CN1958438B - Device and method for producing hydrogen - Google Patents

Device and method for producing hydrogen Download PDF

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Publication number
CN1958438B
CN1958438B CN2005100309092A CN200510030909A CN1958438B CN 1958438 B CN1958438 B CN 1958438B CN 2005100309092 A CN2005100309092 A CN 2005100309092A CN 200510030909 A CN200510030909 A CN 200510030909A CN 1958438 B CN1958438 B CN 1958438B
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hydrogen
water
aqueous vapor
fuel container
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CN1958438A (en
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顾志军
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Haisheng hydrogen Automobile Co.,Ltd.
Shanghai qingneng horiz New Energy Technology Co., Ltd
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QINGNENG FUEL CELL TECHNOLOGY Co Ltd SHANGHAI
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    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30Hydrogen technology
    • Y02E60/36Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

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  • Separation Using Semi-Permeable Membranes (AREA)
  • Hydrogen, Water And Hydrids (AREA)

Abstract

This invention relates to apparatus and method for generating H2. Generation of H2 in this invention is realized by contact reaction between water vapor and a dry mixture of hydride and catalyst. The dry mixture is stored in a fuel container selectively permeable for water vapor, and the permeation rate of water vapor from the water source is adjustable. The fuel container is selectively permeable for water vapor, while liquid-state water, H2, O2, N2 and CO2 are impermeable. After generated in the fuel container, H2 is collected and filtered, and then transported through a gas exit on the fuel container to fuel cells or H2-storage containers. Compared with present techniques, this invention has such advantages as simple structure, high energy efficiency, safe operation and easy control.

Description

A kind of device and method that produces hydrogen
Technical field
The present invention relates to a kind of device and method that produces hydrogen, relate in particular to a kind of hydrogen formation apparatus and hydrogen production process that fuel hydrogen can be provided for fuel cell.
Background technology
A kind of hydrogen storage scheme of safe, reliable, efficient rate is very important for the commercialization of fuel cell.Hydride is a very potential method to the demand of portable power source, has a variety of methods to be studied exploitation at present, produces hydrogen by reacting with hydride and pure water, and this is NaBH wherein 4Reaction can be represented with following chemical equation: NaBH 4+ 2H 2O=4H 2+ NaBO 4
Other hydride has: LiH, LiAlH 4, LiBH 4, NaH, NaAlH 4, MgH 2, KH, KBH 4, CaH 2, NaBH 4
These reactions are quite violent, and we need accurately control could produce the hydrogen of requirement and prevent blast.The U.S. has a company to adopt NaBH 4Solution is with NaBH 4Solution contacts with catalyzer, adjusts the speed that hydrogen produces by the rotating speed of adjusting pump, and this method is very practical concerning high-power fuel cell.Yet for the battery less than 20W, because reaction is violent, there is certain difficulty in difficult control when practical application.
Some technology in the past adopt the gas-selectively film to divide dried up and hydride, and water directly is penetrated into hydride one side from the water side.Owing to exist water partial pressure, when water and hydride produce hydrogen at a touch, yet this porous film all has permeability for water and hydrogen, and reactant just needs to seal the seepage that prevents hydrogen like this.And the water of reaction usefulness, must just be packaged in process of production in the hydrogen generator, so just reduce energy efficiency in transit.
Have a United States Patent (USP) to introduce a system, this system is made up of two parts, and a part is a chemical hydride, and another part is a methanol aqueous solution.Methanol aqueous solution can be diffused into hydride side and the hydride generation hydrogen that reacts by barrier film.A hydrogen outlet is installed on the reaction vessel, still, must have good sealing to deal with the toxicity and the high diffusibility of methyl alcohol.
Another United States Patent (USP) has been introduced the hydrogen formation apparatus that a kind of water selective membrane divides water proof and hydride.This film does not allow H 2, N 2Pass through Deng gas, so just make hydrogen collect the easy of change.Unfortunately, there is sizable defective in this system in the practice utilization, at first owing to do not have catalyzer or acidic substance inside, water and NaBH 4Between chemical reaction become quite slow, and be not enough to supply with needs; Secondly this reaction process will make anti-strained be difficult to control when the water permselective membrane directly contacts with liquid water, because a large amount of water can directly arrive the hydride side by film.
Summary of the invention
Purpose of the present invention be exactly provide in order to overcome the defective that above-mentioned prior art exists a kind of simple in structure, energy efficiency is high, the device and method of operational safety, the generation hydrogen that is easy to control.Apparatus of the present invention are with after fuel cell is connected, because its light characteristic that is easy to carry about with one can be applied in a lot of fields.
Purpose of the present invention can be achieved through the following technical solutions:
A kind of device that produces hydrogen is characterized in that, this device comprises:
A) alternative fuel container by aqueous vapor,
B) this fuel container contains a kind of mixture, and this mixture is made up of a kind of hydride and at least a catalyzer at least,
C) on fuel container, have a hydrogen delivery port at least,
D) have a gas filter at least,
E) this fuel container has at least a face to be made up of following material: the material of the alternative permeate water of one deck and the alternative material that sees through gas of one deck at least at least,
F) water source.
Described hydride is selected from NaBH 4, LiAlH 4, LiBH 4, NaAlH 4, MgH 2, KBH 4In one or more.
Described catalyzer is selected from C O, Ni, Pt, Ru or their compound comprise C OCL 2In one or more.
Described mixture is drying solid powder or particle, and this mixture has been filled 20%~95% volume of fuel container.
The material of described alternative permeate water only allows aqueous vapor to pass through significantly, does not allow to comprise H 2, O 2, N 2, CO 2Gas pass through.
The material of described alternative permeate water is a kind of perfluorinated sulfonic acid (Nafion) film or zylonite (Cellulose) film.
The material that described alternative sees through gas only allows gas to pass through significantly, does not allow liquid water to pass through, and comprises porous polytetrafluoroethylene (PTFE) film.
Described water source is the moisture in the outside air.
Described water source comprises moisture sponge for one deck at least contains the porous material of water.
A kind of method that produces hydrogen is characterized in that, this method comprises:
A) at least a hydride of preparation and at least a catalyst fines or granular mixture,
B) utilize the alternative face that sees through aqueous vapor that said mixture and water source are isolated,
C) allow aqueous vapor be penetrated into this side of hydride by the face that alternative sees through aqueous vapor, produce chemical reaction from the water source side,
D) from fuel container, collect hydrogen,
E) the wherein alternative face that sees through aqueous vapor by the material of the alternative permeate water of one deck at least and at least the alternative material of one deck through gas form.
Described method has also comprised the generation speed of controlling hydrogen by the rate of permeation of control aqueous vapor, and wherein the control of the rate of permeation of aqueous vapor is to be realized with alternative thickness and the porosity that sees through the material of gas by the thickness of the material of regulating alternative permeate water.
The material of alternative permeate water only allows aqueous vapor to pass through significantly in the described method, does not allow to comprise H 2, O 2, N 2, CO 2Gas pass through.
The alternative material that sees through gas only allows gas to pass through significantly in the described method, does not allow liquid water to pass through, and comprises porous polytetrafluoroethylene (PTFE) film.
Described method has also further comprised by the sealed fuel container makes device stop to produce hydrogen.
Compared with prior art, the present invention have simple in structure, energy efficiency is high, operational safety, be easy to advantages such as control.
Description of drawings
Fig. 1 is the structural representation of one embodiment of the invention;
Fig. 2 is the structural representation of another embodiment of the present invention;
Fig. 3 is the structural representation of another embodiment of the present invention.
Embodiment
The invention will be further described below in conjunction with the accompanying drawings and the specific embodiments.
The hydrogen generator of high-energy-density of the present invention adopts multiple factor and technical scheme, and purpose is to improve energy efficiency, and the realization of this purpose is by reducing the amount of carrying of water; Another purpose is hydrogen and the controllable hydrogen generation speed that obtains capacity by hydride.
Dry powdered hydrogenation image LiH, LiAlH 4, LiBH 4, NaH, NaAlH 4, MgH 2, KH, KBH 4, CaH 2, NaBH 4Very high energy density is all arranged, NaBH 4As preferred hydride is because the character of its high-energy-density and the generation of reacting the back unharmful substance, solid NaBH 4Can from environment, absorb aqueous vapor and react, particularly in the higher environment of wetness.If there be not catalyzer to resemble C OCL 2, Ni, Pt or be in the sour environment, this reaction is suitable slowly so that be not enough to the fuel supplying battery under most of occasions.By experiment, we can see at NaBH 4With add catalyzer such as C in the reaction of water OCL 2After, speed of response is obviously accelerated.Why we select C OCL 2Be because its low price and catalysis characteristics efficiently.
The first-selected exsiccant powder of mixture is the contact area for augmenting response.The making method of powder is at first with C OCL 2Be dissolved in the Virahol, then with NaBH 4Powder is put in the solution.NaBH 4Can be from Morton, these companies of Eagle-Picher or Bayer have bought.These materials can vacuum-drying under the state of 60 ℃ of centigradetemperatures.
These NaBH 4And C OCL 2Mixture can put into a fuel container that has one deck aqueous vapor selective membrane at least, and this film allows aqueous vapor to enter into the chemical substance side from the water source side to the full extent, hydrogen promptly produces in container, and discharges from being connected the outlet that container is equipped with strainer.NaBH 4With the reaction product sodium metaborate of water can be at NaBH 4Particle surface forms one deck duricrust, and simultaneously, the volume of chemical substance can increase in reaction in the container, so can not fill up reactant fully in the container, must reserve 5%~80% space, also helps to make aqueous vapor fully contact NaBH 4And C OCL 2Mixture and the discharging of hydrogen.
The aqueous vapor permselective membrane is made up of two-layer at least, one deck is the material of water selective permeation and the material of one deck gas selective permeation, the Nafion film of our first-selected E.I.Du Pont Company of water selectivity permeable material, the Cellulose film also can use, the first-selected porous PTFE film of gas selective material.As shown in Figure 1: 1 is the production well of hydrogen among the figure, and production well can outwards connect accumulator unit or power generation assembly by pipe.Among the figure 4 the expression by NaBH 4With the mixture of catalyzer composition, the 5th, container receives by NaBH for preventing 4The mixture of forming with catalyzer absorbs that aqueous vapor expands and the space reserved, and the 6th, prevent by NaBH 4The mixture of forming with catalyzer produces inflow such as waste residue or cake mass or blocks the strainer of filtrations such as air outlet in reaction process, by NaBH 4The mixture of forming with catalyzer absorbs the aqueous vapor in the surrounding environment, and the water permselective membrane 2 gentle permselective membranes 3 by representing among the figure enter aqueous vapor NaBH is housed 4React in the material fuel container of forming with catalyzer, the hydrogen that reaction produces, 1 outlet flows among fuel cell or the hydrogen storage vessel from figure.
We observe in experiment, if we directly contact the Nafion film with water, the diffusing capacity of water is very big, the NaBH in the container 4Can form solution with water, what chemical reaction will become like this is quite violent and uncontrollable, therefore will avoid the Nafion film directly to contact and control reaction with liquid water, so just need outside the Nafion film, put one deck gas selective material, porous PTFE film is first-selected, and another benefit be can be by adjusting the PTFE film thickness and the aperture diffusivity of adjusting aqueous vapor.When container is placed in the bigger environment of humidity, control the generation speed of hydrogen with regard to the diffusibleness that helps adjusting aqueous vapor, also having a benefit is exactly this gas selective permeation material, can filter the water of low-purity, very useful under this situation that pure water is difficult for seeking out of doors.
In the inboard of water permselective membrane, we can add one deck gas selective permeation film again, as sandwich, form one deck duricrust to avoid resultant of reaction on water permselective membrane surface.
The water source of aqueous vapor can be to be added in outer liquid water of container or the water in the ambient atmosphere environment, and the outside that the porous water wetted material can be placed on fuel container fixes liquid water, by supplying with moisture with tight contact of container.The benefit of doing like this is at first to react water not need to exist in advance in the hydrogen generator, and weight and volume can significantly reduce when transporting like this; Next is the needed water of this hydrogen generator, much smaller than adopting NaBH 4Solution is done the needed water of hydrogen generator of reactant.Use NaBH with previous classics 4The hydrogen generator of solution can only carry about NaBH of 20% to 30% of its reactant weight 4, and the purpose of our first-selection is to make NaBH 4Reach more than 50% of reactant weight.Simultaneously, the water in the surrounding environment also can be utilized, and 5 times of energy densities are to the hydrogen generator that adopts the solution form.If as the water source, the fuel container surface just can contact by direct with indivisible liquid water in the time of at the beginning with the water of surrounding environment, make the hydrogen of its rapid generation aequum.
The hydrogen fueling battery that produces from hydrogen production bioreactor or be collected in the hydrogen storage vessel can obtain highly purified hydrogen through the bed filtration device, and porous PTFE can be preferred.
Fuel container need seal when storing and make it airtight, does not so just have aqueous vapor to enter in the container, in case do not have aqueous vapor to enter in the container after the sealing, reaction will stop.
Embodiment 1
As shown in Figure 1, a kind of device that produces hydrogen, in Fig. 1: the 1st, the hydrogen production well, this production well can outwards connect hydrogen-storing device or fuel cell power generating system by pipe; 4 the expression by NaBH 4Mixture with the catalyzer composition; The 5th, container receives by NaBH for preventing 4The mixture of forming with catalyzer absorbs that aqueous vapor expands and the space reserved; The 6th, prevent by NaBH 4The mixture of forming with catalyzer produces inflow such as waste residue or cake mass or blocks filtration strainer such as production well in reaction process; By NaBH 4The mixture of forming with catalyzer absorbs the aqueous vapor in the surrounding environment, and the water permselective membrane 2 gentle permselective membranes 3 by representing among Fig. 1 enter aqueous vapor NaBH is housed 4React in the material fuel container of forming with catalyzer, the hydrogen that reaction produces, the production well from Fig. 1 flows in fuel cell or the hydrogen-storing device.Hydrogen production well 1 among Fig. 1, water permselective membrane 2 gentle permselective membranes 3 constitute the fuel container 7 of this device.
Embodiment 2
As shown in Figure 2, a kind of device that produces hydrogen, the structure of this device be adopt plastics as materials such as (ABS, PVC) as shell 8, built-in water-absorbing material 10 is as sponge etc., add water by water-in 11, moisture water-absorbing material 10 assurance aqueous vapors can enter by water permselective membrane 2 gentle permselective membranes 3 NaBH is housed 4Among the container of catalyzer composition mixture.Among Fig. 2: the 1st, the hydrogen production well, this production well can outwards connect by pipe; 4 the expression be by NaBH 4Mixture with the catalyzer composition; The 5th, container receives by NaBH for preventing 4The mixture of forming with catalyzer absorbs that aqueous vapor expands and the space reserved; The 9th, the skeleton that a kind of silicon rubber, soft rubber or plastic working form, work to support water permselective membrane 2 gentle permselective membranes 3, when the gentle permselective membrane of water permselective membrane 23 by glue on water-absorbing material, prop up by this skeleton again, make the firm inboard that is fixed on water-absorbing material of water permselective membrane 2 gentle permselective membranes 3 energy; 6 are made up of poly tetrafluoroethylene among the figure, are to prevent by NaBH 4The mixture of forming with catalyzer inflow such as waste residue and cake mass or block the strainer of filtrations such as air outlet in reaction process can be effectively by NaBH 4The mixture of forming with catalyzer absorbs the aqueous vapor that adds; Water permselective membrane 2 gentle permselective membranes 3 by representing among the figure enter aqueous vapor NaBH are housed 4The mixture of forming with catalyzer reacts in fuel container, the hydrogen that reaction produces, and production well flows in power generation assembly or the hydrogen-storing device from figure.
Embodiment 3
As shown in Figure 3, a kind of built-up type produces the device of hydrogen, present embodiment is together in parallel the hydrogen formation apparatus of two groups, four groups, six groups even more embodiment 1 or embodiment 2, hydrogen is finally flowed out by a total air outlet 12, increase the flow of air feed like this, make this hydrogen formation apparatus can supply bigger usefulness device of air and power generation assembly.Among Fig. 3: the 12nd, total air outlet of hydrogen couples together the hydrogen production well 1 of several groups of hydrogen formation apparatus by several group interfaces, is summarized in a house steward, makes hydrogen can put together outflow, improves gas supply capacity and speed.
After the description of the present invention by specification sheets is disclosed out, it will be understood by the professional person in this field, same principle and the object that is not written in the specification sheets can be manufactured comes out, in addition, under the prerequisite of not leaving the principle of the invention, have the variation that many modifications come condition of compatibility and material; Therefore, the product of specification sheets explanation at present of the present invention is just a kind of as expected, and present invention includes any under this principle various forms of devices and directly with the method for this device production hydrogen.

Claims (10)

1. a device that produces hydrogen is characterized in that, this device comprises:
A) alternative fuel container by aqueous vapor,
B) this fuel container contains a kind of mixture, and this mixture is made up of a kind of hydride and at least a catalyzer at least,
C) on fuel container, have a hydrogen delivery port at least,
D) have a gas filter at least,
E) this fuel container has at least a face to be made up of following material: the material of the alternative permeate water of one deck and the alternative material that sees through gas of one deck at least at least,
F) water source;
Described hydride is selected from NaBH 4, LiAlH 4, LiBH 4, NaAlH 4, MgH 2, KBH 4In one or more;
Described catalyzer is selected from C OCl 2
Described water source comprises moisture sponge.
2. a kind of device that produces hydrogen according to claim 1 is characterized in that described mixture is drying solid powder or particle, and this mixture has been filled 20%~95% volume of fuel container.
3. a kind of device that produces hydrogen according to claim 1 is characterized in that, the material of described alternative permeate water only allows aqueous vapor to pass through significantly, does not allow to comprise H 2, O 2, N 2, CO 2Gas pass through.
4. according to claim 1 or 3 described a kind of devices that produce hydrogen, it is characterized in that the material of described alternative permeate water is a kind of perfluoro sulfonic acid membrane or zylonite film.
5. a kind of device that produces hydrogen according to claim 1 is characterized in that, the material that described alternative sees through gas comprises the porous poly tetrafluoroethylene.
6. method of utilizing the described device of claim 1 to produce hydrogen is characterized in that this method comprises:
A) at least a hydride of preparation and at least a catalyst fines or granular mixture,
B) utilize the alternative face that sees through aqueous vapor that said mixture and water source are isolated,
C) allow aqueous vapor be penetrated into this side of hydride by the face that alternative sees through aqueous vapor, produce chemical reaction from the water source side,
D) from fuel container, collect hydrogen,
E) the wherein alternative face that sees through aqueous vapor by the material of the alternative permeate water of one deck at least and at least the alternative material of one deck through gas form.
7. a kind of method that produces hydrogen according to claim 6, it is characterized in that, described method has also comprised the generation speed of controlling hydrogen by the rate of permeation of control aqueous vapor, and wherein the control of the rate of permeation of aqueous vapor is to be realized with alternative thickness and the porosity that sees through the material of gas by the thickness of the material of regulating alternative permeate water.
8. a kind of method that produces hydrogen according to claim 6 is characterized in that, the material of alternative permeate water only allows aqueous vapor to pass through significantly in the described method, does not allow to comprise H 2, O 2, N 2, CO 2Gas pass through.
9. a kind of method that produces hydrogen according to claim 6 is characterized in that, the alternative material that sees through gas comprises the porous poly tetrafluoroethylene in the described method.
10. a kind of method that produces hydrogen according to claim 6 is characterized in that, described method has also further comprised by the sealed fuel container makes device stop to produce hydrogen.
CN2005100309092A 2005-10-31 2005-10-31 Device and method for producing hydrogen Active CN1958438B (en)

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Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101565165B (en) * 2008-04-24 2012-06-27 汉能科技有限公司 Safe hydrogen preparing and purifying method for hydrogen generator
KR20150016492A (en) * 2012-03-23 2015-02-12 인텔리전트 에너지, 인크. Hydrogen producing fuel cartridge
EP2827977A4 (en) 2012-03-23 2015-11-25 Intelligent Energy Ltd Hydrogen producing fuel cartridge and methods for producing hydrogen
EP3623808A1 (en) * 2018-09-17 2020-03-18 Seitz, Peter Electrochemical sensor for the measurement of water content
CN109292946A (en) * 2018-09-20 2019-02-01 中国人民解放军第二军医大学第二附属医院 A kind of reverse osmosis membrane bag for helping to discharge hydrogen
CN110642223A (en) * 2019-09-29 2020-01-03 武汉市能智达科技有限公司 Compound hydrogen storage material composition and hydrogen production reactor composed of same

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4155712A (en) * 1976-04-12 1979-05-22 Taschek Walter G Miniature hydrogen generator
US6645651B2 (en) * 2001-06-01 2003-11-11 Robert G. Hockaday Fuel generator with diffusion ampoules for fuel cells
CN2890023Y (en) * 2005-10-31 2007-04-18 上海清能燃料电池技术有限公司 Hydrogen generating device

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4155712A (en) * 1976-04-12 1979-05-22 Taschek Walter G Miniature hydrogen generator
US6645651B2 (en) * 2001-06-01 2003-11-11 Robert G. Hockaday Fuel generator with diffusion ampoules for fuel cells
CN2890023Y (en) * 2005-10-31 2007-04-18 上海清能燃料电池技术有限公司 Hydrogen generating device

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