CN102849678A - One-off and adjustment method of hydrogen releasing from chemical hydride - Google Patents
One-off and adjustment method of hydrogen releasing from chemical hydride Download PDFInfo
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- CN102849678A CN102849678A CN2012103475840A CN201210347584A CN102849678A CN 102849678 A CN102849678 A CN 102849678A CN 2012103475840 A CN2012103475840 A CN 2012103475840A CN 201210347584 A CN201210347584 A CN 201210347584A CN 102849678 A CN102849678 A CN 102849678A
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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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- 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
A one-off and adjustment method of hydrogen releasing from chemical hydride is provided, which controls the ''one/off'' of hydrogen release by the ''contact/non-contact'' procedures between the reactants. First, at least a hydride powder, a catalyst powder and a reactant containing water are provided, and at least any two of three are mixed to form a mixture. Hydrogen gas is generated by adjusting a contact area between the mixture and the remaining one. The hydrogen-releasing reaction is terminated when a non-contacting state between the mixture and the remaining one occurs. In another embodiment, an inhibitor or an inhibiting method could be used for suppressing or terminating the hydrogen-releasing reaction. The hydrogen-releasing rate could be controlled and adjusted by the extent of suppression.
Description
The application is to be that the application number on August 3rd, 2010 is dividing an application of 201010243281.5 application for a patent for invention (denomination of invention: switch and control method that chemical hydride hydrogen discharges) applying date.
[technical field]
The invention relates to switch and control method that a kind of chemical hydride hydrogen discharges, and particularly about a kind of release that reaches " On/Off " chemical hydride hydrogen through " contact/noncontact ".
[background technology]
Hydrogen supply device the provides fuel cell system indispensable unit of institute is in order to provide fuel power generation function.And the hydrogen generating system that is used for traditionally hydrogen fuel cell needs the equipment of the complexity such as motor, sensor, logical circuit to come Controlling System more.
Please refer to Fig. 1, it illustrates the active schematic diagram of putting hydrogen system of a kind of tradition.This hydrogen generating system system uses sodium borohydride (NaBH
4) aqueous solution is as hydrogen source, can come for giving fuel cell after extracting hydrogen.Traditional active NaBH
4Put hydrogen system as shown in Figure 1, contain a pump (pump) 11 actives with the liquid fuel NaBH of 12 li of fuel containers
4Alkaline aqueous solution squeeze into catalyst bed 13, NaBH
4Alkaline aqueous solution is through producing hydrogen and NaBO behind the catalyzer
2The aqueous solution, its chemical equation (1) is as follows:
Hydrogen and NaBO
2The aqueous solution because the difference of proportion can be with hydrogen and NaBO
2The aqueous solution separate NaBO
2Water solution flow to spent fuel storage tank 15, hydrogen is then discharged by the outlet 161 on the gas/liquid separation device (gas/liquid separator) 16 and does use, at any time monitor hydrogen atmospheric pressure of pressure sensor 17 is then arranged above gas/liquid separation device 16, the pressure signal of feedback is reference value, see through the output that formula controller 18 comes control pump 11 liquid towards fuel, to reach switch and to regulate flow and the pressure of putting hydrogen.
Please refer to Fig. 2, it illustrates the schematic diagram that a kind of traditional passive type is put hydrogen system.This hydrogen generating system mainly utilizes the difference of pressure to make NaBH
4Produce hydrogen with HCl aqueous solution contact reacts, and when hydrogen desorption capacity is enough build-up of pressure rise force the HCl aqueous solution can't with NaBH
4The contact and can't the sustained reaction releasing hydrogen gas.When namely just having begun, fill in advance hydrogen in the system, make pressure greater than the default force value of the 1st valve (Valve-1) 231, this moment the 1st valve 231 for opening, system's internal pressure is balance, HCl and NaBH
4Be in original state and contactless.When using hydrogen, open the 3rd valve (Valve-3) 233, this moment, system's internal pressure descended, when pressure is lower than the pressure set points of the 1st valve 231, the 1st valve 231 is for cutting out, because the 3rd valve 233 or opened condition (but the 1st valve 231 is for cutting out), the pressure continuous decrease causes NaBH
4Cavity 24 internal pressures are less than hydrogenchloride/catalyzer cavity 25 internal pressures, and force the HCl aqueous solution to enter solid NaBH
4, and react with it releasing hydrogen gas and discharged by the 3rd valve 233 and to use.When lasting releasing hydrogen gas, cause NaBH
4Cavity 24 pressure force the HCl aqueous solution to reflux greater than hydrogenchloride/catalyzer cavity 25 internal pressures, impel reaction to stop, and system just no longer discharges hydrogen.The 2nd valve (Valve-2) the 232nd, pressure release valve, when pressure during greater than the setting pressure of the 2nd valve 232, hydrogen just be disposed in the atmosphere and can be in system cumulative stress.
Yet above-mentioned traditional hydrogen generating system is the complicated and bulky Heavy Weight of mechanism design not only, is unsuitable for mobilely, and the holistic cost that involves great expense is high, consider with regard to entity and cost all to be unfavorable for routine use and to carry, therefore use quite restricted.
[summary of the invention]
Present invention is directed to switch and the control method of the release of a kind of chemical hydride hydrogen, mainly is the release that reaches " On/Off " chemical hydride hydrogen by " contact/noncontact ".
According to one embodiment of the invention, it is the method that proposes the release of a kind of chemical hydride hydrogen.At first, provide that solid hydrides, solid are put hydrogen catalyst and aqueous reaction thing at least.And mix this solid hydrides, this solid puts hydrogen catalyst and this aqueous reaction thing is wherein appointed both, forms mixture.Adjust this mixture and described solid hydrides, solid and put that remaining a kind of material contacts to control hydrogen discharge reaction in hydrogen catalyst and the aqueous reaction thing, produce hydrogen, when wherein being this contact condition, this solid hydride system and this aqueous reaction thing carry out this hydrogen discharge reaction, and this solid is put this hydrogen discharge reaction of hydrogen catalyst catalysis.If make described mixture and described remaining a kind of material be contactless state, to stop hydrogen discharge reaction, stop release hydrogen.Among the other embodiment, also can inject at least inhibitor or utilize the inhibition method suppressing or to close carrying out of this hydrogen discharge reaction, but the hydrogen rate of release during by this hydrogen discharge reaction of degree modulation of inhibition.
For foregoing of the present invention can be become apparent, embodiment cited below particularly, and cooperate appended graphicly, be described in detail below:
[description of drawings]
Fig. 1 illustrates the active schematic diagram of putting hydrogen system of a kind of tradition.
Fig. 2 illustrates the schematic diagram that a kind of traditional passive type is put hydrogen system.
Fig. 3 A, 3B are according to the switch of the chemical hydride hydrogen release of the embodiment of the invention and the experiment module schematic diagram of control method.
Fig. 4 is the experimental data figure that one-phase in the experimental example is put hydrogen opening and closing (on/off).
Fig. 5 is put the experimental data figure of hydrogen opening and closing (on/off) for two stages in another experimental example.
Fig. 6 illustrates and reaches switch and the schematic diagram of regulating the experiment module that chemical hydride hydrogen discharges according to another embodiment of the present invention with inhibitor.
[main element nomenclature]
11: pump
12: fuel container
13: catalyst bed
15: fuel storage tank
16: the gas/liquid separation device
17: pressure sensor
18: the formula controller
231: the 1 valves
232: the 2 valves
233: the 3 valves
24: the sodium borohydride cavity
25: hydrogenchloride/catalyzer cavity
31: sealed shell of tank
33: gas piping
35: solid hydrogen fuel
36: the pulling type pillar
37: solid water
[embodiment]
The present invention is switch and the control method that proposes the release of a kind of chemical hydride hydrogen, mainly be to utilize " contact/noncontact " between the reactant to reach the release of " On/Off " chemical hydride hydrogen, also can utilize in addition the injection of inhibitor or inhibition method to reach the release of closing chemical hydride hydrogen.
Below be to propose embodiment according to the present invention, describing switch and the control method of chemical hydride hydrogen of the present invention release in detail, and assistant with the part related experiment to clearly demonstrate embodiment.Yet constituent, material and the hydrogen supply flow process that is proposed in embodiment and the experiment be the usefulness for illustrating only, is not the usefulness as limit protection domain of the present invention.Those skilled in the art can be according to the disclosure of embodiment and experiment, and its step of demand of physical condition is slightly made modifications during for application.Moreover the diagram of embodiment only illustrates the related elements of the technology of the present invention, omits unnecessary element, with the clear technical characterstic that shows the present invention.
The present invention system utilizes " contact/noncontact " between reactant to reach the release of " On/Off " chemical hydride hydrogen.And the speed that the adjustable variation hydride of the number that utilizes contact area hydrogen discharges, contact area is more so that reaction area is larger, and the generation speed of hydrogen is just faster.When being contact condition between the reactant, the solid hydride system can carry out hydrogen discharge reaction with water (from the aqueous reaction thing), and solid is put hydrogen catalyst system in order to this hydrogen discharge reaction of catalysis, thereby starts hydrogen release; When being contactless state between the reactant, hydrogen discharge reaction stops and stopping the generation of hydrogen.
Wherein reactant comprises that solid hydrides, solid are put hydrogen catalyst and aqueous reaction thing at least, and can select appointing both and remaining one and be and contact/contactless state among this three.Wherein, solid hydrides and solid are put hydrogen catalyst and be can be described as again solid hydrogen fuel.In one embodiment, but blended solid hydride, solid puts hydrogen catalyst and the aqueous reaction thing is at least wherein appointed both, forms mixture.And adjust this mixture and contact with the control hydrogen discharge reaction with residue one of one, generation hydrogen, when wherein being this contact condition, this solid hydride system and this aqueous reaction thing carry out this hydrogen discharge reaction, and this solid is put this hydrogen discharge reaction of hydrogen catalyst catalysis.Wherein, this mixture is directly proportional with hydrogen-producing speed with residue one of one contact area, when this contact area greater than 1/2 the time, hydrogen-producing speed is greater than 1/2 of design discharge.
Moreover, in one embodiment, powder simultaneously after can be first solid hydrides and solid being put hydrogen catalyst and evenly mix or mix behind the powder respectively, form afterwards and press caked mass, when pressing caked mass to contact with solid water, can carry out hydrogen discharge reaction, the release of " startup " hydrogen.Wherein, when both real contact area greater than the maximum contact area 1/2 the time, hydrogen-producing speed is greater than 1/2 of design discharge.When pressing caked mass and solid water noncontact, hydrogen discharge reaction no longer carries out, and can " close " release of hydrogen.Wherein, solid water for example is glue, also can carry out first pre-treatment before use, for example adds water in the reaction flask of placing glue, makes to press caked mass to be in contact with it again.
In another embodiment, also can make solid hydrides and solid water evenly mix behind the powder respectively, form afterwards and press caked mass; Same, when pressing caked mass and solid to put hydrogen catalyst to contact, can carry out hydrogen discharge reaction, the release of " startup " hydrogen.When pressing caked mass and solid to put the hydrogen catalyst noncontact, hydrogen discharge reaction no longer carries out, and can " close " release of hydrogen.Because the catalyzer price comparison is expensive, this kind method can make catalyzer over and over again repeat to be utilized, and not only the waste of resource is avoided in environmental protection, and also escapable cost also is easy to reclaim catalyzer afterwards.
Among the embodiment, aforementioned solid hydrides can be hydroborate, nitrogen hydride, hydrocarbons, metal hydride, boron nitrogen hydride, boron hydrocarbons, nitrogen hydrocarbons, metal borohydride, metal nitrogen hydride, metal hydrocarbons, metal boron nitrogen hydride, metal boron hydrocarbons, metal carbonitride hydride, boron nitrogen hydrocarbons, metal boron nitrogen hydrocarbons or above-mentioned combination.Among the embodiment, solid hydrides for example is sodium borohydride (NaBH
4), lithium aluminum hydride (LiAlH
4), sodium aluminum hydride (NaAlH
4), hydrogenation magnalium (Mg (AlH
4)
2), calcium aluminum hydride (Ca (AlH
4)
2), lithium borohydride (LiBH
4), POTASSIUM BOROHYDRIDE (KBH
4), hydroboration beryllium (Be (BH
4)
2), magnesium borohydride (Mg (BH
4)
2), calcium borohydride (Ca (BH
4)
2), lithium hydride (LiH), sodium hydride (NaH), magnesium hydride (MgH
2) and hydrolith (CaH
2) group that forms.
Moreover solid hydrides also can be chemical hydride or the compound with Formula B xNyHz.Ammonia borine (H for example
3BNH
3), the diamino diborane, H
2B (NH
3)
2BH
4, poly--(amino borane), borazine (B
3N
3H
6), borine-tetrahydrofuran (THF) mixture, diborane and the similar group that forms.
Among the embodiment, aforementioned solid put hydrogen catalyst for example be comprise solid peracid, contain ruthenium, metal ion, atoms metal, metal nanoparticle or the micron particle of nanoparticle, micron particle or the aforementioned metal of the metallic salt of cobalt, nickel, copper, iron or aforementioned metal be attached to solid catalyst made on the carrier.
In one application examples, solid can also comprise soft polymer base material (moulding dose) when putting hydrogen catalyst and solid hydrides (solid hydrogen fuel) mixing, its composition comprises the hydrophobic polymer elastomerics, such as being the materials such as silica gel, rubber, silicon rubber, make the solid hydrogen fuel of making have the plasticity of flexible.
Among the embodiment, aforementioned aqueous reaction thing can be liquid or solid-state.Liquid aqueous reactant for example is water, alcohols, the aqueous solution, salts solution or the acidic aqueous solution of alcohol or the aqueous solution of aforementioned combination.Solid-state aqueous reaction thing for example is the macromolecule water uptake material, and this polymer comprises polyacrylic ester, polyvinyl alcohol, acetate ethylene copolymer, urethane, polyethylene oxide, starch graft copolymer or rubber blend etc.
Yet, aforesaid solid hydrides, solid put hydrogen catalyst and aqueous reaction thing (with moulding dose) is not limited with above-claimed cpd, can be through grinding or milled processed not during preparation, and its kenel can be that wherein the two forms piece with each self-pressure of another one, or wherein the two pressure is formed piece, another one is loose shape distribution or aqueous, be familiar with this skill person when knowing that visual practical application condition and situation (such as the grouping situation of three kinds of reactants) make appropriate selection, the present invention is to this and seldom be restricted.
Below be related experiment and the experimental result thereof that proposes the embodiment of the invention.Observation utilizes " contact/noncontact " between the reactant for the effect that reaches " On/Off " hydrogen and discharge, and related experiment is as follows.
＜related experiment 〉
Fig. 3 A, 3B are according to the switch of the chemical hydride hydrogen release of one embodiment of the invention and the experiment module schematic diagram of control method.Experiment switch designs system uses the pulling type device shown in Fig. 3 A, 3B, utilize sealed shell of tank 31 (such as sealed plasthetic) to pick out gas piping 33, this pipeline 33 connects product hydrogen tank body and sensed flow meter, again plastic solid hydrogen fuel 35 is fixed on the pulling type pillar 36 moving up and down, and in sealed shell of tank 31 interior placement solid waters 37.
Whole On/Off (on/off) is released hydrogen and is controlled to be the following stated: when pulling type pillar 36 moves down, plastic solid hydrogen fuel 35 can be pushed in the solid water 36, form the action of on, begin reaction and produce hydrogen, as shown in Figure 3A.After producing the lifting of hydrogen speed, solid hydrogen fuel is detached solid water, attempt to make the off behavior, shown in Fig. 3 B figure, produce hydrogen speed and become slow decreasing this moment.
In an experimental example, be to use 1 gram NaBH
4(solid hydrides), 0.3 gram cobalt resin catalyst and 0.8 gram silicon rubber (Silicone rubber, moulding dose).The result shows after tested, pillar 36 pushed namely begin to put hydrogen (on), reach 13sccm behind the hydrogen discharging speed to 2000 second, with its pillar 36 pull-ups, (off) action is closed in execution, the remaining a small amount of water of fuel surface reacts after closing (off), hydrogen-producing speed begins to drop to 6sccm after the several seconds, if consideration background value, produce hydrogen speed and roughly be down to 1 ~ 2sccm, finished and closed (off), Fig. 4 is the experimental data figure that one-phase in the experimental example is put hydrogen opening and closing (on/off).
For confirming the mechanism of contact on-off switch, fixedly the pillar 36 of hydrogen fuel pushes with solid water 37 in conjunction with producing hydrogen again, on for the second time in the time of 4200 seconds, hydrogen-producing speed is rising also, when arriving 5800 seconds, with pillar 36 pull-ups, start for the second time off, in the time of 7800 seconds, just be down to the identical 6sccm of the off first time about, such as Fig. 5, it puts the experimental data figure of hydrogen opening and closing (on/off) for two stages in another experimental example.Above-mentioned on-off switch experiment, although the flow curve of the unlatching of on and off and termination reaction is slightly slow, the design of this device has the effect of the on-off of reaching really.
Shown by experimental result, utilize " contact/noncontact " between the reactant really can reach the effect of " On/Off " hydrogen release, and this start can repeat, still have the effect of opening and closing.
In addition, except stopping hydrogen discharge reaction with contactless state, among another embodiment also can by, inject at least inhibitor or inhibition method to suppress or to close carrying out of hydrogen discharge reaction, and hydrogen rate of release in the time of can coming the modulation hydrogen discharge reaction by the implantation concentration number of inhibitor affects the speed that hydrogen discharges.For example work as aqueous reaction thing and solid hydrogen fuel (solid hydrides and solid are put hydrogen catalyst) and be mixed into a body, and can't utilize contact/cordless switch, then can use inhibitor at least or inhibition method suppressing or to close the carrying out of this hydrogen discharge reaction, but and hydrogen rate of release during by the degree modulation hydrogen discharge reaction of inhibition.
Among one embodiment, the kind of inhibitor for example be alkaline liquid, Virahol, can with water be reacted into oxide compound material, can with water strong adsorption or the material of removing, maybe can be with the material of water and solid state hydrogen isolation.
Wherein, the material that can be reacted into oxide compound with water for example is iron powder, aluminium powder, magnesium powder, calcium powder, calcium hydroxide, calcium oxide or the nano-powder of above-mentioned substance as inhibitor, to form oxide compound with the water reaction.But the compound with aforementioned list is not limited.
Wherein, can select water strong adsorption or the material removed as inhibitor, such as being the materials such as sulfuric acid or sodium-acetate.
Wherein, can utilize tensio-active agent as inhibitor, with water and solid state hydrogen (comprise solid hydrides and solid put hydrogen catalyst) isolation.
In addition, except inhibitor, also can suppress or close carrying out of this hydrogen discharge reaction by the inhibition method, this inhibition method can be any method that water can be removed, for example utilize the High Temperature Furnaces Heating Apparatus heating means with moisture removal, Heating temperature for example is between 40 ℃ ~ 400 ℃ scopes, adjusts depending on the practical application situation.Moreover, also can utilize the anti-Heat of Formation of inhibitor and water to heat, wherein this inhibitor is iron powder, aluminium powder, magnesium powder, calcium powder, calcium hydroxide, calcium oxide or the nano-powder of above-mentioned substance.
Below be to utilize calcium oxide to be example as inhibitor, illustrate to reach the effect that " On/Off " hydrogen discharges, related description is as follows.
Please refer to Fig. 6, its illustrate according to another embodiment of the present invention with inhibitor reach switch with regulate releases of chemical hydride hydrogen test the module schematic diagram.Wherein solid hydrides, the solid mixture of putting hydrogen catalyst and aqueous reaction thing is being put hydrogen.Be the water that adds 1.5mL with the briquetting thing of 2g lime powder in the experiment, it is thermopositive reaction, and the heat that produces evaporates water, and calcium oxide also falls the water consumption of this mixture, the water that participates in reaction in this system is removed, and therefore can suppress the generation of hydrogen.In five times reproducibility research,
Have and all can keep more than the 30min not aerogenesis for four times, having one only is aerogenesis inferior to 19min, supposition may be that water suitably contact with calcium oxide briquetting thing (inhibitor), causes effect not cite.
Switch and control method that the disclosed chemical hydride hydrogen of the above embodiment of the present invention discharges see through the release that " contact/noncontact " can effectively reach " On/Off " chemical hydride hydrogen.The speed that wherein utilizes the adjustable variation hydride of the number hydrogen of contact area to discharge, contact area is directly proportional with hydrogen-producing speed, and this contact area is greater than 1/2 o'clock, and hydrogen-producing speed is greater than 1/2 of design discharge.Also can utilize in addition the injection of inhibitor or inhibition method to reach to close hydrogen to discharge, and the speed that can utilize the degree of inhibition to come modulation chemical hydride hydrogen to discharge.The disclosed method of embodiment need not be used complicated and huge physical construction just can be controlled the hydrogen of releasing that chemical hydride is hydrolyzed speed and the unlatching when putting hydrogen or closes chemical hydride, not only working method is very simple, on using, also has volume little, the characteristics that are convenient for carrying, integral body can significantly be saved manufacturing cost, is rich in economic worth.Moreover, the disclosed mode of the present invention can be arranged in pairs or groups with the mechanism design of system and product easily mutually, makes outside the design comparatively simply of hydrogen generating system, and solid hydrogen fuel also can discharge and close hydrogen effectively, plurality of advantages can promote user's use wish, and makes product application more extensive.
In sum, although the present invention discloses as above with embodiment, so it is not to limit the present invention.The persond having ordinary knowledge in the technical field of the present invention, without departing from the spirit and scope of the invention, when doing various changes and retouching.Therefore, protection scope of the present invention is as the criterion when looking claims.
The present invention includes following:
1. the method that discharges of a chemical hydride hydrogen comprises:
Provide and comprise that solid hydrides, solid put hydrogen catalyst and the elastomeric mixture of hydrophobic polymer and aqueous reaction thing; With
Adjust the contact area of this mixture and this aqueous reaction thing with the control hydrogen discharge reaction, produce hydrogen, when wherein this mixture and this aqueous reaction thing were contact condition, this solid hydrides and this aqueous reaction thing carried out hydrogen discharge reaction, and this solid is put this hydrogen discharge reaction of hydrogen catalyst catalysis.
2. such as 1 a described method, wherein make this mixture and this aqueous reaction thing be contactless state, to stop this hydrogen discharge reaction, stop release hydrogen.
3. such as 1 a described method, wherein this aqueous reaction thing is water, alcohols, the aqueous solution, salts solution or the acidic aqueous solution of alcohol or the aqueous solution of aforementioned combination.
4. such as 1 a described method, wherein this aqueous reaction thing is solid water.
5. such as 4 a described method, wherein this solid water is the macromolecule water uptake material, and this polymer comprises polyacrylic ester, polyvinyl alcohol, acetate ethylene copolymer, urethane, polyethylene oxide, starch graft copolymer or rubber blend.
6. such as 4 a described method, wherein after providing this solid hydrides, this solid to put hydrogen catalyst and this solid water, with comprise that this solid hydrides and this solid are put hydrogen catalyst evenly to be mixed to form this mixture behind the powder respectively, afterwards this mixture is formed and press caked mass, this pressure caked mass is contacted, to carry out this hydrogen discharge reaction with the aqueous reaction thing.
7. such as 1 a described method, wherein solid hydrides is to comprise hydroborate, nitrogen hydride, hydrocarbons, metal hydride, boron nitrogen hydride, boron hydrocarbons, nitrogen hydrocarbons, metal borohydride, metal nitrogen hydride, metal hydrocarbons, metal boron nitrogen hydride, metal boron hydrocarbons, metal carbonitride hydride, boron nitrogen hydrocarbons, metal boron nitrogen hydrocarbons or above-mentioned combination.
8. as 1 a described method, wherein this hydrophobic polymer elastomerics is silica gel, rubber or silicon rubber, or wherein appoints both or three's combination.
9. the method that discharges of a chemical hydride hydrogen comprises:
Provide at least solid hydrides, solid to put hydrogen catalyst and aqueous reaction thing, wherein this aqueous reaction thing and this solid hydrides and this solid are put hydrogen catalyst and are mixed into a body;
Provide at least inhibitor or inhibition method to suppress or to close carrying out of this hydrogen discharge reaction, hydrogen-producing speed with control and adjustment hydrogen discharge reaction, wherein by the addition of this inhibitor or with the water strong adsorption or remove or add can be with the material of water and solid state hydrogen isolation, to suppress and to adjust this hydrogen-producing speed.
10. such as 9 a described method, wherein the kind of this inhibitor be alkaline liquid, Virahol, be reacted into the material of oxide compound with water, with water strong adsorption or the material of removing or material that water and solid state hydrogen are isolated, and should the inhibition method be the method that water is removed.
11. such as 10 a described method, wherein this inhibitor is iron powder, aluminium powder, magnesium powder, calcium powder, calcium hydroxide, calcium oxide or the nano-powder of above-mentioned substance, to be reacted into oxide compound with water.
12. as 10 described methods, wherein this inhibitor is sulfuric acid or sodium-acetate, with the water strong adsorption or remove.
13. as 10 described methods, wherein should the inhibition method for heating with moisture removal.
14. such as 13 a described method, wherein heating means are utilized the High Temperature Furnaces Heating Apparatus heating.
15. such as 13 a described method, wherein heating means utilize this inhibitor and the anti-Heat of Formation of water to heat, wherein this inhibitor is iron powder, aluminium powder, magnesium powder, calcium powder, calcium hydroxide, calcium oxide or the nano-powder of above-mentioned substance.
16. such as 13 a described method, wherein the temperature range of heating is approximately 40 ℃ ~ 400 ℃.
17. as 10 described methods, wherein this inhibitor is tensio-active agent, water and this solid hydrides and this solid is put hydrogen catalyst isolate.
18. such as 9 a described method, wherein this aqueous reaction thing is the aqueous solution of water, alcohols, its aqueous solution, salts solution or acidic aqueous solution or aforementioned combination.
19. such as 9 a described method, wherein this aqueous reaction thing is solid water.
20. such as 19 a described method, wherein this solid water is the macromolecule water uptake material, this polymer comprises polyacrylic ester, polyvinyl alcohol, acetate ethylene copolymer, urethane, polyethylene oxide, starch graft copolymer or rubber blend.
Claims (14)
1. the method that discharges of a chemical hydride hydrogen comprises:
Provide at least solid hydrides, solid to put hydrogen catalyst and aqueous reaction thing, wherein this aqueous reaction thing and this solid hydrides and this solid are put hydrogen catalyst and are mixed into a body;
Provide at least inhibitor or inhibition method to suppress or to close carrying out of this hydrogen discharge reaction, hydrogen-producing speed with control and adjustment hydrogen discharge reaction, wherein by the addition of this inhibitor or with the water strong adsorption or remove or add can be with the material of water and solid state hydrogen isolation, to suppress and to adjust this hydrogen-producing speed.
2. the method for claim 1, wherein the kind of this inhibitor be alkaline liquid, Virahol, be reacted into the material of oxide compound with water, with water strong adsorption or the material of removing or material that water and solid state hydrogen are isolated, and should the inhibition method be the method that water is removed.
3. method as claimed in claim 2, wherein this inhibitor is iron powder, aluminium powder, magnesium powder, calcium powder, calcium hydroxide, calcium oxide or the nano-powder of above-mentioned substance, to be reacted into oxide compound with water.
4. method as claimed in claim 2, wherein this inhibitor is sulfuric acid or sodium-acetate, with the water strong adsorption or remove.
5. method as claimed in claim 2, wherein should the inhibition method for heating with moisture removal.
6. method as claimed in claim 5, wherein heating means are utilized the High Temperature Furnaces Heating Apparatus heating.
7. method as claimed in claim 5, wherein heating means utilize this inhibitor and the anti-Heat of Formation of water to heat, and wherein this inhibitor is iron powder, aluminium powder, magnesium powder, calcium powder, calcium hydroxide, calcium oxide or the nano-powder of above-mentioned substance.
8. method as claimed in claim 5, wherein the temperature range of heating is approximately 40 ℃ ~ 400 ℃.
9. method as claimed in claim 2, wherein this inhibitor is tensio-active agent, and water and this solid hydrides and this solid are put the hydrogen catalyst isolation.
10. the method for claim 1, wherein this aqueous reaction thing is the aqueous solution of water, alcohols, its aqueous solution, salts solution or acidic aqueous solution or aforementioned combination.
11. the method for claim 1, wherein this aqueous reaction thing is solid water.
12. method as claimed in claim 11, wherein this solid water is the macromolecule water uptake material, and this polymer comprises polyacrylic ester, polyvinyl alcohol, acetate ethylene copolymer, urethane, polyethylene oxide, starch graft copolymer or rubber blend.
13. the method for claim 1, wherein solid hydrides is to comprise hydroborate, nitrogen hydride, hydrocarbons, metal hydride, boron nitrogen hydride, boron hydrocarbons, nitrogen hydrocarbons, metal borohydride, metal nitrogen hydride, metal hydrocarbons, metal boron nitrogen hydride, metal boron hydrocarbons, metal carbonitride hydride, boron nitrogen hydrocarbons, metal boron nitrogen hydrocarbons or above-mentioned combination.
14. the method for claim 1, wherein solid put hydrogen catalyst be comprise solid peracid, contain ruthenium, metal ion, atoms metal, metal nanoparticle or the micron particle of nanoparticle, micron particle or the aforementioned metal of the metallic salt of cobalt, nickel, copper, iron or aforementioned metal be attached to solid catalyst made on the carrier or above-mentioned combination.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US28546709P | 2009-12-10 | 2009-12-10 | |
| US61/285,467 | 2009-12-10 |
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|---|---|---|---|
| CN2010102432815A Division CN102092682B (en) | 2009-12-10 | 2010-08-03 | One-off and adjustment method of hydrogen releasing from chemical hydride |
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| CN102849678A true CN102849678A (en) | 2013-01-02 |
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| CN2010102432196A Pending CN102097639A (en) | 2009-12-10 | 2010-07-30 | Hydrogen generation system using solid hydrogen fuel and method for providing hydrogen and providing hydrogen for fuel cell using the same |
| CN2010102432815A Active CN102092682B (en) | 2009-12-10 | 2010-08-03 | One-off and adjustment method of hydrogen releasing from chemical hydride |
| CN2012103475840A Pending CN102849678A (en) | 2009-12-10 | 2010-08-03 | One-off and adjustment method of hydrogen releasing from chemical hydride |
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|---|---|---|---|
| CN2010102432196A Pending CN102097639A (en) | 2009-12-10 | 2010-07-30 | Hydrogen generation system using solid hydrogen fuel and method for providing hydrogen and providing hydrogen for fuel cell using the same |
| CN2010102432815A Active CN102092682B (en) | 2009-12-10 | 2010-08-03 | One-off and adjustment method of hydrogen releasing from chemical hydride |
Country Status (3)
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| JP (1) | JP2013129594A (en) |
| CN (3) | CN102097639A (en) |
| TW (2) | TWI507354B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108975344A (en) * | 2018-08-22 | 2018-12-11 | 成都理工大学 | The preparation method of amorphous Cu-B-N-H nano material |
| CN109415205A (en) * | 2017-04-22 | 2019-03-01 | 银河测试有限公司 | Equipment for generating hydrogen |
| CN113428834A (en) * | 2020-11-24 | 2021-09-24 | 艾氢技术(苏州)有限公司 | Hydrogen release control system for solid hydrogen generation device |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| TWI485104B (en) * | 2012-08-31 | 2015-05-21 | Nat Inst Chung Shan Science & Technology | A balance system for generating hydrogen by chemical method |
| JP5916686B2 (en) * | 2013-11-12 | 2016-05-11 | 株式会社Tkx | Hydrogen gas production method and hydrogen gas production apparatus |
| KR101981691B1 (en) * | 2017-11-03 | 2019-05-23 | 조선대학교산학협력단 | Chemical hydride based microbubbles generating agent and Bubble generation adjustable microbubbles generating agent that can control the timming of bubble generation |
| CN111232919A (en) * | 2020-01-21 | 2020-06-05 | 西安医学院 | Preparation method of synergistic oxidation-resistant hydrogen storage coral calcium |
| CN114122419B (en) * | 2021-03-24 | 2023-12-12 | 包头稀土研究院 | Direct sodium borohydride fuel cell DBFC anode and preparation method thereof |
| CN113975401B (en) * | 2021-09-29 | 2023-09-22 | 中国科学院深圳先进技术研究院 | Medical hydrogen storage material and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101049970A (en) * | 2007-04-02 | 2007-10-10 | 武汉理工大学 | Method for preparing stable sol of composite oxides of vanadium and tungsten |
| CN101249941A (en) * | 2007-06-19 | 2008-08-27 | 汉能科技有限公司 | Preparation of hydrogen-storage material used for fuel cell |
| CN101283075A (en) * | 2005-10-03 | 2008-10-08 | 法商Bic公司 | Optimizing hydrogen generating efficiency in fuel cell cartridges |
| CN101410326A (en) * | 2006-03-15 | 2009-04-15 | 法商Bic公司 | Fuel compositions for fuel cells and gas generators utilizing same |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB8723034D0 (en) * | 1987-10-01 | 1988-03-23 | Dowty Maritime Systems Ltd | Gas generating devices |
| US6709778B2 (en) * | 2000-04-10 | 2004-03-23 | Johnson Electro Mechanical Systems, Llc | Electrochemical conversion system |
| US6645651B2 (en) * | 2001-06-01 | 2003-11-11 | Robert G. Hockaday | Fuel generator with diffusion ampoules for fuel cells |
| US7641889B1 (en) * | 2003-05-14 | 2010-01-05 | Lynntech Power Systems, Ltd. | Hydrogen generator |
| US7481858B2 (en) * | 2005-02-25 | 2009-01-27 | Societe Bic | Hydrogen generating fuel cell cartridges |
| TWI295118B (en) * | 2004-03-10 | 2008-03-21 | Black & Decker Inc | Thermal management systems for battery packs |
| US20060257313A1 (en) * | 2005-02-17 | 2006-11-16 | Alan Cisar | Hydrolysis of chemical hydrides utilizing hydrated compounds |
| JP2007315546A (en) * | 2006-05-29 | 2007-12-06 | Taiheiyo Cement Corp | Hydrogen storage vessel and hydrogen absorption and desorption device |
-
2010
- 2010-04-26 TW TW099113137A patent/TWI507354B/en active
- 2010-07-06 TW TW099122243A patent/TW201119938A/en unknown
- 2010-07-30 CN CN2010102432196A patent/CN102097639A/en active Pending
- 2010-08-03 CN CN2010102432815A patent/CN102092682B/en active Active
- 2010-08-03 CN CN2012103475840A patent/CN102849678A/en active Pending
-
2013
- 2013-02-06 JP JP2013021415A patent/JP2013129594A/en not_active Withdrawn
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101283075A (en) * | 2005-10-03 | 2008-10-08 | 法商Bic公司 | Optimizing hydrogen generating efficiency in fuel cell cartridges |
| CN101410326A (en) * | 2006-03-15 | 2009-04-15 | 法商Bic公司 | Fuel compositions for fuel cells and gas generators utilizing same |
| CN101049970A (en) * | 2007-04-02 | 2007-10-10 | 武汉理工大学 | Method for preparing stable sol of composite oxides of vanadium and tungsten |
| CN101249941A (en) * | 2007-06-19 | 2008-08-27 | 汉能科技有限公司 | Preparation of hydrogen-storage material used for fuel cell |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109415205A (en) * | 2017-04-22 | 2019-03-01 | 银河测试有限公司 | Equipment for generating hydrogen |
| CN108975344A (en) * | 2018-08-22 | 2018-12-11 | 成都理工大学 | The preparation method of amorphous Cu-B-N-H nano material |
| CN113428834A (en) * | 2020-11-24 | 2021-09-24 | 艾氢技术(苏州)有限公司 | Hydrogen release control system for solid hydrogen generation device |
| CN113428834B (en) * | 2020-11-24 | 2023-02-28 | 艾氢技术(苏州)有限公司 | Hydrogen release control system for solid hydrogen generation device |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2013129594A (en) | 2013-07-04 |
| TWI507354B (en) | 2015-11-11 |
| TW201119938A (en) | 2011-06-16 |
| CN102092682A (en) | 2011-06-15 |
| TW201119937A (en) | 2011-06-16 |
| CN102097639A (en) | 2011-06-15 |
| CN102092682B (en) | 2013-02-13 |
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