CN101327909A - Hydrogen storage material, preparation and use thereof - Google Patents
Hydrogen storage material, preparation and use thereof Download PDFInfo
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- CN101327909A CN101327909A CNA2007101190520A CN200710119052A CN101327909A CN 101327909 A CN101327909 A CN 101327909A CN A2007101190520 A CNA2007101190520 A CN A2007101190520A CN 200710119052 A CN200710119052 A CN 200710119052A CN 101327909 A CN101327909 A CN 101327909A
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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 storage material for fuel cell, a preparation method and the usage thereof. The hydrogen storage material comprises a borohydride, a hydroxide and an absorption material and has advantages of stable performance, easy storage and carry which can control the releasing speed of the hydrogen without filtering the prepared hydrogen and belong to the field of fuel cell.
Description
Technical field
The present invention relates to a kind of hydrogen storage material of fuel cell, be specifically related to a kind of hydrogen storage material of fuel cell of may command hydrogen release rate.The invention still further relates to the preparation method and its usage of above-mentioned hydrogen storage material.
Background technology
Sodium borohydride is the solvay-type hydride of using always, be at first by people such as Schlesinger at the nineteen forty-two synthetic because it has excellent reductibility and purposes widely, be used for industrial production at present in a large number in American-European market, but the use range in China is also very little, expands space in addition.
U.S. Pat 6 358 488 has been reported the method that adopts nickel, cobalt or hydrogen-bearing alloy powder catalysis sodium borohydride hydrolysis generation hydrogen.Reaction equation is as follows:
NaBH
4+2H
2O→4H
2+NaBO
2
This hydrogen supplying method has the advantage of the following aspects: (1) sodium borohydride storage hydrogen fuel is a kind of eco-friendly material, and carbon containing and nitrogenous obnoxious flavour are not discharged in whole hydrogen and use; (2) compare with other storage hydrogen modes, can adopt the liquid mode that stores hydrogen, the hydrogen-storage amount height of fuel can reach 10.8wt%, is 10 times of hydride hydrogen-storing; (3) owing to use solid sodium borohydride, storage, safe in utilization, delivery are conveniently; (4) hydrogen purity height can not cause poisoning of electrode catalyst of fuel cell, does not have accompanying gas yet, can not cause the pollution of atmospheric environment; (5) energy utilization rate height does not need the external energy just can be NaBH in the reaction process
4And the hydrogen release in a part of water is come out.
Recently, sodium borohydride is used for very big interest and the further investigation that hydrogen supply device has caused people as the storage hydrogen carrier.Prior art can only be used sodium borohydride aqueous solution, hydrolysis immediately was complete after sodium borohydride aqueous solution added reactor, this method can be used for the device of general collection hydrogen, and resulting hydrogen is to collect with special container, hydrogen supply equipment for fuel cell, a lot of drawbacks have been used, the 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 directly dropped in the hydrogen supply equipment and use, and directly sodium borohydride are used for the hydrogen storage plenum system of fuel cell exactly, utilize its hydrolysis gained hydrogen to produce electric energy.Iff using sodium borohydride aqueous solution, can't achieve effective control to reaction process and hydrogen supply speed.
Publication number is please disclose a kind of hydrogen generator in the patent of invention of CN1845873A, its employed solid hydrogen source is with water wetted material zone and solid hydride object area form layers shape roller volume, but the water wetted material direct fluid makes it that hydrolysis reaction take place to solid hydrides, preparation hydrogen.This solid hydrogen source is owing to have water wetted material zone and solid hydride object area, and the solid hydrides unstable properties can not be deposited, and must use immediately after the preparation.And owing to contain catalyzer, wayward speed of response.And form the intersection of borate calmness in the reaction process, make water wetted material lose the effect of direct fluid, hinder the further reaction of solid hydrides, reduced the product hydrogen rate of solid hydrides at water wetted material zone and solid hydride object area.
Publication number is that CN1918268A discloses a kind of fuel mixture that is used for hydrogen generator, described aqueous fuel comprises hydroborate and is used for the stablizer of described borohydride salt that in water-bearing media described stablizer comprises the oxyhydroxide that is selected from sodium hydroxide, lithium hydroxide and potassium hydroxide.Positive ion electric charge in this fuel mixture (+ICs) mol ratio with the boron atom is 0.2-0.4, be preferably 0.2-0.3, perhaps 0.6-0.99, be preferably 0.7-0.8, if ratio surpasses this scope, the borate of generation forms precipitation and occluding device, if ratio is less than above-mentioned scope, the hydroborate instability, as seen its proportion requirement to hydroborate and stablizer is very strict, otherwise influences the transformation efficiency of hydrogen.
Therefore, need a kind ofly to store easy to carry, stable performance, hydrogen conversion height, can control the hydrogen release rate and do not need the filtering hydrogen storage material of hydrogen preparation.
Summary of the invention
The purpose of this invention is to provide and a kind ofly store easy to carry, stable performance, hydrogen conversion height, can control the hydrogen release rate and do not need the filtering hydrogen storage material of hydrogen preparation.
Another object of the present invention provides the preparation method of above-mentioned hydrogen storage material.
A further object of the present invention provides the method for utilizing above-mentioned hydrogen storage material to prepare hydrogen.
For achieving the above object, the present inventor has carried out a large amount of research and performing creative labour on the basis of existing technology, developed stable performance, be convenient to deposit, easy to carry and can control the hydrogen storage material of hydrogen release rate, obtained unexpected effect.Comprise following components by part by weight: hydroborate 100, oxyhydroxide 0.01-50, water-absorbing material 0.1-25.
Described hydroborate is sodium borohydride, POTASSIUM BOROHYDRIDE, lithium borohydride or its mixture.
Described oxyhydroxide is a kind of or wherein several mixture in sodium hydroxide, potassium hydroxide, ammoniacal liquor, the calcium hydroxide.
Described water-absorbing material is that starch is high absorbency material and/or cellulose high water-absorbing material.
Described starch is that high absorbency material is a kind of or wherein several mixture in starch-grafted vinyl cyanide, starch graft acrylic acid, starch graft acrylamide, 2-acrylamide-2-methyl propane sulfonic acid, acrylamide, sodium acrylate, Methacrylamide and the MALEIC ANHYDRIDE.
Described starch is that high absorbency material is the water-absorbing material of treated starch and derivative preparation thereof.
Described water-absorbing material is a kind of or wherein several mixture in starch ester graft phenylethene high-absorbent material, Starch debranching enzyme system hydrogel, formaldehyde treated starch grafted propylene lonitrile copolymer, epoxychloropropane modified starch-grafted acrylonitrile copolymer, the glycidyl ether cross-linking starch grafted propylene lonitrile copolymer.
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 or wherein several mixture in Natvosol/acrylamide/silicon dioxide composite material.
A kind of method for preparing described hydrogen storage material comprises the steps:
Hydroborate, oxyhydroxide and water are mixed with alkaline borohydride solution, alkaline borohydride solution is injected water-absorbing material, water-absorbing material absorbs alkaline borohydride solution, form the hydroborate gelating soln, through room temperature vacuum-drying, make water content be lower than 1wt%, obtain the hydroborate hydrogen storage material that water-absorbing material coats.
A kind of method of utilizing described hydrogen storage material to prepare hydrogen comprises the steps: catalyst precursor solution is joined in the described hydrogen storage material, and catalyst precursor solution is absorbed by the hydroborate hydrogen storage material that water-absorbing material coats, and forms gel; Complex catalyst precursor is become catalyst metal to be evenly distributed in the gel by borohydride reduction, and hydrolysis reaction takes place on catalyst metal hydroborate, produces hydrogen.
Described complex catalyst precursor is nickel salt, cobalt salt, platinum salt or palladium salt, and described catalyst precursor solution is that nickel salt, cobalt salt, platinum salt or palladium salt are dissolved in water, is mixed with the aqueous solution.
Described nickel salt is NiCl
2, Ni (NO
3)
2, NiSO
4, it contains crystal water salt or its aqueous solution; Described cobalt salt is CoSO
4, CoCl
2, Co (NO
3)
2, it contains crystal water salt or its aqueous solution; Described platinum salt is 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
2Or platinum nitrate Pt (NO
3)
2Described palladium salt is 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
4Or potassium palladichloride K
2PdCl
4
Compared with prior art, hydrogen storage material provided by the invention is that hydroborate, oxyhydroxide and water are mixed with alkaline borohydride solution, alkaline borohydride solution is injected water-absorbing material, water-absorbing material absorbs alkaline borohydride solution, form the hydroborate gelating soln, through room temperature vacuum-drying, obtain the hydroborate hydrogen storage material that water-absorbing material coats.There are not water-absorbing material zone and hydroborate zone in the hydrogen storage material, avoided forming precipitation in the reaction process, improved the transformation efficiency of hydrogen.The oxyhydroxide that contains can be stablized hydroborate, and therefore hydroborate hydrolysis reaction can not take place when depositing.The add-on of oxyhydroxide can be adjusted according to actual needs, if the shelf-time is longer, then can add into some oxyhydroxide, otherwise, can lack the hydro-oxidation thing.Proportion requirement to hydroborate and oxyhydroxide does not have strict restriction.The present invention relatively is applicable to the purposes that needs to produce continuously hydrogen.Add catalyst precursor solution to described hydrogen storage material, catalyst precursor solution is absorbed by the hydroborate hydrogen storage material that water-absorbing material coats, and forms gel; Complex catalyst precursor is become catalyst metal to be evenly distributed in the gel by borohydride reduction, and hydrolysis reaction takes place on catalyst metal hydroborate, produces hydrogen.Complex catalyst precursor can be nickel salt, cobalt salt, platinum salt or palladium salt, and hydrogen discharging speed can be controlled by the amount of the nickel salt, cobalt salt, platinum salt or the palladium salt brine solution that add.The add-on of the amount of nickel salt, cobalt salt, platinum salt or palladium salt brine solution is big more, and hydrogen discharging speed is high more.Because complex catalyst precursor can consume a part of hydroborate when being reduced into catalyst metal, so the ratio of hydroborate and nickel salt, cobalt salt, platinum salt or palladium salt is between 100: 0.15～30.
Because reaction is carried out in the gel hydrogen storage material, thereby does not need gas-liquid separation, there be not flowing of liquid yet, system is simple, does not have the restriction of orientation, is suitable for disposable continuous use.By adjustment, just can make the hydrogen discharging speed of this system satisfy the demand of fuel cell to hydrogen to the catalyst precursor solution addition.Unexpectedly, the hydrogen purity height of hydrogen storage material preparation provided by the invention need not steps such as filtration, has simplified operation, and equipment is further simplified.
Embodiment
Further elaborate the present invention below in conjunction with embodiment.
Water-absorbing material among the embodiment all is commercial goods.
In order to determine the consumption of water-absorbing material, need to determine its water-intake rate that the mensuration process is as follows:
Use tap water to do and be absorbed body, water-absorbing material carries out blank assay as absorption agent, add a certain amount of water-absorbing material, glass rod stirs, and partly generated gel in the solution this moment, and the gel particles suspended dispersed is in water, gel poured in the sand core funnel together with solution filter, to substantially no longer following of drop (after about 15 minutes), weighing gel weight promptly gets the pick up of water-absorbing material.The pick up measurement result of cellulose high water-absorbing material sees Table 1; Starch is that the pick up measurement result of high absorbency material sees Table 2; The pick up measurement result of treated starch and derivative thereof sees Table 3.
Embodiment 1
Hydrogen storage material: sodium borohydride 100g, sodium hydroxide 25g, Starch debranching enzyme system hydrogel 18g.
The preparation method: sodium borohydride, sodium hydroxide and 500g water are mixed with alkaline sodium borohydride solution, alkaline sodium borohydride solution is injected the water-absorbing material Starch debranching enzyme, water-absorbing material absorbs alkaline sodium borohydride solution, forms the sodium borohydride gelating soln.Through room temperature vacuum-drying, make water content be lower than 1wt%, obtain the sodium borohydride hydrogen storage material that water-absorbing material coats.
Utilize this hydrogen storage material to prepare the method for hydrogen: will contain 1g nickelous chloride NiCl
2Catalyst precursor solution 100g join in the described hydrogen storage material, the sodium borohydride hydrogen storage material that catalyst precursor solution is coated by water-absorbing material absorbs, and forms gel.Complex catalyst precursor is become catalyst metal nickel to be evenly distributed in the gel by sodium borohydride reduction, and hydrolysis reaction takes place on metallic nickel sodium borohydride, produces hydrogen.
Embodiment 2
Hydrogen storage material: sodium borohydride 100g, potassium hydroxide 0.01g, cellulose xanthate high absorbency material 25g;
Preparation method: sodium borohydride, potassium hydroxide and 1000g water are mixed with alkaline sodium borohydride solution, alkaline sodium borohydride solution is injected the cellulose xanthate high absorbency material, water-absorbing material absorbs alkaline sodium borohydride solution, forms the sodium borohydride gelating soln.Through room temperature vacuum-drying, make water content be lower than 1wt%, obtain the sodium borohydride hydrogen storage material that water-absorbing material coats.
Utilize this hydrogen storage material to prepare the method for hydrogen: will contain 3g cobalt chloride CoCl
2Catalyst precursor solution 100g join in the described hydrogen storage material, the sodium borohydride hydrogen storage material that catalyst precursor solution is coated by water-absorbing material absorbs, and forms gel.Complex catalyst precursor is become the catalyst metal cobalt to be evenly distributed in the gel by sodium borohydride reduction, and hydrolysis reaction takes place on cobalt metal sodium borohydride, produces hydrogen.
Embodiment 3
Hydrogen storage material: POTASSIUM BOROHYDRIDE 100g, sodium hydroxide 20g, cellulose graft acrylamide high water absorption material 0.1g.
Preparation method: POTASSIUM BOROHYDRIDE, sodium hydroxide and 600g water are mixed with alkaline solution of potassium borohydride, alkaline solution of potassium borohydride is injected cellulose graft acrylamide high water absorption material, water-absorbing material absorbs alkaline solution of potassium borohydride, forms the POTASSIUM BOROHYDRIDE gelating soln.Through room temperature vacuum-drying, make water content be lower than 1wt%, obtain the POTASSIUM BOROHYDRIDE hydrogen storage material that water-absorbing material coats.
Utilize this hydrogen storage material to prepare the method for hydrogen: will contain 4.5g single nickel salt NiSO
4Catalyst precursor solution 100g join in the described hydrogen storage material, the POTASSIUM BOROHYDRIDE hydrogen storage material that catalyst precursor solution is coated by water-absorbing material absorbs, and forms gel.Complex catalyst precursor is become catalyst metal nickel to be evenly distributed in the gel by potassium borohydride reduction, and POTASSIUM BOROHYDRIDE is nickel generation hydrolysis reaction on metal, produces hydrogen.
Embodiment 4
Hydrogen storage material: lithium borohydride 100g, sodium hydroxide 50g, Natvosol/acrylamide/silicon dioxide composite material 1g;
Preparation method: lithium borohydride, sodium hydroxide and 400g water are mixed with alkaline lithium borohydride solution, alkaline lithium borohydride solution is injected water-absorbing material Natvosol/acrylamide/silicon dioxide composite material, water-absorbing material absorbs alkaline lithium borohydride solution, forms the lithium borohydride gelating soln.Through room temperature vacuum-drying, make water content be lower than 1wt%, obtain the lithium borohydride hydrogen storage material that water-absorbing material coats.
Utilize this hydrogen storage material to prepare the method for hydrogen: will contain 2.5g rose vitriol CoSO
4Catalyst precursor solution 100g join in the described hydrogen storage material, the lithium borohydride hydrogen storage material that catalyst precursor solution is coated by water-absorbing material absorbs, and forms gel.Complex catalyst precursor is reduced into the catalyst metal cobalt by lithium borohydride and is evenly distributed in the gel, and hydrolysis reaction takes place on cobalt metal lithium borohydride, produces hydrogen.
Embodiment 5
Hydrogen storage material: sodium borohydride 100g, 10wt% ammoniacal liquor 10ml, starch-grafted vinyl cyanide 10g;
The preparation method: sodium borohydride, ammoniacal liquor and 500g water are mixed with alkaline sodium borohydride solution, alkaline sodium borohydride solution is injected the starch-grafted vinyl cyanide of water-absorbing material, water-absorbing material absorbs alkaline sodium borohydride solution, forms the sodium borohydride gelating soln.Through room temperature vacuum-drying, make water content be lower than 1wt%, obtain the sodium borohydride hydrogen storage material that water-absorbing material coats.
Utilize this hydrogen storage material to prepare the method for hydrogen: will contain 1g nitric acid nickel (NO
3)
2Catalyst precursor solution 100g join in the described hydrogen storage material, the sodium borohydride hydrogen storage material that catalyst precursor solution is coated by water-absorbing material absorbs, and forms gel.Complex catalyst precursor is become catalyst metal nickel to be evenly distributed in the gel by sodium borohydride reduction, and hydrolysis reaction takes place on metallic nickel sodium borohydride, produces hydrogen.
Embodiment 6
Hydrogen storage material: sodium borohydride 100g, sodium hydroxide 10g, 2-acrylamide-2-methyl propane sulfonic acid 15g;
Preparation method: sodium borohydride, sodium hydroxide and 800g water are mixed with alkaline sodium borohydride solution, alkaline sodium borohydride solution is injected water-absorbing material 2-acrylamide-2-methyl propane sulfonic acid, water-absorbing material absorbs alkaline sodium borohydride solution, forms the sodium borohydride gelating soln.Through room temperature vacuum-drying, make water content be lower than 1wt%, obtain the sodium borohydride hydrogen storage material that water-absorbing material coats.
Utilize this hydrogen storage material to prepare the method for hydrogen: will contain 5g Xiao Suangu Co (NO
3)
2Catalyst precursor solution 100g join in the described hydrogen storage material, the sodium borohydride hydrogen storage material that catalyst precursor solution is coated by water-absorbing material absorbs, and forms gel.Complex catalyst precursor is become the catalyst metal cobalt to be evenly distributed in the gel by sodium borohydride reduction, and hydrolysis reaction takes place on cobalt metal sodium borohydride, produces hydrogen.
Embodiment 7
Hydrogen storage material: POTASSIUM BOROHYDRIDE 100g, sodium hydroxide 35g, Methacrylamide 20g;
The preparation method: POTASSIUM BOROHYDRIDE, sodium hydroxide and 300g water are mixed with alkaline solution of potassium borohydride, alkaline solution of potassium borohydride is injected the water-absorbing material Methacrylamide, water-absorbing material absorbs alkaline solution of potassium borohydride, forms the POTASSIUM BOROHYDRIDE gelating soln.Through room temperature vacuum-drying, make water content be lower than 1wt%, obtain the POTASSIUM BOROHYDRIDE hydrogen storage material that water-absorbing material coats.
Utilize this hydrogen storage material to prepare the method for hydrogen: will contain 4g ammonium chloroplatinate (NH
4)
2PtCl
6Catalyst precursor solution 100g join in the described hydrogen storage material, the POTASSIUM BOROHYDRIDE hydrogen storage material that catalyst precursor solution is coated by water-absorbing material absorbs, and forms gel.Complex catalyst precursor is become catalyst metal platinum to be evenly distributed in the gel by potassium borohydride reduction, and hydrolysis reaction takes place on metal platinum POTASSIUM BOROHYDRIDE, produces hydrogen.
Embodiment 8
Hydrogen storage material: sodium borohydride 100g, sodium hydroxide 40g, MALEIC ANHYDRIDE 5g;
The preparation method: sodium borohydride, sodium hydroxide and 400g water are mixed with alkaline sodium borohydride solution, alkaline sodium borohydride solution is injected the water-absorbing material MALEIC ANHYDRIDE, water-absorbing material absorbs alkaline sodium borohydride solution, forms the sodium borohydride gelating soln.Through room temperature vacuum-drying, make water content be lower than 1wt%, obtain the sodium borohydride hydrogen storage material that water-absorbing material coats.
Utilize this hydrogen storage material to prepare the method for hydrogen: will contain 5g potassium platinichloride K
2PtCl
6Catalyst precursor solution 100g join in the described hydrogen storage material, the sodium borohydride hydrogen storage material that catalyst precursor solution is coated by water-absorbing material absorbs, and forms gel.Complex catalyst precursor is become catalyst metal platinum to be evenly distributed in the gel by sodium borohydride reduction, and hydrolysis reaction takes place on metal platinum sodium borohydride, produces hydrogen.
Embodiment 9
Hydrogen storage material: lithium borohydride 100g, sodium hydroxide 5g, starch ester graft phenylethene high-absorbent material 8g;
Preparation method: lithium borohydride, sodium hydroxide and 600g water are mixed with alkaline lithium borohydride solution, alkaline lithium borohydride solution is injected starch ester graft phenylethene high-absorbent material, water-absorbing material absorbs alkaline lithium borohydride solution, forms the lithium borohydride gelating soln.Through room temperature vacuum-drying, make water content be lower than 1wt%, obtain the lithium borohydride hydrogen storage material that water-absorbing material coats.
Utilize this hydrogen storage material to prepare the method for hydrogen: will contain 0.15g Palladous nitrate Pd (NO
3)
2Catalyst precursor solution 100g join in the described hydrogen storage material, the lithium borohydride hydrogen storage material that catalyst precursor solution is coated by water-absorbing material absorbs, and forms gel.Complex catalyst precursor is reduced into the catalyst metal palladium by lithium borohydride and is evenly distributed in the gel, and hydrolysis reaction takes place on palladium metal lithium borohydride, produces hydrogen.
Embodiment 10
Hydrogen storage material: sodium borohydride 100g, calcium hydroxide 30g, epoxychloropropane modified starch-grafted acrylonitrile copolymer 12g;
Preparation method: sodium borohydride, calcium hydroxide and 900g water are mixed with alkaline sodium borohydride solution, alkaline sodium borohydride solution is injected the epoxychloropropane modified starch-grafted acrylonitrile copolymer of water-absorbing material, water-absorbing material absorbs alkaline sodium borohydride solution, forms the sodium borohydride gelating soln.Through room temperature vacuum-drying, make water content be lower than 1wt%, obtain the sodium borohydride hydrogen storage material that water-absorbing material coats.
Utilize this hydrogen storage material to prepare the method for hydrogen: will contain 3.5g palladium Pd (OAC)
2Catalyst precursor solution 100g join in the described hydrogen storage material, the sodium borohydride hydrogen storage material that catalyst precursor solution is coated by water-absorbing material absorbs, and forms gel.Complex catalyst precursor is become the catalyst metal palladium to be evenly distributed in the gel by sodium borohydride reduction, and hydrolysis reaction takes place on palladium metal sodium borohydride, produces hydrogen.
Embodiment 11
Hydrogen storage material: sodium borohydride 100g, sodium hydroxide 15g, glycidyl ether cross-linking starch grafted propylene lonitrile copolymer 0.5g;
Preparation method: sodium borohydride, sodium hydroxide and 850g water are mixed with alkaline sodium borohydride solution, alkaline sodium borohydride solution is injected water-absorbing material glycidyl ether cross-linking starch grafted propylene lonitrile copolymer, water-absorbing material absorbs alkaline sodium borohydride solution, forms the sodium borohydride gelating soln.Through room temperature vacuum-drying, make water content be lower than 1wt%, obtain the sodium borohydride hydrogen storage material that water-absorbing material coats.
Utilize this hydrogen storage material to prepare the method for hydrogen: will contain 2g Tetrachloroplatinum PtCl
4Catalyst precursor solution 100g join in the described hydrogen storage material, the sodium borohydride hydrogen storage material that catalyst precursor solution is coated by water-absorbing material absorbs, and forms gel.Complex catalyst precursor is become catalyst metal platinum to be evenly distributed in the gel by sodium borohydride reduction, and hydrolysis reaction takes place on metal platinum sodium borohydride, produces hydrogen.
It is high absorbency material that water-absorbing material in the foregoing description can also use starch: a kind of or wherein several mixture in starch graft acrylic acid, starch graft acrylamide, 2-acrylamide-2-methyl propane sulfonic acid, acrylamide, acrylate, starch graft acrylic acid and the sodium acrylate;
The water-absorbing material of treated starch and derivative preparation thereof: Starch debranching enzyme system hydrogel, formaldehyde treated starch grafted propylene lonitrile copolymer;
Cellulose high water-absorbing material: a kind of or wherein several mixture in Natvosol high absorbency material, carboxymethyl cellulose high absorbency material, Graft Copolymerization of Cellulose high absorbency material, cellulose graft acrylonitrile high water-absorption material, cellulose graft vinylformic acid high absorbency material, the Natvosol graft acrylamide high absorbency material.
Catalyzer is ammonium chloroplatinite (NH
4)
2PtCl
4, potassium chloroplatinite K
2PtCl
4, platinum dichloride PtCl
2, platinum nitrate Pt (NO
3)
2, Palladous chloride PdCl
2, palladous sulfate PdSO
4, ammonium palladic chloride (NH
4)
2PdCl
4, chlorine palladium acid sodium Na
2PdCl
4Or potassium palladichloride K
2PdCl
4
Claims (12)
1, a kind of hydrogen storage material that is used for fuel cell is characterized in that described hydrogen storage material comprises following components by part by weight: hydroborate 100, oxyhydroxide 0.01-50, water-absorbing material 0.1-25.
2,, it is characterized in that described hydroborate is sodium borohydride, POTASSIUM BOROHYDRIDE, lithium borohydride or its mixture according to the described hydrogen storage material of claim 1.
3,, it is characterized in that described oxyhydroxide is a kind of or wherein several mixture in sodium hydroxide, potassium hydroxide, ammoniacal liquor, the calcium hydroxide according to the described hydrogen storage material of claim 1.
4,, it is characterized in that described water-absorbing material is that starch is high absorbency material and/or cellulose high water-absorbing material according to the described hydrogen storage material of claim 1.
5,, it is characterized in that described starch is that high absorbency material is a kind of or wherein several mixture in starch-grafted vinyl cyanide, starch graft acrylic acid, starch graft acrylamide, 2-acrylamide-2-methyl propane sulfonic acid, acrylamide, sodium acrylate, Methacrylamide and the MALEIC ANHYDRIDE according to the described hydrogen storage material of claim 4.
6,, it is characterized in that described starch is that high absorbency material is the water-absorbing material of treated starch and derivative preparation thereof according to the described hydrogen storage material of claim 4.
7,, it is characterized in that described water-absorbing material is a kind of or wherein several mixture in starch ester graft phenylethene high-absorbent material, Starch debranching enzyme system hydrogel, formaldehyde treated starch grafted propylene lonitrile copolymer, epoxychloropropane modified starch-grafted acrylonitrile copolymer, the glycidyl ether cross-linking starch grafted propylene lonitrile copolymer according to the described hydrogen storage material of claim 6.
8, according to the described hydrogen storage material of claim 4, it is characterized in that 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 or wherein several mixture in Natvosol/acrylamide/silicon dioxide composite material.
9, a kind of method for preparing the described hydrogen storage material of claim 1 is characterized in that described method comprises the steps:
Hydroborate, oxyhydroxide and water are mixed with alkaline borohydride solution, alkaline borohydride solution is injected water-absorbing material, and water-absorbing material absorbs alkaline borohydride solution, forms the hydroborate gelating soln, through room temperature vacuum-drying, obtain the hydroborate hydrogen storage material that water-absorbing material coats.
10, a kind of method of utilizing the described hydrogen storage material of claim 1 to prepare hydrogen, it is characterized in that described method comprises the steps: catalyst precursor solution is joined in the described hydrogen storage material, catalyst precursor solution is absorbed by the hydroborate hydrogen storage material that water-absorbing material coats, and forms gel; Complex catalyst precursor is become catalyst metal to be evenly distributed in the gel by borohydride reduction, and hydrolysis reaction takes place on catalyst metal hydroborate, produces hydrogen.
11, in accordance with the method for claim 10, it is characterized in that described complex catalyst precursor is nickel salt, cobalt salt, platinum salt or palladium salt.
12, in accordance with the method for claim 11, it is characterized in that described nickel salt is NiCl
2, Ni (NO
3)
2, NiSO
4, it contains crystal water salt or its aqueous solution; Described cobalt salt is CoSO
4, CoCl
2, Co (NO
3)
2, it contains crystal water salt or its aqueous solution; Described platinum salt is 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
2Or platinum nitrate Pt (NO
3)
2Described palladium salt is 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
4Or potassium palladichloride K
2PdCl
4
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007101190520A CN101327909A (en) | 2007-06-19 | 2007-06-19 | Hydrogen storage material, preparation and use thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007101190520A CN101327909A (en) | 2007-06-19 | 2007-06-19 | Hydrogen storage material, preparation and use thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2242140A1 (en) | 2009-04-16 | 2010-10-20 | Industrial Technology Research Institute | Hydrogen supply device |
| CN102211757A (en) * | 2010-04-09 | 2011-10-12 | 中国科学院金属研究所 | System and method for producing hydrogen by controllably hydrolyzing sodium borohydride/aluminum powder mixed solid fuel |
| CN101877411B (en) * | 2009-04-29 | 2012-10-10 | 财团法人工业技术研究院 | Hydrogen supplying device |
| US8658055B2 (en) | 2009-03-13 | 2014-02-25 | Industrial Technology Research Institute | Solid-state hydrogen fuel with polymer matrix and fabrication methods thereof |
| CN108059126A (en) * | 2017-12-04 | 2018-05-22 | 上海交通大学 | One kind contains NiB12Reversible composite hydrogen storage material and preparation method thereof |
| CN112599798A (en) * | 2020-12-16 | 2021-04-02 | 北京大学 | NaBH4Sponge and preparation method thereof |
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2007
- 2007-06-19 CN CNA2007101190520A patent/CN101327909A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8658055B2 (en) | 2009-03-13 | 2014-02-25 | Industrial Technology Research Institute | Solid-state hydrogen fuel with polymer matrix and fabrication methods thereof |
| EP2242140A1 (en) | 2009-04-16 | 2010-10-20 | Industrial Technology Research Institute | Hydrogen supply device |
| JP2010248053A (en) * | 2009-04-16 | 2010-11-04 | Ind Technol Res Inst | Hydrogen supply device |
| US7959898B2 (en) | 2009-04-16 | 2011-06-14 | Industrial Technology Research Institute | Hydrogen supply device |
| CN101877411B (en) * | 2009-04-29 | 2012-10-10 | 财团法人工业技术研究院 | Hydrogen supplying device |
| CN102211757A (en) * | 2010-04-09 | 2011-10-12 | 中国科学院金属研究所 | System and method for producing hydrogen by controllably hydrolyzing sodium borohydride/aluminum powder mixed solid fuel |
| CN108059126A (en) * | 2017-12-04 | 2018-05-22 | 上海交通大学 | One kind contains NiB12Reversible composite hydrogen storage material and preparation method 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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