But sodium borohydride is hydrolysis very easily, even at normal temperatures, sodium borohydride 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 sodium borohydride.Remaining hydroborate also all must remain in the strong alkali solution.The sodium borohydride hydrolysis is a thermopositive reaction, every generation 1molH 2Emit the 75kJ heat, thereby make the temperature of reaction solution raise.Under higher temperature, the hydrogen of generation can be taken the alkali lye in the solution out of.If do not remove the alkaline impurities in the hydrogen, then can the pile of fuel cell be caused damage, shortened the work-ing life of pile.
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 this system exists structure compact inadequately, is difficult to be applicable to the small-sized hydrogen storage equipment of using, and its used permeable membrane is dirty easily stifled, need periodic cleaning and replacing, increased the difficulty of running cost and routine maintenance.
Summary of the invention
The technical problem to be solved in the present invention provides a kind of compact construction, with low cost, simple to operate, hydrogen production device by borohydride that clean hydrogen can be provided.
For solving the problems of the technologies described above, hydrogen production device by borohydride of the present invention comprises fuel container and is located at the interior interior pipe reactor of fuel container that concrete structure is as follows:
Described fuel container comprises housing, which is provided with dismountable gas-liquid separation part; Pipe reactor upper end open in described, its lower end and fuel container internal communication; The top of described gas-liquid separation part is provided with pneumatic outlet.
Described gas-liquid separation part can be connected sealing by spiral with housing, also can the clamping sealing.
The pipe reactor lower end is provided with valve in described.
The bottom of described gas-liquid separation part is provided with a ventilation property dividing plate, filling foamed metal on it, and the foamed metal that hydrogen partly loads through gas-liquid separation can be realized effective gas-liquid separation.Hydrogen can remove most liquid wherein through behind the foamed metal.
Described foamed metal is a kind of in nickel foam, foam iron, foam copper, the foam ambrose alloy.
Described gas outlet also is provided with one and removes the alkali device.
Molecular sieve, absorbent cotton, sodium polyacrylate, polyacrylamide, gac, discolour silica gel and FeCl are equipped with in the described alkali device inside of removing 3H 2A kind of or wherein several mixture among the O.
The described alkali device that removes detachably is located at gas outlet.
Described molecular sieve is a kind of or wherein several mixture in 3A molecular sieve, 4A molecular sieve, 5A molecular sieve, 13X HP molecular sieve, 13X PG molecular sieve, 13XAPG molecular sieve, the XH-5 molecular sieve.
Hydrogen production device by borohydride provided by the invention, the gas-liquid separation part is disassembled from housing, then fuel solution is injected in the fuel container, with catalyst loading in interior pipe reactor, again the gas-liquid separation part is fitted together with housing, the two can helixseal connect also and can clamping seal.When needing to start device for producing hydrogen, the valve of pipe reactor bottom in opening, fuel solution then can flow into interior pipe reactor, under the effect of catalyzer, begin to produce hydrogen, because the speed of reaction of hydroborate catalyzing manufacturing of hydrogen is very fast, gush on a large amount of hydrogen of generation are quick, the reaction solution in the interior pipe reactor is constantly taken out of from the opening part of interior pipe reactor upper end, again turn back in the fuel container, form fuel returns fuel container to interior pipe reactor from fuel container circulation.Catalyticreactor of the present invention is built-in, need not transport pipe, the valve of external fuel solution, also need not external recycle pump, and is simple and compact for structure, is particularly useful for the small-sized hydrogen storage equipment of using, or volume had the hydrogen storage equipment of using of strict restriction.
The hydrogen that generates is from the effusion suitable for reading of interior pipe reactor, the hydrogen of this moment contains more alkali lye, after it is overflowed, the alkali lye that hydrogen contains can fall under the effect of self gravitation, hydrogen then can rise, therefore the hydrogen of overflowing from interior pipe reactor upper end open is partly finished primary gas-liquid separation in gas-liquid separation, and most alkali lye can further be removed at this.Partly load foamed metal in gas-liquid separation and can more effectively realize gas-liquid separating function, can make the alkali lye and the Hydrogen Separation of the overwhelming majority.Only contain a small amount of alkali lye through the hydrogen after the gas-liquid separation portion, remove the alkali device and can further remove the alkali lye that contains in the hydrogen through what the exit was provided with again.Remove in the alkali device and be equipped with, as molecular sieve, absorbent cotton, sodium polyacrylate, polyacrylamide, gac, discolour silica gel and FeCl except that alkaline agent 3H 2A kind of or wherein several mixture among the O, it is cheap and easy to get that these remove alkaline agent, and good impurity removing effect, removing the alkali device is detachable apparatus, therefore can with the supporting use of the fuel solution in the fuel container, promptly in advance in the based on fuel container amount of fuel solution dispose except that the amount of removing alkaline agent that needs in the alkali device, fuel solution runs out of, stop to produce hydrogen, what more renew simultaneously when changing fresh fuel solution removes the alkali device.Exhausted removes alkaline agent and both can reprocessing cycle use, and also can directly throw aside.Since use to remove alkaline agent cheap and easy to get, it is effective to remove alkali, and removes the alkali device and can match with fuel solution and change easily, so the present invention has advantage with low cost, simple to operate, that clean hydrogen can be provided.
Description of drawings
The present invention is further detailed explanation below in conjunction with the drawings and specific embodiments.
Fig. 1 is a structural representation of the present invention;
Fig. 2 is the structural representation of the present invention that is provided with except that the alkali device.
Embodiment
A kind of device for producing hydrogen of hydroborate, as shown in Figure 1 and Figure 2, the device for producing hydrogen of hydroborate of the present invention comprises fuel container 1 and the interior pipe reactor 3 that is located in the fuel container 1, concrete structure is as follows:
Described fuel container comprises housing 4, which is provided with dismountable gas-liquid separation part 5; Pipe reactor 3 upper end open in described, its lower end and fuel container 1 internal communication; The top of described gas-liquid separation part 5 is provided with pneumatic outlet 6.
Pipe reactor 3 lower ends are provided with valve 2 in described.
The bottom of described gas-liquid separation part 5 is provided with a ventilation property dividing plate, filling foamed metal 8 on it.
Described foamed metal 8 is a kind of in nickel foam, foam iron, foam copper, the foam ambrose alloy.
Described pneumatic outlet 6 places also are provided with one and remove alkali device 7.
Molecular sieve, absorbent cotton, sodium polyacrylate, polyacrylamide, gac, discolour silica gel and FeCl are equipped with in described alkali device 7 inside of removing 3H 2A kind of or wherein several mixture among the O.
The described alkali device 7 that removes detachably is located at pneumatic outlet 6 places.
Described molecular sieve is a kind of or wherein several mixture in 3A molecular sieve, 4A molecular sieve, 5A molecular sieve, 13X HP molecular sieve, 13X PG molecular sieve, 13XAPG molecular sieve, the XH-5 molecular sieve.
Above-mentioned fuel solution is the alkaline solution of hydroborate.
Alkali in the above-mentioned hydroborate alkaline solution can be a kind of or wherein several mixture in sodium hydroxide, potassium hydroxide, hydrated barta, the lithium hydroxide.
Above-mentioned hydroborate comprises 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.
Above-mentioned catalyzer be can catalysis hydroborate decomposing hydrogen-production fixed bed catalyst, for example fixed-bed Raney nickel, thunder Buddhist nun cobalt, Raney's nickel cobalt, fixed-bed Raney nickel, thunder Buddhist nun cobalt, the Raney's nickel cobalt of load minute amount of noble metal such as platinum, ruthenium, rhodium etc., one or several in the nickel foam of load minute amount of noble metal such as platinum, ruthenium, rhodium etc., foam cobalt, the nickel foam cobalt etc.
The use of the device for producing hydrogen of hydroborate of the present invention is as follows:
As shown in Figure 1, gas-liquid separation part 5 is disassembled from housing 4, then fuel solution is injected in the fuel container 1, with catalyst loading in interior pipe reactor 3, again gas-liquid separation part 5 and housing 4 are fitted together, the two can helixseal connect also and can clamping seal.When needing to start device for producing hydrogen, the valve 2 of pipe reactor 3 bottoms makes fuel solution flow into interior pipe reactor 3 in opening, fuel solution begins to produce hydrogen under the effect of catalyzer, because the speed of reaction of the catalyzing manufacturing of hydrogen of hydroborate is very fast, gush on a large amount of hydrogen that generate are quick, reaction solution in the interior pipe reactor 3 is constantly taken out of from the opening part of interior pipe reactor 3 upper ends, reacted fuel solution is turned back in the fuel container 1 again, form fuel solution returns fuel container 1 to interior pipe reactor 3 from fuel container 1 circulation.The hydrogen that generates is from pneumatic outlet 6 outputs.The hydrogen that generates is after the effusion suitable for reading of interior pipe reactor 3, the hydrogen of this moment contains more alkali lye, after it is overflowed, alkali lye in the hydrogen can fall under the effect of self gravitation, hydrogen then can rise, therefore the hydrogen of overflowing from interior pipe reactor 3 upper end open is finished primary gas-liquid separation in rising to gas-liquid separation part 5 these processes, and most alkali lye can be removed in this step.
As shown in Figure 2, gas-liquid separating function can be more effectively realized, the alkali lye and the Hydrogen Separation of the overwhelming majority can be made at gas-liquid separation part 5 filling foamed metals 8.The hydrogen that contains a small amount of alkali lye removes alkali device 7 and can further remove the alkali lye that contains in the hydrogen through what outlet 6 places was provided with.Remove in the alkali device 7 molecular sieve, absorbent cotton, sodium polyacrylate, polyacrylamide, gac, discolour silica gel and FeCl are housed 3H 2A kind of or wherein several mixture among the O, it is cheap and easy to get that these remove alkaline agent, and good impurity removing effect, removing alkali device 7 is detachable apparatus, therefore can with the supporting use of the fuel solution in the fuel container 1, promptly in advance in the based on fuel container 1 amount of fuel solution calculate except that the amount of removing alkaline agent that needs in the alkali device 7, fuel solution runs out of, stop to produce hydrogen, what more renew simultaneously when changing fresh fuel solution removes alkali device 7.Exhausted removes alkaline agent and both can reprocessing cycle use, and also can directly throw aside.

Claims (8)

  1. [claim 1] a kind of hydrogen production device by borohydride comprises fuel container (1) and is located at the interior interior pipe reactor (3) of fuel container (1) that it is characterized in that: described fuel container comprises housing (4), which is provided with dismountable gas-liquid separation part (5); Pipe reactor (3) upper end open in described, its lower end and fuel container (1) internal communication; The top of described gas-liquid separation part (5) is provided with pneumatic outlet (6).
  2. [claim 2] hydrogen production device by borohydride according to claim 1 is characterized in that being that described interior pipe reactor (3) lower end is provided with valve (2).
  3. [claim 3] hydrogen production device by borohydride according to claim 1 and 2 is characterized in that the bottom that is described gas-liquid separation part (5) is provided with a ventilation property dividing plate, filling foamed metal (8) on it.
  4. [claim 4] hydrogen production device by borohydride according to claim 3 is characterized in that being a kind of in nickel foam, foam iron, foam copper, the foam ambrose alloy of described foamed metal (8).
  5. [claim 5] hydrogen production device by borohydride according to claim 1 and 2 is characterized in that being that described pneumatic outlet (6) locates also to be provided with one and remove alkali device (7).
  6. [claim 6] hydrogen production device by borohydride according to claim 5 is characterized in that being described except that molecular sieve, absorbent cotton, sodium polyacrylate, polyacrylamide, gac, discolour silica gel and FeCl being housed alkali device (7) inside 36H 2A kind of or wherein several mixture among the O.
  7. [claim 7] hydrogen production device by borohydride according to claim 5 is characterized in that being that the described alkali device (7) that removes detachably is located at pneumatic outlet (6) and locates.
  8. [claim 8] hydrogen production device by borohydride according to claim 6 is characterized in that being that described molecular sieve is a kind of or wherein several mixture in 3A molecular sieve, 4A molecular sieve, 5A molecular sieve, 13X HP molecular sieve, 13X PG molecular sieve, 13X APG molecular sieve, the XH-5 molecular sieve.
CNA2007102025022A 2007-11-13 2007-11-13 Hydrogen production device by borohydride Pending CN101434378A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
CN110790222A (en) * 2019-12-03 2020-02-14 河南中氢动力研究院有限公司 Device and method for preparing hydrogen

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
CN110790222A (en) * 2019-12-03 2020-02-14 河南中氢动力研究院有限公司 Device and method for preparing hydrogen
CN110790222B (en) * 2019-12-03 2021-04-27 河南中氢动力研究院有限公司 Device and method for preparing hydrogen

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Open date: 20090520