CN103552982B - Sodium borohydride hydrolysis/alcoholysis hydrogen production reactor - Google Patents
Sodium borohydride hydrolysis/alcoholysis hydrogen production reactor Download PDFInfo
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- CN103552982B CN103552982B CN201310587007.3A CN201310587007A CN103552982B CN 103552982 B CN103552982 B CN 103552982B CN 201310587007 A CN201310587007 A CN 201310587007A CN 103552982 B CN103552982 B CN 103552982B
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- chamber
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- hydrogen
- gas
- sodium borohydride
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- 239000001257 hydrogen Substances 0.000 title claims abstract description 50
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 50
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 239000012279 sodium borohydride Substances 0.000 title claims abstract description 26
- 229910000033 sodium borohydride Inorganic materials 0.000 title claims abstract description 26
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 23
- 238000006136 alcoholysis reaction Methods 0.000 title claims abstract description 11
- 238000006460 hydrolysis reaction Methods 0.000 title claims abstract description 11
- 230000007062 hydrolysis Effects 0.000 title claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 52
- 239000002994 raw material Substances 0.000 claims abstract description 23
- 239000007788 liquid Substances 0.000 claims abstract description 18
- 239000007789 gas Substances 0.000 claims abstract description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 6
- 238000010276 construction Methods 0.000 claims description 5
- 229910052878 cordierite Inorganic materials 0.000 claims description 3
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000008187 granular material Substances 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 230000009257 reactivity Effects 0.000 claims description 2
- 230000008649 adaptation response Effects 0.000 claims 1
- 229910052763 palladium Inorganic materials 0.000 claims 1
- 229910052697 platinum Inorganic materials 0.000 claims 1
- 239000010970 precious metal Substances 0.000 claims 1
- 229910052703 rhodium Inorganic materials 0.000 claims 1
- 229910052707 ruthenium Inorganic materials 0.000 claims 1
- 238000000926 separation method Methods 0.000 abstract description 6
- 239000003054 catalyst Substances 0.000 abstract description 5
- 239000000047 product Substances 0.000 abstract description 5
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 229910052799 carbon Inorganic materials 0.000 abstract 1
- 239000012263 liquid product Substances 0.000 abstract 1
- 239000002923 metal particle Substances 0.000 abstract 1
- 239000000446 fuel Substances 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 238000003860 storage Methods 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- 239000006227 byproduct Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- NVIFVTYDZMXWGX-UHFFFAOYSA-N sodium metaborate Chemical compound [Na+].[O-]B=O NVIFVTYDZMXWGX-UHFFFAOYSA-N 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 239000011232 storage material Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 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
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- OAKJQQAXSVQMHS-UHFFFAOYSA-N hydrazine Substances NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000004904 shortening 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
Classifications
-
- 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
Landscapes
- Hydrogen, Water And Hydrids (AREA)
Abstract
The invention relates to a sodium borohydride hydrolysis/alcoholysis hydrogen production reactor. The main body of the reactor has a double-layer sleeve structure, wherein the inner layer is a reaction chamber and the outer layer comprises a raw material chamber and a gas/liquid separation chamber. The raw material chamber consists of an upper part and a lower part which are communicated with each other through a tube bundle with a deflection baffle, and the space outside the tube bundle serves as the gas/liquid separation chamber. Reaction raw materials from the nether raw material chamber are input into the reaction chamber by a hydraulic pump and enter a catalyst bed layer through a distribution plate. The catalyst bed layer of the reaction chamber is divided into an upper section and a lower section, wherein the upper section is active carbon loaded with a noble metal particles, and the lower section is an overall structure catalyst. A product leaving the reaction chamber enters the gas/liquid separation chamber, and exchanges heat with the raw materials in the tube bundle through a pipe wall to ensure that the raw materials can be preheated, and the separation of hydrogen and a liquid product is realized at the same time. According to the sodium borohydride hydrolysis/alcoholysis hydrogen production reactor, the sodium borohydride hydrolysis/alcoholysis hydrogen production reaction can be performed under a natural condition; the reactor is compact in structure, integrates reaction, heat exchange and product separation, and can meet requirements for real-time hydrogen production under various environmental conditions.
Description
Technical field
The present invention relates to a kind of reactor utilizing catalyzer and sodium borohydride to produce hydrogen, the needs of instant hydrogen manufacturing under can meeting various varying environment temperature.
Background technology
Hydrogen Energy is regarded as 21 century the most potential clean energy and energy carrier.In recent years, take fuel cell technology as the great attention that the Hydrogen Energy development and utilization of representative is subject to countries in the world, and beginning realize commercialization.Wherein, Proton Exchange Membrane Fuel Cells is considered to the third generation power system after steamer and oil engine, has broad application prospects in fields such as stationary electric power plant, power truck, military special type power supply, movable power sources.
Proton Exchange Membrane Fuel Cells uses pure hydrogen as fuel, but existing hydrogen storage material and technology are in quality and volume hydrogen-storage density, working temperature, reversible cycle performance and security etc., can't meet practical and requirement that is mass-producing.Therefore, method that situ conversion prepares hydrogen is the effective means meeting fuel cell practical needs present stage to adopt hydrogen-rich fuel to carry out.
In recent years, hydroborate particularly sodium borohydride (NaBH
4) be subject to extensive concern as novel hydrogen storage material.Compared with the high temperature reformation hydrogen production reaction of hydro carbons and alcohols, sodium borohydride catalyzing hydrolyzation reaction can be carried out at normal temperatures, do not need additionally to provide energy to carry out initiation reaction, reaction liberated heat can maintain reaction to carry out with speed faster under self-heat condition, easily realizes instant hydrogen manufacturing and instant hydrogen supply.In addition, not containing CO and other impurity in prepared hydrogen, can be directly used in fuel cell, moisture contained in hydrogen can also play to the effect of fuel battery proton exchange film humidification.
The alcoholysis reaction of sodium borohydride and methyl alcohol can be carried out at the temperature of 0 DEG C even lower.The freezing point of methyl alcohol is-97 DEG C is that sodium borohydride alcoholysis hydrogen production process can be applied under extremely cold environment, has greatly expanded the environmental compatibility of sodium borohydride hydrogen manufacturing.
With regard to preparing hydrogen by sodium borohydride hydrolysis practical with regard to, generally need adopt flow reactor, this just require raw material sodium borohydride and by product sodium metaborate completely soluble in water.But sodium borohydride hydrolysising by-product sodium metaborate exists with the form stable of hydrate.At 25 DEG C, sodium borohydride concentration in aqueous is only in solution state lower than guarantee sodium metaborate during 28g/100g water, and at this moment the gravimetric hydrogen storage density of system only has 2.9wt%.The vehicle-mounted hydrogen storage system of USDOE to fuel cell car proposes following medium-term and long-term target: the quality hydrogen-storage density of 2005-2010 reaches 6.5%, and volume hydrogen-storage density reaches 62kg/m
3; The quality hydrogen-storage density of 2015 reaches 9%, and volume hydrogen-storage density reaches 80kg/m
3.Therefore, sodium borohydride hydrolysis reaction system is also not suitable for use in the hydrogen-feeding system of on-vehicle fuel, but the method still has potential application prospect at portable electric source domain.
In sum, although be subject to raw materials cost and hydrogen-storage density restriction, be that the hydrogen production process of raw material is still suitable for, at different ambient temperatures for portable fuel battery provides instant hydrogen manufacturing and hydrogen supply, having become the focus of fuel cell hydrogen source area research and exploitation with hydroborate.From research report and patent content, the research of this method is focused mostly in catalyzer and reaction kinetics, but less for the research report of reactor.
Chinese patent (CN101049907B) discloses a kind of method and device of instant self-controlled hydrogen supply of chemical borohydride hydrolytic hydrogen production.The method is the effect of the hydrogen pressure difference utilized between inner two encloses containers of device, makes to flow between two containers of reaction material in device, regulates the Exposure of reaction material and catalyzer, thus control generation speed and the pressure of hydrogen.This apparatus structure is simple, can realize instant hydrogen supply.Chinese patent (CN100560477C) discloses a kind of preparation method of tubular reactor of hydrogen production by sodium borohydride-hydrazine mixed fuel, metal support after dealuminzation is packed into tubular reactor as catalyzer, continuous hydrogen supply can be realized and with stable speed hydrogen supply.But the reactor function singleness in existing method and apparatus, and not for reaction characteristics design bed structure and the management of consideration reaction heat.
Summary of the invention
The invention provides a kind of sodium borohydride hydrolysis/alcoholysis hydrogen-manufacturing reactor.This reactor can improve the compactness of reactor; The start time of reacting under reducing envrionment temperature; Reduce the resistance to mass transfer of the material in beds, improve reaction efficiency.
To achieve these goals, reactor body part provided by the invention is double-layer sleeve structure, is from inside to outside followed successively by reaction chamber and feed chamber.Wherein, feed chamber by upper (12), under (18) two portions form, and be connected by built-in tube bank (4), the space outside tube bank is as gas/liquid separate chamber (8).
After reaction starts, utilize small-scale liquid press pump (1) that reaction raw materials is exported (2) by below feed chamber and extract out and be transported to reaction chamber entrance (10) through pipeline (7), the under meter (5) on pipeline 7 is in order to measure reaction raw materials.Reaction chamber beds is formed by upper and lower two sections.Epimere is activated carbon supported noble metal granule catalyzer (14), and hypomere is one-piece construction catalyzer (16).Grid distributor 9 and 6 is had respectively in two-stage catalytic oxidant layer upper end.The product leaving reaction chamber enters gas/liquid separate chamber through check valve (17), in this and the raw material counter-current flow in tube bank, by tube wall and its heat exchange, makes raw material obtain preheating, realizes being separated of hydrogen and product liquid simultaneously.Baffle plate (3) tube wall is equipped with for improving heat exchange efficiency, in gas/liquid separate chamber.
Native system can carry out under self-heat condition.When reaction raw materials enters in reactor, need the hydrogen output that certain start time just can reach stable.By the impact of envrionment temperature, have certain fluctuation start time.Under autothermal reaction condition, in order to reduce start time, loading activated carbon supported noble metal granule catalyzer at reaction chamber epimere, ensureing that reaction is carried out with speed faster at ambient temperature.
Major part reactant completes conversion at reaction chamber epimere, and for sodium borohydride aqueous solution system, by product sodium metaborate exists with the form stable of hydrate, and along with the consumption of water in reaction process, system viscosity increases, and mobility is deteriorated.For avoiding reaction chamber to block, adopting honeycomb integral catalyst at reaction chamber hypomere, improving the mobility of reaction mixture, complete the conversion of residue sodium borohydride simultaneously.
Hydrogen after separation is left by the upper outlet (13) of gas/liquid separate chamber, and by-product solution is discharged by the centre exit (15) of gas/liquid separate chamber.
Compared with prior art, advantage of the present invention and positively effect are:
One, by reaction chamber, Heat Room and the integrated reactor of gas/liquid separate chamber effective integration, improve the compactness of reactor, small volume, the instant hydrogen manufacturing needs of miniaturization can be met;
Two, upper and lower two-stage catalytic agent bed has been constructed for reaction characteristics.Epimere adopts high reactivity noble metal support catalyzer, and hypomere adopts honeycomb integral catalyst.Both met the requirement that reaction starts fast, overcoming again the reaction later stage causes the problem that in beds, resistance to mass transfer increases due to soltion viscosity increase;
Three, by the heat exchange of product and raw material, material temperature is raised, be conducive to shortening and react start time, the needs of instant hydrogen manufacturing under meeting cold environmental conditions;
Four, reaction product is by with raw material heat exchange and arrange plate washer, enhances being separated of hydrogen and reaction mixture.
Accompanying drawing explanation
Fig. 1 is sodium borohydride hydrolysis/alcoholysis hydrogen-manufacturing reactor schematic diagram of the present invention.
Fig. 2 is baffle schematic diagram in sodium borohydride hydrolysis/alcoholysis hydrogen-manufacturing reactor gas/liquid separate chamber of the present invention.
Embodiment
Be described in further detail technical scheme of the present invention below in conjunction with the drawings and specific embodiments, the present invention is not limited to these embodiments.
Embodiment 1
Sodium borohydride hydrogen making reaction device according to Fig. 1, beds epimere is activated carbon supported Pt catalyzer, and hypomere is that honeycomb cordierite supports Co and Ni one-piece construction catalyzer.The aqueous solution adopting sodium borohydride and naoh concentration to be respectively 10% and 5% is raw material, (20 DEG C) carry out instant hydrogen manufacturing at ambient temperature, the flow velocity of reaction raw materials is 20ml/min, and the hydrogen flow rate produced after reaction reaches steady state is 5L/min.
Embodiment 2
Sodium borohydride hydrogen making reaction device according to Fig. 1, beds epimere is activated carbon supported Pt catalyzer, and hypomere is that honeycomb cordierite supports Co and Ni one-piece construction catalyzer.The methanol solution adopting sodium borohydride and naoh concentration to be respectively 5% and 2% is raw material, under outdoor conditions, (about 0 DEG C) carries out instant hydrogen manufacturing in the winter time, the flow velocity of reaction raw materials is 20ml/min, and the hydrogen flow rate produced after reaction reaches steady state is 2.4L/min.
Above embodiment only in order to technical scheme of the present invention to be described, but not is limited; Although with reference to previous embodiment to invention has been detailed description, for the person of ordinary skill of the art, still can modify to the technical scheme described in previous embodiment, or equivalent replacement is carried out to wherein portion of techniques feature; And these amendments or replacement, do not make the essence of appropriate technical solution depart from the spirit and scope of the present invention's technical scheme required for protection.
Claims (3)
1. a sodium borohydride hydrolysis/alcoholysis hydrogen-manufacturing reactor, is characterized in that: main part is tube-in-tube structure, and internal layer is reaction chamber, and skin is feed chamber and gas/liquid separate chamber; Feed chamber is made up of upper and lower two portions, and is connected by built-in tube bank, and the space outside tube bank is as gas/liquid separate chamber; Reaction raw materials from below feed chamber pumps into reaction chamber after metering, reaction chamber beds is formed by upper and lower two sections, epimere adopts high reactivity noble metal support catalyzer, the needs started fast are reacted under meeting low temperature environment, hypomere adopts one-piece construction catalyzer, the situation that the mobility caused because soltion viscosity increases with the adaptive response later stage is deteriorated; The product leaving reaction chamber enters gas/liquid separate chamber through check valve, in this and the raw material counter-current flow in tube bank, by tube wall and its heat exchange, makes raw material obtain preheating, realizes being separated of hydrogen and product liquid simultaneously.
2. reactor according to claim 1, restrains outer wall with baffle plate in gas/liquid separate chamber, feed chamber and gas/liquid separate chamber form tube and shell heat exchanger.
3. reactor according to claim 1, reaction chamber beds epimere is activated carbon supported noble metal granule catalyzer, and precious metal is one or more in Pt, Pd, Rh, Ru; Hypomere is that honeycomb cordierite supports Co and Ni one-piece construction catalyzer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310587007.3A CN103552982B (en) | 2013-11-20 | 2013-11-20 | Sodium borohydride hydrolysis/alcoholysis hydrogen production reactor |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310587007.3A CN103552982B (en) | 2013-11-20 | 2013-11-20 | Sodium borohydride hydrolysis/alcoholysis hydrogen production reactor |
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| Publication Number | Publication Date |
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| CN103552982A CN103552982A (en) | 2014-02-05 |
| CN103552982B true CN103552982B (en) | 2015-07-01 |
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Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110550599A (en) * | 2018-05-31 | 2019-12-10 | 吉林大学 | Hydrolysis hydrogen production system |
| 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 |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007084142A2 (en) * | 2005-01-28 | 2007-07-26 | Millennium Cell, Inc. | Hydrogen generation system and method |
| CN101027247A (en) * | 2004-06-14 | 2007-08-29 | 千年电池公司 | Catalytic reactor for hydrogen generation systems |
| CN101054160A (en) * | 2006-04-10 | 2007-10-17 | 中国科学院大连化学物理研究所 | Mini reforming hydrogen-preparation reactor |
| CN101597023A (en) * | 2008-06-03 | 2009-12-09 | 中国科学院金属研究所 | Be applicable to the chemical hydride catalytic-hydrolysis device for producing hydrogen and the method for onboard hydrogen source |
-
2013
- 2013-11-20 CN CN201310587007.3A patent/CN103552982B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101027247A (en) * | 2004-06-14 | 2007-08-29 | 千年电池公司 | Catalytic reactor for hydrogen generation systems |
| WO2007084142A2 (en) * | 2005-01-28 | 2007-07-26 | Millennium Cell, Inc. | Hydrogen generation system and method |
| CN101054160A (en) * | 2006-04-10 | 2007-10-17 | 中国科学院大连化学物理研究所 | Mini reforming hydrogen-preparation reactor |
| CN101597023A (en) * | 2008-06-03 | 2009-12-09 | 中国科学院金属研究所 | Be applicable to the chemical hydride catalytic-hydrolysis device for producing hydrogen and the method for onboard hydrogen source |
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