CN100503426C - Hydrogen generation device for hydrolyzing metal hydride to produce hydrogen and hydrogen generation method - Google Patents
Hydrogen generation device for hydrolyzing metal hydride to produce hydrogen and hydrogen generation method Download PDFInfo
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- CN100503426C CN100503426C CNB2005101091329A CN200510109132A CN100503426C CN 100503426 C CN100503426 C CN 100503426C CN B2005101091329 A CNB2005101091329 A CN B2005101091329A CN 200510109132 A CN200510109132 A CN 200510109132A CN 100503426 C CN100503426 C CN 100503426C
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- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 165
- 239000001257 hydrogen Substances 0.000 title claims abstract description 165
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 105
- 238000000034 method Methods 0.000 title claims description 15
- 229910052987 metal hydride Inorganic materials 0.000 title claims description 5
- 150000004681 metal hydrides Chemical class 0.000 title claims description 5
- 230000003301 hydrolyzing effect Effects 0.000 title description 6
- 239000007788 liquid Substances 0.000 claims abstract description 117
- 239000002699 waste material Substances 0.000 claims abstract description 80
- 238000006243 chemical reaction Methods 0.000 claims description 82
- 239000000243 solution Substances 0.000 claims description 77
- 238000006555 catalytic reaction Methods 0.000 claims description 59
- 150000002431 hydrogen Chemical class 0.000 claims description 56
- 230000015572 biosynthetic process Effects 0.000 claims description 45
- 238000004140 cleaning Methods 0.000 claims description 43
- 238000003860 storage Methods 0.000 claims description 38
- 239000007789 gas Substances 0.000 claims description 28
- 229920005989 resin Polymers 0.000 claims description 24
- 239000011347 resin Substances 0.000 claims description 24
- 238000004519 manufacturing process Methods 0.000 claims description 23
- -1 polyoxymethylene Polymers 0.000 claims description 23
- 238000011084 recovery Methods 0.000 claims description 16
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 14
- 229910000000 metal hydroxide Inorganic materials 0.000 claims description 13
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- 229910001220 stainless steel Inorganic materials 0.000 claims description 8
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- 239000004593 Epoxy Substances 0.000 claims description 6
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 6
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
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- 239000004645 polyester resin Substances 0.000 claims description 6
- 229920006324 polyoxymethylene Polymers 0.000 claims description 6
- 229920006380 polyphenylene oxide Polymers 0.000 claims description 6
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 5
- 230000002378 acidificating effect Effects 0.000 claims description 5
- 239000003456 ion exchange resin Substances 0.000 claims description 5
- 229920003303 ion-exchange polymer Polymers 0.000 claims description 5
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 5
- 239000012279 sodium borohydride Substances 0.000 claims description 5
- 239000012429 reaction media Substances 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- WEHMXWJFCCNXHJ-UHFFFAOYSA-N propa-1,2-dienylbenzene Chemical compound C=C=CC1=CC=CC=C1 WEHMXWJFCCNXHJ-UHFFFAOYSA-N 0.000 claims description 2
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 238000004064 recycling Methods 0.000 abstract 2
- 239000000446 fuel Substances 0.000 description 11
- 239000000463 material Substances 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 5
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 5
- 230000007797 corrosion Effects 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 5
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- 239000002184 metal Substances 0.000 description 5
- 238000000746 purification Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- HBGPNLPABVUVKZ-POTXQNELSA-N (1r,3as,4s,5ar,5br,7r,7ar,11ar,11br,13as,13br)-4,7-dihydroxy-3a,5a,5b,8,8,11a-hexamethyl-1-prop-1-en-2-yl-2,3,4,5,6,7,7a,10,11,11b,12,13,13a,13b-tetradecahydro-1h-cyclopenta[a]chrysen-9-one Chemical compound C([C@@]12C)CC(=O)C(C)(C)[C@@H]1[C@H](O)C[C@]([C@]1(C)C[C@@H]3O)(C)[C@@H]2CC[C@H]1[C@@H]1[C@]3(C)CC[C@H]1C(=C)C HBGPNLPABVUVKZ-POTXQNELSA-N 0.000 description 1
- PFRGGOIBYLYVKM-UHFFFAOYSA-N 15alpha-hydroxylup-20(29)-en-3-one Natural products CC(=C)C1CCC2(C)CC(O)C3(C)C(CCC4C5(C)CCC(=O)C(C)(C)C5CCC34C)C12 PFRGGOIBYLYVKM-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- SOKRNBGSNZXYIO-UHFFFAOYSA-N Resinone Natural products CC(=C)C1CCC2(C)C(O)CC3(C)C(CCC4C5(C)CCC(=O)C(C)(C)C5CCC34C)C12 SOKRNBGSNZXYIO-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 229910052728 basic metal Inorganic materials 0.000 description 1
- 150000003818 basic metals Chemical class 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Images
Classifications
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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
Abstract
The invention discloses a hydrogen generating device, which comprises the following parts: reserving chamber (21) of reacting liquid, catalytic reacting chamber (22), waste liquid recycling chamber (23) and hydrogen purifying unit (24), wherein the catalytic reacting chamber (22) interconnects reserving chamber (21) of reacting liquid and waste liquid recycling chamber (23); the hydrogen purifying unit (24) interconnects the catalytic reacting chamber (22).
Description
Technical field
The present invention relates to a kind of hydrogen formation apparatus and hydrogen production process, relate more specifically to a kind of hydrogen formation apparatus and hydrogen production process of compound metal hydroxide hydrolytic hydrogen production.
Background technology
Fuel cell generally is that raw material produces electric energy with hydrogen, has distinguishing features such as high-energy-density, cleanliness without any pollution, is the electrical source of power of ideal portable power source or power truck.People proposed many methods with storing hydrogen in fuel cell, such as high-pressure gaseous storage hydrogen, liquid storage hydrogen, carbon nanotube storage hydrogen, hydrogen storage alloy storage hydrogen.But all there is certain defective in these methods.For example, the poor stability of gaseous state storage hydrogen; The liquefaction cost of liquid storage hydrogen is higher; The speed for hydrogen absorbing and releasing of carbon nanotube is slow, the poor stability of loading capacity; The hydrogen-storage amount of hydrogen storage alloy is lower.
In recent years the someone proposes the method for compound metal hydroxide such as borohydride hydrolytic hydrogen production again, and the advantage of this method is that the storage rate height of hydrogen is (with NaBH
4Be example, hydrogen-storage amount reaches 10.9 weight %), produce hydrogen purity height (not containing other in the gas of generation), safety non-pollution etc. to the influential gas of cell catalyst.The principle of this method is shown below:
Wherein, M can be basic metal such as potassium, sodium, lithium.
The compound metal hydroxide hydrolytic hydrogen production generally is to carry out in hydrogen formation apparatus.For example, " gas chemical industry " 2003 the 28th the 5th phases of volume 52 pages of Hydrogen onDemand that introduced by Millennium Cell Inc.'s exploitation
TMThe sodium borohydride hydrogen generating system.As shown in Figure 1, this system comprises NaBH successively
4Fuel container 11, charge pump 12, catalytic reaction chamber 13, gas/liquid separation 14, (NaBO
2Return case 15), heat exchanger/coolant loop 16, the hydrogen that obtains enters into fuel cell or hydrogen engine 17.
Because the employed reaction solution of catalytic hydrolytic decomposition of metallic hydride hydrogen production process is alkalescence, therefore the hydrogen that makes also can show alkalescence, can produce harm to fuel cell system if directly enter fuel cell system, for example make the poisoning of catalyst of fuel cell, have a strong impact on electrode performance.And existing hydrogen formation apparatus does not all possess the hydrogen cleaning function.
Summary of the invention
The objective of the invention is to overcome the shortcoming that existing hydrogen formation apparatus does not possess the hydrogen cleaning function, a kind of hydrogen formation apparatus that possesses the hydrogen cleaning function is provided.
Another object of the present invention provides the hydrogen production process that uses this hydrogen formation apparatus.
The invention provides a kind of hydrogen formation apparatus, this hydrogen formation apparatus comprises that reaction solution storage room 21, catalyzed reaction room 22, waste liquid reclaim room 23, catalyzed reaction room 22 is stored room 21 with reaction solution respectively, waste liquid reclaims room 23 and is communicated with, wherein, this hydrogen formation apparatus also comprises hydrogen cleaning unit 24, and hydrogen cleaning unit 24 is communicated with catalyzed reaction room 22.
The present invention also provides a kind of hydrogen production process, this method comprises that reaction solution is stored room 21 from reaction solution to be transported to react the catalyzed reaction room 22 and to make hydrogen, the waste liquid that reaction obtains is transported to waste liquid from catalyzed reaction room 22 and reclaims the room 23, wherein, the process of described hydrogen manufacturing is carried out in hydrogen formation apparatus provided by the invention, and this method also comprises the step that purifies with the 24 pairs of hydrogen that make in hydrogen cleaning unit.
Because hydrogen formation apparatus provided by the invention also comprises the hydrogen cleaning unit, therefore can purify hydrogen, reduced infringement to fuel cell system.
Description of drawings
Fig. 1 is the Hydrogen on Demand of expression prior art
TMThe synoptic diagram of sodium borohydride hydrogen generating system;
Fig. 2 is the sectional view of expression hydrogen formation apparatus provided by the invention;
Fig. 3 is the sectional view of expression according to the hydrogen formation apparatus of another embodiment of the invention;
Fig. 4 is the unitary partial enlarged drawing of hydrogen cleaning of expression hydrogen formation apparatus provided by the invention,
Fig. 4 a-4c is respectively A, B shown in Figure 2, the enlarged view in C zone;
Fig. 5 is the schema of expression hydrogen production process provided by the invention.
Embodiment
As shown in Figure 2, hydrogen formation apparatus provided by the invention comprises that reaction solution storage room 21, catalyzed reaction room 22, waste liquid reclaim room 23, catalyzed reaction room 22 is stored room 21 with reaction solution respectively, waste liquid reclaims room 23 and is communicated with, wherein, this hydrogen formation apparatus also comprises hydrogen cleaning unit 24, and hydrogen cleaning unit 24 is communicated with catalyzed reaction room 22.
The position relation that the present invention stores between room 21, catalyzed reaction room 22, waste liquid recovery room 23, the hydrogen cleaning unit 24 reaction solution does not have concrete qualification.But for the ease of the carrying out of reaction, under the preferable case, reaction solution is stored room 21 and is reclaimed the below that room 23 is positioned at catalyzed reaction room 22 with waste liquid, and hydrogen cleaning unit 24 is positioned at the top of catalyzed reaction room 22.
Described hydrogen cleaning unit 24 can adopt the existing any processing unit that can remove gas alkalescence, and under the preferable case, shown in Fig. 4 a, described hydrogen cleaning unit 24 contains at least one section Zeo-karb 41 and at least one section anionite-exchange resin 42.Described Zeo-karb 41 and anionite-exchange resin 42 preferably are placed in the tubular vessel, and are separated by ion exchange resin obstruct net 43 between Zeo-karb 41 and the anionite-exchange resin 42.Described Zeo-karb 41 can be that strongly-acid also can be a slightly acidic, for example can be for being selected from strongly acidic styrene's type Zeo-karb, slightly acidic phenylallene type Zeo-karb, the acidulous acrylic acid's type Zeo-karb
Kind or several; Described anionite-exchange resin can be that strong basicity also can be a weakly alkaline, for example can be for being selected from strong-basicity styrene type anionite-exchange resin, strong basicity quaternary ammonium type vinylbenzene anionresin fat, the weakly alkaline styrene type anionite-exchange resin one or more.It is stainless steel mesh that described ion exchange resin intercepts net 43.When hydrogen cleaning unit 24 contains multistage Zeo-karb 41 and anionite-exchange resin 42, Zeo-karb 41 and anionite-exchange resin 42 preferred interval are placed, and are separated by ion exchange resin obstruct net 43 between Zeo-karb 41 and the anionite-exchange resin 42.In order to increase the contact area and the duration of contact of hydrogen cleaning unit 24 and hydrogen, and save the space, described tubular vessel is preferably serpentine tube.
As shown in Figure 2, described hydrogen cleaning unit 24 can be communicated with catalyzed reaction room 22 by known any way, under the preferable case, the top of catalyzed reaction room 22 or have air guide port 25 near the side at top, hydrogen cleaning unit 24 links to each other with air guide port 25.In order to prevent that reaction solution or waste liquid in the catalyzed reaction room 22 from entering into hydrogen cleaning unit 24, preferably is provided with gas-liquid filter net 26 between hydrogen cleaning unit 24 and catalyzed reaction room 22.Described gas-liquid filter net 26 can be existing various gas-liquid filter nets, and for example gas-liquid filter net 26 is one or more layers foamed metal.
Described catalyzed reaction room 22 can be made by existing various materials corrosion-resistant, satisfactory mechanical property, and described material can be stainless steel or engineering plastics.Described engineering plastics comprise polycarbonate resin, polyoxymethylene resinoid, polyester resin, polyamide-based resin, polyphenylene oxide resinoid, ABS (acrylonitrile-butadiene-styrene (ABS)) and epoxy plastics.Shape to catalyzed reaction room 22 does not have concrete restriction, but for the ease of combination is installed, catalyzed reaction room 22 is preferably a cube cylindricality.Be placed with catalyzer in the described catalyzed reaction room 22, this catalyzer can be placed one or more layers, and the kind of catalyzer has been conventionally known to one of skill in the art, and the present invention is unqualified to this.The bottom of described catalyzed reaction room 22 is preferably wavy, can increase the catalytic time of reaction solution and catalyzer like this.
Described reaction solution is stored room 21 and can be communicated with catalyzed reaction room 22 by known any way, and reaction solution storage room 21 is communicated with catalyzed reaction room 22 by liquid conducting pipes 27 under the preferable case.Reaction solution is stored room 21 and is had reaction solution outlet 28, and catalyzed reaction room 22 has reaction solution import 29, and liquid conducting pipes 27 links to each other with reaction solution outlet 28, reaction solution import 29 respectively.Under the preferable case, reaction solution outlet 28 is positioned at that reaction solution is stored the bottom of room 21 or near the side of bottom; Reaction solution import 29 is positioned at the top of catalyzed reaction room 22 or near the side at top, helps like this total overall reaction liquid that reaction solution is stored in the room 21 is transported in the catalyzed reaction room 22.
To store the amount that room 21 is transported to the reaction solution the catalyzed reaction room 22 in order controlling, liquid feeding control device 30 preferably to be set on liquid conducting pipes 27 from reaction solution.Described liquid feeding control device 30 can use existing various liquid feeding control device, as water pump, volume pump, is preferably water pump.
Described reaction solution is stored room 21 and can be made by existing various materials corrosion-resistant, satisfactory mechanical property, and described material can be stainless steel or engineering plastics.Described engineering plastics comprise polycarbonate resin, polyoxymethylene resinoid, polyester resin, polyamide-based resin, polyphenylene oxide resinoid, ABS and epoxy plastics.The shape of reaction solution being stored room 21 does not have concrete restriction, but for the ease of combination is installed, reaction solution is stored room 21 and is preferably a cube cylindricality.The top of reaction solution storage room 21 is provided with the charging opening 31 of tool plug.When needs are stored toward reaction solution when adding reaction solution in the room 21, the stopper of the charging opening 31 of tool plug is opened, inject reaction solution from charging opening.
Described waste liquid reclaims room 23 and can be communicated with catalyzed reaction room 22 by known any way, under the preferable case, catalyzed reaction room 22 bottoms have waste liquid outlet 32, waste liquid reclaims the top of room 23 or has waste liquid import 33 near the side at top, is connected by waste liquid transport pipe 34 between waste liquid outlet 32 and the waste liquid import 33.Be coated with on the described waste liquid outlet 32 and filter silk screen 35.Described waste liquid transport pipe 34 is provided with valve 36, when needs are discharged to waste liquid the waste liquid recovery room 23 from catalyzed reaction room 22, opens valve 36, reclaims in the room 23 because the action of gravity waste liquid is transported to waste liquid by waste liquid transport pipe 34 automatically.
Described waste liquid reclaims room 23 and can be made by existing various materials corrosion-resistant, satisfactory mechanical property, and described material can be stainless steel or engineering plastics.Described engineering plastics comprise polycarbonate resin, polyoxymethylene resinoid, polyester resin, polyamide-based resin, polyphenylene oxide resinoid, ABS and epoxy plastics.The shape that waste liquid is reclaimed room 23 does not have concrete restriction, but for the ease of combination is installed, waste liquid reclaims room 23 and is preferably a cube cylindricality.Described waste liquid reclaims the bottom of room 23 or is provided with the liquid outlet 37 of tool plug near the side of bottom.In the time waste liquid need being reclaimed waste liquid in the room 23 and discharge, the stopper of the liquid outlet 37 of tool plug opened get final product.
It can be independent enclosed space with waste liquid recovery room 23 that described reaction solution is stored room 21, and (as Fig. 2, shown in Figure 3) also can be integrated.When the two is integrated, can the recycle reaction solution, compound metal hydroxide is wherein decomposed fully, and can save the space, so the present invention preferably stores reaction solution room 21 and reclaims room 23 with waste liquid and be integrated.When reaction solution storage room 21 is integrated with waste liquid recovery room 23, if from the waste liquid that catalyzed reaction room 22 transfers out, contain undecomposed compound metal hydroxide, then waste liquid can be transported in the catalyzed reaction room 22 again by liquid conducting pipes 27 and react.
According to hydrogen formation apparatus provided by the invention, the air that purifies through described hydrogen cleaning unit 24 can directly enter into fuel cell system, also can store for future use.As shown in Figure 3, according to another one embodiment of the present invention, hydrogen formation apparatus provided by the invention can also comprise gas storage room 51.Described gas storage room 51 is communicated with hydrogen cleaning unit 24.
Described gas storage room 51 can be made by existing various materials corrosion-resistant, satisfactory mechanical property, and described material can be stainless steel or engineering plastics.Described engineering plastics comprise polycarbonate resin, polyoxymethylene resinoid, polyester resin, polyamide-based resin, polyphenylene oxide resinoid, ABS and epoxy plastics.Shape to gas storage room 51 does not have concrete restriction, but for the ease of combination is installed, gas storage room 51 is preferably a cube cylindricality.
Described gas storage room 51 can adopt existing the whole bag of tricks to be communicated with hydrogen cleaning unit 24, and under the preferable case, as shown in Figure 3, described hydrogen cleaning unit 24 is installed in the gas storage room 51.Can save the space like this, reduce the volume of hydrogen formation apparatus.
The top of described gas storage room 51 or have hydrogen outlet 52 near the side at top, hydrogen outlet 52 is connected with gas fittings 53.Described gas fittings 53 can external tracheae and barometric control unit.
Hydrogen formation apparatus provided by the invention can also comprise housing, and the gas storage room 51 that described reaction solution storage room 21, catalyzed reaction room 22, waste liquid recovery room 23, hydrogen cleaning unit 24 and selectivity comprise all is arranged in housing.Described housing can be made by existing various materials corrosion-resistant, satisfactory mechanical property, and described material can be stainless steel or engineering plastics.Described engineering plastics comprise polycarbonate resin, polyoxymethylene resinoid, polyester resin, polyamide-based resin, polyphenylene oxide resinoid, ABS and epoxy plastics.Shape to housing does not have concrete restriction, but for the ease of combination is installed, housing is preferably a cube cylindricality.
Hydrogen production process provided by the invention comprises that reaction solution is stored room 21 from reaction solution to be transported to react the catalyzed reaction room 22 and to make hydrogen, the waste liquid that reaction obtains is transported to waste liquid from catalyzed reaction room 22 and reclaims the room 23, wherein, the process of described hydrogen manufacturing is carried out in hydrogen formation apparatus provided by the invention, and this method also comprises the step that purifies with the 24 pairs of hydrogen that make in hydrogen cleaning unit.
The composition of described reaction solution has been conventionally known to one of skill in the art, and there is no particular limitation to this in the present invention.For example, reaction solution can be for by being added to compound metal hydroxide the reaction medium that forms in the alkaline aqueous solution.
The kind of described metal hydride has been conventionally known to one of skill in the art.For example, the general formula of described metal hydride is MQH4 or M ' (QH
4)
2, wherein M is an alkali metal, and M ' is an alkali earth metal, and Q is a kind of element that is selected from boron, aluminium, the gallium.Described metal hydride is preferably sodium borohydride, POTASSIUM BOROHYDRIDE or its mixture, more preferably sodium borohydride.
The kind of described alkaline aqueous solution has been conventionally known to one of skill in the art, for example sodium hydroxide solution, potassium hydroxide solution, ammoniacal liquor.Described alkaline aqueous solution is preferably sodium hydroxide solution or potassium hydroxide solution.The concentration of alkaline aqueous solution is not specifically limited, and for example the concentration of alkaline aqueous solution is 5-30 weight %.
The concentration of described compound metal hydroxide in described reaction medium is 2-50 weight %, is preferably 5-30 weight %.
Fig. 5 is the schema of hydrogen production process provided by the invention.Wherein, dotted line is represented the step that selectivity is carried out.
Below in conjunction with device shown in Figure 2, a preferred implementation of hydrogen production process provided by the invention is described in detail.
The above-mentioned reaction solution that contains compound metal hydroxide is joined reaction solution by charging opening 31 store in the room 21, utilize liquid feeding control device 30 that reaction solution is transported in the catalyzed reaction room 22 by liquid conducting pipes 27 then;
The hydrolysis in catalyzed reaction room 22 of compound metal hydroxide in the reaction solution generates hydrogen, the hydrogen that obtains enters into hydrogen cleaning unit 24 by air guide port 25, hydrogen is purified by at least one section Zeo-karb 41 and at least one section anionite-exchange resin 42 that hydrogen cleaning unit 24 contains, and the hydrogen after the purification directly enters into fuel cell system utilization;
After reaction is finished, open valve 36, reacted reaction solution is that waste liquid is transported in the waste liquid recovery room 23 by waste liquid transport pipe 34, if it is independent enclosed spaces with waste liquid recovery room 23 that reaction solution is stored room 21, then waste liquid is stored in waste liquid recovery room 23 and discharges by liquid outlet 37; If reaction solution is stored room 21 and is integrated with waste liquid recovery room 23, then utilize the waste liquid that liquid feeding control device 30 will contain the unreacted metal hydrogen compound again promptly to be transported to the catalyzed reaction room 22 from waste liquid recovery room 23 (reaction solution is stored room 21) by liquid conducting pipes 27, in waste liquid, contain when containing the unreacted metal hydrogen compound on a small quantity or not, waste liquid is discharged the effect of can reach the recycle reaction solution like this, increasing operation rate by liquid outlet 37.
Below in conjunction with device shown in Figure 3, the another one preferred implementation of hydrogen production process provided by the invention is described in detail.
The above-mentioned reaction solution that contains compound metal hydroxide is joined reaction solution by charging opening 31 store in the room 21, utilize liquid feeding control device 30 that reaction solution is transported in the catalyzed reaction room 22 by liquid conducting pipes 27 then;
The hydrolysis in catalyzed reaction room 22 of compound metal hydroxide in the reaction solution generates hydrogen, the hydrogen that obtains enters into hydrogen cleaning unit 24 by air guide port 25, hydrogen is purified by at least one section Zeo-karb 41 and at least one section anionite-exchange resin 42 that hydrogen cleaning unit 24 contains, hydrogen after the purification enters into gas storage room 51 and stores for future use, when needs used, the hydrogen of purification entered into fuel cell system utilization by hydrogen outlet 52;
After reaction is finished, open valve 36, reacted reaction solution is that waste liquid is transported in the waste liquid recovery room 23 by waste liquid transport pipe 34, if it is independent enclosed spaces with waste liquid recovery room 23 that reaction solution is stored room 21, then waste liquid is stored in waste liquid recovery room 23 and discharges by liquid outlet 37; If reaction solution is stored room 21 and is integrated with waste liquid recovery room 23, then utilize the waste liquid that liquid feeding control device 30 will contain the unreacted metal hydrogen compound again promptly to be transported to the catalyzed reaction room 22 from waste liquid recovery room 23 (reaction solution is stored room 21) by liquid conducting pipes 27, in waste liquid, contain when containing the unreacted metal hydrogen compound on a small quantity or not, waste liquid is discharged the effect of can reach the recycle reaction solution like this, increasing operation rate by liquid outlet 37.
Claims (21)
1, a kind of hydrogen formation apparatus, this hydrogen formation apparatus comprises that reaction solution storage room (21), catalyzed reaction room (22), waste liquid reclaim room (23), catalyzed reaction room (22) is stored room (21) with reaction solution respectively, waste liquid reclaims room (23) and is communicated with, it is characterized in that, this hydrogen formation apparatus also comprises the hydrogen cleaning unit (24) that can remove gas alkalescence, and hydrogen cleaning unit (24) are communicated with catalyzed reaction room (22).
2, hydrogen formation apparatus according to claim 1, wherein, described hydrogen cleaning unit (24) contains at least one section Zeo-karb (41) and at least one section anionite-exchange resin (42).
3, hydrogen formation apparatus according to claim 2, wherein, described Zeo-karb (41) is selected from one or more in strongly acidic styrene's type Zeo-karb, slightly acidic phenylallene type Zeo-karb, the acidulous acrylic acid's type Zeo-karb; Described anionite-exchange resin is selected from one or more in strong-basicity styrene type anionite-exchange resin, strong basicity quaternary ammonium type vinylbenzene anionresin fat, the weakly alkaline styrene type anionite-exchange resin.
4, hydrogen formation apparatus according to claim 2, wherein, described Zeo-karb (41) and anionite-exchange resin (42) are placed in the tubular vessel, and are separated by ion exchange resin obstruct net (43) between Zeo-karb (41) and the anionite-exchange resin (42).
5, hydrogen formation apparatus according to claim 4, wherein, described tubular vessel is a serpentine tube; It is stainless steel mesh that described ion exchange resin intercepts net (43).
6, hydrogen formation apparatus according to claim 1, wherein, described hydrogen cleaning unit (24) is positioned at the top of described catalyzed reaction room (22); The top of described catalyzed reaction room (22) or have air guide port (25) near the side at top, hydrogen cleaning unit (24) links to each other with air guide port (25), and is provided with gas-liquid filter net (26) between hydrogen cleaning unit (24) and catalyzed reaction room (22).
7, hydrogen formation apparatus according to claim 1 wherein, is placed with catalyzer in the described catalyzed reaction room (22), and the bottom of described catalyzed reaction room (22) is wavy.
8, hydrogen formation apparatus according to claim 1, wherein, described reaction solution is stored the below that room (21) is positioned at catalyzed reaction room (22); Described reaction solution is stored the bottom of room (21) or is had reaction solution outlet (28) near the side of bottom, the top of catalyzed reaction room (22) or have reaction solution import (29) near the side at top, described reaction solution is stored between room (21) and the catalyzed reaction room (22) and is provided with liquid conducting pipes (27); Described liquid conducting pipes (27) links to each other with reaction solution outlet (28), reaction solution import (29) respectively.
9, hydrogen formation apparatus according to claim 8, wherein, described liquid conducting pipes (27) is provided with liquid feeding control device (30); Described liquid feeding control device (30) is a water pump.
10, hydrogen formation apparatus according to claim 1, wherein, described waste liquid reclaims the below that room (23) is positioned at catalyzed reaction room (22); Described catalyzed reaction room (22) bottom has waste liquid outlet (32), and waste liquid reclaims the top of room (23) or has waste liquid import (33) near the side at top, is connected by waste liquid transport pipe (34) between waste liquid outlet (32) and the waste liquid import (33); Be coated with on the described waste liquid outlet (32) and filter silk screen (35); Described waste liquid transport pipe (34) is provided with valve (36).
11, hydrogen formation apparatus according to claim 1, wherein, described waste liquid reclaims the bottom of room (23) or is provided with the liquid outlet (37) with stopper near the side of bottom.
12, hydrogen formation apparatus according to claim 1, wherein, described reaction solution is stored room (21) and is integrated with waste liquid recovery room (23).
13, hydrogen formation apparatus according to claim 1, wherein, described reaction solution storage room (21), catalyzed reaction room (22), waste liquid reclaim room (23) and are made by stainless steel or engineering plastics; Described engineering plastics comprise polycarbonate resin, polyoxymethylene resinoid, polyester resin, polyamide-based resin, polyphenylene oxide resinoid, acrylonitrile-butadiene-styrene (ABS) and epoxy plastics.
14, hydrogen formation apparatus according to claim 1, wherein, this hydrogen formation apparatus also comprises gas storage room (51); Described gas storage room (51) is communicated with hydrogen cleaning unit (24).
15, hydrogen formation apparatus according to claim 14, wherein, described hydrogen cleaning unit (24) is installed in the gas storage room (51); The top of described gas storage room (51) or have hydrogen outlet (52) near the side at top, hydrogen outlet (52) is connected with gas fittings (53); External tracheae of described gas fittings (53) and barometric control unit.
16, hydrogen formation apparatus according to claim 1, wherein, this hydrogen formation apparatus also comprises housing, described reaction solution storage room (21), catalyzed reaction room (22), waste liquid reclaim room (23), hydrogen cleaning unit (24) are arranged in housing.
17, a kind of hydrogen production process, this method comprises that reaction solution is stored room (21) from reaction solution to be transported to react the catalyzed reaction room (22) and to make hydrogen, the waste liquid that reaction obtains is transported to waste liquid from catalyzed reaction room (22) and reclaims the room (23), it is characterized in that, the process of described hydrogen manufacturing is carried out in the described hydrogen formation apparatus of claim 1, and this method also comprises the step that the hydrogen that makes is purified with the hydrogen cleaning unit (24) that can remove gas alkalescence.
18, hydrogen production process according to claim 17, wherein, described reaction solution is by compound metal hydroxide being added to the reaction medium that forms in the alkaline aqueous solution; Described metal hydride is a sodium borohydride.
19, hydrogen production process according to claim 17, wherein, described hydrogen cleaning unit (24) contains at least one section Zeo-karb (41) and at least one section anionite-exchange resin (42), and the described hydrogen that makes is by described Zeo-karb (41) and anionite-exchange resin (42).
20, hydrogen production process according to claim 17, wherein, described reaction solution is stored room (21) and is reclaimed room (23) with waste liquid and be integrated, and the waste liquid that reaction obtains is stored room (21) from reaction solution and is transported to again the catalyzed reaction room (22) and reacts.
21, hydrogen production process according to claim 17, wherein, described hydrogen formation apparatus also comprises gas storage room (51), described gas storage room (51) is communicated with hydrogen cleaning unit (24), and the hydrogen storage that process hydrogen cleaning unit (24) purifies is in gas storage room (51).
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| CN104591088A (en) | 2013-10-30 | 2015-05-06 | 扬光绿能股份有限公司 | Fuel treatment device and hydrogen purification device thereof |
| CN106744678B (en) * | 2016-12-19 | 2019-01-29 | 江苏师范大学 | The more bed reaction units of sodium borohydride alcoholysis hydrogen manufacturing |
| CN106829857A (en) * | 2017-03-08 | 2017-06-13 | 苏州芷宁信息科技有限公司 | Fast Persistence based on borohydride hydrolytic produces hydrogen methods |
| CN109216738A (en) * | 2018-08-07 | 2019-01-15 | 深圳亚华伟翌科技有限公司 | Fuel cell system |
| CN108862190B (en) * | 2018-08-07 | 2023-10-31 | 哈尔滨海微智芯科技有限公司 | Hydrogen production device by sodium borohydride hydrolysis |
| CN108862191B (en) * | 2018-08-16 | 2020-05-19 | 深圳亚华伟翌科技有限公司 | Sodium borohydride hydrolysis hydrogen production unit |
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| Title |
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| 燃料电池汽车供氢新技术－硼氢化钠水解制氢. 潘相敏，马建新.天然气化工（C1化学与化工），第28卷第5期. 2008 |
| 燃料电池汽车供氢新技术－硼氢化钠水解制氢. 潘相敏，马建新.天然气化工(C1化学与化工)，第28卷第5期. 2008 * |
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