CN103159172A - Hydrogen fuel synthetic method - Google Patents
Hydrogen fuel synthetic method Download PDFInfo
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- CN103159172A CN103159172A CN2012105329016A CN201210532901A CN103159172A CN 103159172 A CN103159172 A CN 103159172A CN 2012105329016 A CN2012105329016 A CN 2012105329016A CN 201210532901 A CN201210532901 A CN 201210532901A CN 103159172 A CN103159172 A CN 103159172A
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- Prior art keywords
- water
- hydrogen
- starch
- hydrogen fuel
- hydrogen storage
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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Abstract
The invention discloses a hydrogen fuel synthetic method which comprises the following steps: mixing well hydroboron, water absorbing materials, hydroxide and catalytic agents, and obtaining hydrogen storage materials; injecting water into the hydrogen storage materials, and dissolving the hydroboron and the hydroxide to form alkaline solutions, wherein the water absorbing materials absorb the alkaline solutions to form gel-like hydrogen storage materials; and hydrolyzing the hydroboron under the action of the catalytic agents to produce hydrogen gas. According to the hydrogen fuel synthetic method, the releasing speed of the hydrogen gas can be controlled, and the prepared hydrogen gas is high in purity, and is not required to be further filtered.
Description
Technical field
The invention belongs to the hydrogen fuel technical field, be specifically related to a kind of synthetic method of controlling the hydrogen of release rate.
Background technology
Sodium borohydride is the solvay-type hydride of commonly using, because it has excellent reductibility and purposes widely, at present at European ﹠ American Market in a large number for industrial production, but also very little in the use range of China, expand space in addition.
US Patent No. 6358488 has been reported the method that adopts nickel, cobalt or hydrogen-bearing alloy powder catalysis sodium borohydride hydrolysis generating hydrogen, and reaction equation is as follows:
NaBH
4+2H
2O→4H
2+NaBO
2
This hydrogen supplying method has advantages of the following aspects:
(1), sodium borohydride storage hydrogen fuel is a kind of eco-friendly material, carbon containing and nitrogenous obnoxious flavour are not discharged in whole hydrogen and use procedure;
(2), compare with other storage hydrogen modes, but Bian with the mode of storage in liquid hydrogen, the hydrogen-storage amount of fuel is high, can reach 10.8wt%, is 10 times of hydride hydrogen-storing;
(3), owing to using the solid sodium borohydride, store, use safety, delivery is convenient;
(4), hydrogen purity is high, can not cause poisoning of electrode catalyst of fuel cell, also there is no accompanying gas, can not cause the pollution of atmospheric environment;
(5), energy utilization rate is high, do not need the external energy just can be the hydrogen release in NaBH4 and a part of water out in reaction process.
Recently, sodium borohydride is used for hydrogen supply device as the storage hydrogen carrier and has caused people's very big interest and further investigation.Prior art can only be used the sodium borohydride aqueous solution, after the sodium borohydride aqueous solution adds reactor, hydrolysis immediately fully, this method can be used for the device of general collection hydrogen, and resulting hydrogen is to collect with special container, the hydrogen storage equipment that supplies for fuel cell, a lot of drawbacks have been used, sodium metaborate and the sodium hydroxide droplet of association when for example system approach is restricted, needs strainer to absorb the hydrogen generation.In fuel cell, we more need hydrogen storage material is directly dropped into in hydrogen storage equipment, are exactly directly sodium borohydride to be used for the hydrogen storage plenum system of fuel cell, utilize its hydrolysis gained hydrogen to produce electric energy.But only use sodium borohydride aqueous solution, can't achieve effective control to reaction process and hydrogen supply speed; And it is harsher to matching requirements, if sealing is not tight, leaking appears in solution, operation inconvenience.Therefore, need to a kind ofly both the hydrogen release rate can be controlled, the method for high-purity hydrogen can be obtained again.
Summary of the invention
The purpose of this invention is to provide a kind of the preparation of hydrogen method for fuel cell, described method can be controlled the hydrogen release rate, and the hydrogen purity of preparation is high, and feed stock conversion is high, need not its further filtration.
Technical scheme of the present invention comprises the steps: hydroborate, oxyhydroxide, water-absorbing material and catalyst mix are all hooked, get hydrogen storage material, the weight part ratio of described hydroborate, oxyhydroxide, water-absorbing material, catalyzer is 100:0.01-50:0.1-25:0.01-50, is preferably 100:10-35:2-15:2-30;
Water is injected described hydrogen storage material, survey the dissolving of hydride and oxyhydroxide and form basic solution, water-absorbing material absorbs basic solution and forms the gel hydrogen storage material; The hydrolysis of canopy hydride, produce hydrogen under the effect of catalyzer.
Described hydroborate is sodium borohydride, POTASSIUM BOROHYDRIDE, lithium borohydride or its mixture.
Described oxyhydroxide is a kind of in sodium hydroxide, potassium hydroxide, calcium hydroxide or several mixture wherein.
Described water-absorbing material is starch-series high absorbency material and/or cellulose high water-absorbing material.
Described starch-series high absorbency material is a kind of in starch-grafted vinyl cyanide, starch graft acrylic acid, starch graft acrylamide, 2-acrylamide-2-methyl propane sulfonic, acrylamide, sodium acrylate, Methacrylamide and MALEIC ANHYDRIDE or several mixture wherein.
Described starch-series high absorbency material is the water-absorbing material of treated starch and derivative preparation thereof.
Described water-absorbing material is a kind of in starch ester graft phenylethene high-absorbent material, Starch debranching enzyme hydrogel processed, modified formaldehyde starch-grafted third rare lonitrile copolymer, epoxychloropropane modified starch-grafted acrylonitrile copolymer, Racemic glycidol etherified crosslinked starch grafted propylene lonitrile copolymer or several mixture wherein.
described cellulose high water-absorbing material is polypropylene-based absorbing resin material, the Natvosol high absorbency material, the carboxymethyl cellulose high absorbency material, the cellulose xanthate high absorbency material, the Graft Copolymerization of Cellulose high absorbency material, cellulose graft acrylonitrile high water-absorption material, cellulose graft vinylformic acid high absorbency material, cellulose graft acrylamide high water absorption material, Natvosol graft acrylamide high absorbency material, a kind of in Natvosol/acrylamide/silicon dioxide composite material or several mixture wherein.
Described catalyzer is nickel and its esters, cobalt and its esters, platinum and its esters, palladium and its esters, or their mixture, and wherein nickel salt can be nickelous chloride NiCl
2, single nickel salt NiSO
4, nitric acid nickel (NO
3)
2Cobalt salt is cobalt chloride CoCl
2, sulfuric acid bores COSO
4, nitric acid bores Co (NO
3)
2Platinum salt can be ammonium chloroplatinate (NH
4)
2PtCl
6, potassium platinichloride K
2PtCl
6, ammonium chloroplatinite (NH
4)
2PtCl
4, potassium chloroplatinite K
2PtCl
4, Tetrachloroplatinum PtCl
4, platinum dichloride PtCl
2, platinum nitrate Pt (NO
3)
2Palladium salt can be Palladous nitrate Pd (NO
3)
2, palladium Pd (OAC)
2, Palladous chloride PdCl
2, palladous sulfate PdSO
4, ammonium palladic chloride (NH
4)
2PdCl
4, chlorine palladium acid sodium Na
2PdCl
4, potassium palladichloride K
2PdCl
4
Technique effect of the present invention: the method for preparing hydrogen provided by the invention comprises the preparation hydrogen storage material and utilizes hydrogen storage material to prepare two steps of hydrogen, wherein hydrogen storage material is that hydroborate, water-absorbing material, oxyhydroxide and catalyzer are evenly mixed, do not exist water-absorbing material zone and hydroborate regional in hydrogen storage material, avoided forming precipitation in the knock back process, improved the transformation efficiency of hydrogen.The oxyhydroxide that contains has the performance of further stablizing hydrogen storage material.The add-on of oxyhydroxide can be adjusted according to actual needs, if the shelf-time is longer, can add into some oxyhydroxide, otherwise, can add less or hydro-oxidation thing not, the proportion requirement of hydroborate and oxyhydroxide is not had strict restriction.Because oxyhydroxide can be stablized hydroborate, when the mixture of oxyhydroxide and hydroborate was dissolved in water, borohydride hydrolytic speed was extremely slow, need to add catalyzer facilitation of hydrolysis speed of response.The contriver is through designing after deep research easy and simple to handle and can controlling the hydrogen storage material of hydrogen formation speed.When water injects this hydrogen storage material, if the water-retaining agent absorption speed is greater than the hydroborate dissolution rate, water-absorbing material absorbs water and forms gel, and catalyzer all hooks and is distributed between gel, and the water in hydroborate and gel issues the unboiled water solution and produces hydrogen in the effect of catalyzer.The speed of this hydrolysis reaction is relevant with the rate of water loss of water-absorbing material, can pass through to select the speed of water-absorbing material controlled hydrolysis reaction, thereby controls the release rate of hydrogen.The consumption of catalyzer can add according to actual needs,, can add into some catalyzer faster during the hydrogen formation speed when needs, otherwise, can reduce the addition of catalyzer.Because reaction is carried out, thereby do not need gas-liquid separation in the gel hydrogen storage material, there is no flowing of liquid yet, system's cylinder list does not have the restriction of orientation, is suitable for disposable continuous use.By to the selection of water-absorbing material and the adjustment of catalyst loading, just can make the hydrogen discharging speed of this system satisfy fuel cell to the demand of hydrogen.Form gelling material because hydrogen storage material can absorb water, avoided the particular requirement of hydroborate solution hydrolysis to device, make it be more convenient for using.Unexpectedly, the hydrogen purity of hydrogen storage material preparation provided by the invention is high, need not the steps such as filtration, and cylinder has been changed operation, and equipment is further simplified.
Embodiment
The invention will be further described below in conjunction with embodiment:
Embodiment 1
Hydrogen storage material: sodium borohydride 100g, sodium hydroxide 38g, Natvosol high absorbency material 22g, catalyzer potassium platinichloride K
2PtCl
64.5g;
Preparation method: with sodium borohydride, sodium hydroxide, Natvosol high absorbency material, catalyzer potassium platinichloride K
2PtCl
6Mix, get hydrogen storage material;
Utilize this hydrogen storage material to prepare the method for hydrogen: 500g water is injected described hydrogen storage material, and sodium borohydride and sodium hydroxid dissolving form basic solution, and water-absorbing material absorbs basic solution and forms the gel hydrogen storage material; Catalyzer potassium platinichloride K
2PtCl
6Become metal platinum to be evenly distributed in the basic solution of sodium borohydride by sodium borohydride reduction, the sodium borohydride hydrolysis, produce hydrogen under the effect of metal platinum.
Embodiment 2
Hydrogen storage material: sodium borohydride 100g, sodium hydroxide 0.01g, cellulose xanthate high absorbency material 25g, catalyzer Sample powder 30g;
Preparation method: sodium borohydride, sodium hydroxid, cellulose xanthate high absorbency material, catalyzer nickel powder are mixed all hooking, get hydrogen storage material;
Utilize this hydrogen storage material to prepare the method for hydrogen: 500g water is injected described hydrogen storage material, and sodium borohydride and dissolution of sodium hydroxide form basic solution, and water-absorbing material absorbs basic solution and forms the gel hydrogen storage material; Catalyzer is evenly distributed in the basic solution of sodium borohydride, and the sodium borohydride hydrolysis, produce hydrogen under the effect of catalyzer.
Embodiment 3
Hydrogen storage material: POTASSIUM BOROHYDRIDE 100g, sodium hydroxide 2g, cellulose graft acrylamide high water absorption material 0.1g, catalyzer drillings 45g;
Preparation method: POTASSIUM BOROHYDRIDE, sodium hydroxid, cellulose graft acrylamide high water absorption material, catalyzer cobalt powder are mixed all hooking, get hydrogen storage material;
Utilize this hydrogen storage material to prepare the method for hydrogen: 500g water is injected described hydrogen storage material, and POTASSIUM BOROHYDRIDE and hydrogen-oxygen are received the thing dissolving and are formed basic solution, and water-absorbing material absorbs basic solution and forms the gel hydrogen storage material; Catalyzer is evenly distributed in the basic solution of POTASSIUM BOROHYDRIDE, and the POTASSIUM BOROHYDRIDE hydrolysis, produce hydrogen under the effect of catalyzer.
Embodiment 4
Hydrogen storage material: sodium borohydride 100g, potassium hydroxide 50g, Natvosol/acrylamide/silicon dioxide composite material 1g, catalyzer platinum powder 50g;
Preparation method: sodium borohydride, potassium hydroxide, Natvosol/acrylamide/silicon dioxide composite material, catalyzer platinum powder are mixed all hooking, get hydrogen storage material;
Utilize this hydrogen storage material to prepare the method for hydrogen: 100g water is injected described hydrogen storage material, and sodium borohydride and potassium hydroxide dissolving form basic solution, and water-absorbing material absorbs basic solution and forms the gel hydrogen storage material; Catalyzer is evenly distributed in the basic solution of sodium borohydride, and the sodium borohydride hydrolysis, produce hydrogen under the effect of catalyzer.
Embodiment 5
Hydrogen storage material: POTASSIUM BOROHYDRIDE 100g, potassium hydroxide 45g, starch-grafted vinyl cyanide 10g, palladium catalyst powder 20g;
Preparation method: POTASSIUM BOROHYDRIDE, potassium hydroxide, starch-grafted vinyl cyanide, palladium catalyst powder are mixed, get hydrogen storage material;
Utilize this hydrogen storage material to prepare the method for hydrogen: 300g water is injected described hydrogen storage material, and POTASSIUM BOROHYDRIDE and potassium hydroxide dissolving form basic solution, and water-absorbing material absorbs basic solution and forms the gel hydrogen storage material; Catalyzer all hooks in the basic solution that is distributed in POTASSIUM BOROHYDRIDE, and the POTASSIUM BOROHYDRIDE hydrolysis, produce hydrogen under the effect of catalyzer.
Water-absorbing material in above-described embodiment can also use the starch-series high absorbency material: a kind of during starch graft acrylic acid, starch graft acrylamide, 2-acrylamide-2-methyl propane sulfonic, acrylamide, acrylate, starch graft acrylic acid and vinylformic acid are received or several mixture wherein;
The water-absorbing material of treated starch and derivative preparation thereof: Starch debranching enzyme hydrogel processed, the starch-grafted acrylonitrile copolymer of modified formaldehyde;
Cellulose high water-absorbing material: a kind of in carboxymethyl cellulose high absorbency material, Graft Copolymerization of Cellulose high absorbency material, cellulose graft acrylonitrile high water-absorption material, cellulose graft the third Xi acid high absorbency material, Natvosol graft acrylamide high absorbency material or several mixture wherein.
Catalyzer is potassium platinichloride K
2PtCl
6, ammonium chloroplatinite (NH
4)
2PtCl
4, potassium chloroplatinite K
2PtCl
4, Tetrachloroplatinum PtCl
4, platinum dichloride PtCl
2, platinum nitrate Pt (N0
3)
2, palladium Pd (OAC)
2, Palladous chloride PdCl
2, palladous sulfate PdSO
4, ammonium palladic chloride (NH
4)
2PdCl
4, the acid of chlorine palladium receives Na
2PdCl
4, potassium palladichloride K
2PdCl
4
The above is only the preferred embodiments of the present invention; not thereby limit protection scope of the present invention; the equivalent structure of doing on specification sheets of the present invention basis, or directly, indirectly be used in other relevant technical field, within all in like manner being included in protection scope of the present invention.
Claims (8)
1. the method for a synthetic hydrogen fuel, is characterized in that, comprises the steps:
Hydroborate, oxyhydroxide, water-absorbing material and catalyst mix are all hooked, get hydrogen storage material, the weight part ratio of described hydroborate, oxyhydroxide, water-absorbing material, catalyzer is 100:0.01-50:0.1-25:0.01-50;
Water is injected described hydrogen storage material, and hydroborate and oxyhydroxide dissolving form basic solution, and water-absorbing material absorbs basic solution and forms the gel hydrogen storage material; Borohydride hydrolytic under the effect of catalyzer produces hydrogen.
2. the method for synthetic hydrogen fuel according to claim 1, is characterized in that, described hydrogen storage material comprises the component of following weight parts: hydroborate 100, oxyhydroxide 10-35, water-absorbing material 2-15, catalyzer 2-30.
3. the method for synthetic hydrogen fuel according to claim 1 and 2, is characterized in that, described hydroborate is sodium borohydride, POTASSIUM BOROHYDRIDE, lithium borohydride or its mixture.
4. the method for synthetic hydrogen fuel according to claim 1 and 2, is characterized in that, described oxyhydroxide is a kind of in sodium hydroxide, potassium hydroxide, calcium hydroxide or several mixture wherein.
5. the method for synthetic hydrogen fuel according to claim 1 and 2, is characterized in that, described water-absorbing material is starch-series high absorbency material and/or cellulose high water-absorbing material.
6. the method for synthetic hydrogen fuel according to claim 5, it is characterized in that, described starch-series high absorbency material is a kind of in starch-grafted vinyl cyanide, starch graft acrylic acid, starch graft acrylamide, 2-acrylamide-2-methyl propane sulfonic, acrylamide, sodium acrylate, Methacrylamide and MALEIC ANHYDRIDE or several mixture wherein.
7. the method for synthetic hydrogen fuel according to claim 5, is characterized in that, described starch-series high absorbency material is the water-absorbing material of treated starch and derivative preparation thereof.
8. the method for synthetic hydrogen fuel according to claim 1 and 2, is characterized in that, described catalyzer is nickel and its esters, cobalt and its esters, platinum and its esters, palladium and its esters, or their mixture.
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| CN2012105329016A CN103159172A (en) | 2012-12-11 | 2012-12-11 | Hydrogen fuel synthetic method |
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|---|---|---|---|
| CN2012105329016A CN103159172A (en) | 2012-12-11 | 2012-12-11 | Hydrogen fuel synthetic method |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106684406A (en) * | 2017-02-14 | 2017-05-17 | 武汉市能智达科技有限公司 | MgH2 hydrogen-storage material reaction cavity and fuel cell generation device thereof |
| CN112599798A (en) * | 2020-12-16 | 2021-04-02 | 北京大学 | NaBH4Sponge and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101249947A (en) * | 2007-06-19 | 2008-08-27 | 汉能科技有限公司 | Preparation of hydrogen gas used for fuel cell |
| CN101327910A (en) * | 2007-06-19 | 2008-12-24 | 汉能科技有限公司 | Hydrogen storage material, preparation and use thereof |
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2012
- 2012-12-11 CN CN2012105329016A patent/CN103159172A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101249947A (en) * | 2007-06-19 | 2008-08-27 | 汉能科技有限公司 | Preparation of hydrogen gas used for fuel cell |
| CN101327910A (en) * | 2007-06-19 | 2008-12-24 | 汉能科技有限公司 | Hydrogen storage material, preparation and use thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106684406A (en) * | 2017-02-14 | 2017-05-17 | 武汉市能智达科技有限公司 | MgH2 hydrogen-storage material reaction cavity and fuel cell generation device thereof |
| CN112599798A (en) * | 2020-12-16 | 2021-04-02 | 北京大学 | NaBH4Sponge and preparation method thereof |
| CN112599798B (en) * | 2020-12-16 | 2021-12-07 | 北京大学 | NaBH4Sponge and preparation method thereof |
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Application publication date: 20130619 |