CN101428756A - Automatic hydrogen production method by using hydroboron composition - Google Patents
Automatic hydrogen production method by using hydroboron composition Download PDFInfo
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- CN101428756A CN101428756A CNA2008102194557A CN200810219455A CN101428756A CN 101428756 A CN101428756 A CN 101428756A CN A2008102194557 A CNA2008102194557 A CN A2008102194557A CN 200810219455 A CN200810219455 A CN 200810219455A CN 101428756 A CN101428756 A CN 101428756A
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- hydrogen
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- hydroborate
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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 method for spontaneously producing hydrogen by utilizing a hydroboron composition. The method comprises the following steps: (1), hydroboron, an activating agent and a filling agent are respectively dried and crashed, and then uniformly mixed in a certain proportion to obtain the hydroboron composition; and (2), the hydroboron composition is added to water, so as to stably produce hydrogen. The composition proportion of the hydroboron composition is changed, or the proportion of the hydroboron composition and the water is changed, so as to control a hydrogen production speed. The method of the invention has the advantages of convenient operation and high controllability and stability during hydrogen production process, and can meet the requirements of stable hydrogen production and hydrogen supply on a small scale or a large scale on site.
Description
Technical field
The present invention relates to the Hydrogen Technology field, be specifically related to a kind of composition of hydroborate that utilizes and carry out the method that spontaneous hydrolysis is produced hydrogen.
Background technology
Hydrogen is a kind of very promising renewable and clean energy resource, and compared with other the energy, Hydrogen Energy has very obvious superiority, because the energy density of hydrogen is big, the heat energy that the unit mass H-H reaction is discharged is three times of gasoline.And the unique product of hydrogen and oxygen reaction is exactly a water, can not cause negative impact to environment.Realize the extensive utilization of Hydrogen Energy, at first must solve two problems: 1, the scene of hydrogen supply; 2, the storage of hydrogen transportation.Hydrogen production process commonly used at present has water electrolysis hydrogen production, fossil energy hydrogen manufacturing, biological hydrogen production, decomposition of hydrocarbons hydrogen manufacturing, ammonia cracking hydrogen production, hydrogen sulfide decomposing hydrogen-production, the direct photoelectricity hydrogen manufacturing of sun power, the hydrogen manufacturing of radiativity catalyzer, electron resonance splitting water, hydride hydrolytic hydrogen production or the like.And main hydrogen storage method has high-pressure gaseous storage hydrogen, liquefaction storage hydrogen, metal oxide storage hydrogen, carbonaceous adsorption hydrogen-storing and chemical hydride storage hydrogen.
Hydrogen is the highly effective fuel of Proton Exchange Membrane Fuel Cells, still, the production of hydrogen, transports and is stored on the industrial structure and also to have very big problem, and for the application of portable fuel battery, the foundation of on-the-spot hydrogen manufacturing and hydrogen-feeding system is very urgent especially.The hydride hydrogen-storing technology is a kind of hydrogen storage technology method of Miniaturizable, the reversible hydrogen of charging and discharging is good, advantage such as have extended cycle life although this hydrogen storage method has, but, because the density of metal is big, hydrogen storage capability is low, the easy efflorescence of hydrogen storage alloy, the storage hydrogen massfraction of most metals is 1.5%～3%, can't satisfy the practicability requirement.And produce in the hydrogen technology at existing chemical, magnesium hydride is wherein a kind of product hydrogen material, and it meets water, and hydrolysis can take place, and speed of reaction is fast, has very good hydrogen desorption kinetics character.But the magnesium hydride hydrolysis reaction is very fierce, and hydrogen-producing speed is difficult to control, but meets the air spontaneous combustion, has certain risk, be unfavorable for preserving, and, magnesium hydride cost an arm and a leg hydrogen manufacturing cost height.
Hydroborate is a class chemistry hydrogen storage material, is example with the sodium borohydride, and when it began as reductive agent in nineteen fifties, people just recognized the characteristic of its energy hydrolysis product hydrogen, and are used.Sodium borohydride can be stablized preservation under certain condition as a kind of good hydrogen storage material, and its long half time is adding energy stable existence under the alkali situation.The method of utilizing borohydride hydrolytic hydrogen production at present mainly is to utilize catalyst decomposes.Produce the hydrogen effect in order to improve, generally all can be to the substrate of high-specific surface area with catalyst cupport, but this method still has significant limitation: 1, catalyst cupport is arrived suprabasil complex technical process, in making processes, can cause simultaneously the loss of catalyzer, increase the Production Time and the cost of catalyzer; 2, catalyzer because the hydrogen that produces in the reaction process can constantly impact suprabasil catalyzer, makes catalyzer come off from substrate, the effect of influence reaction in suprabasil poor adhesive force; 3, hydroborate solution needs at first stable with highly basic, not only practical application difficulty, and cause problems such as climbing alkali, bonding, corrosion easily; 4, hydroborate can constantly generate metaborate in reaction process, for the hydroborate solution of high density, along with the continuous consumption of water in the hydrolysis reaction, metaborate can exist in solution with the colloidal form, and these colloids can cover substrate surface, the catalytic effect that suppresses catalyzer, make the very fast decay of speed of reaction, thereby be difficult to realize large-scale stable hydrogen [E.Y.Marrero-Alfonso, the et al. of producing, Int.J.Hydrogen Energy, 2007,32,4723-4730].The present invention finds sodium borohydride under not additivated situation, and its self-decomposition speed is slow.And hydrolysis product hydrogen can take place rapidly after adding some additive, and hydrogen-producing speed can change by the add-on that changes additive, and the hydrogen-producing speed stable and controllable helps realizing the field fabrication and the supply of hydrogen.These characteristics of sodium borohydride make it receive publicity in the research of hydrogen manufacturing at the scene [H.I.Schlesinger, et al., J.Am.Chem.Soc., 1953,75,215-219].
Summary of the invention
The objective of the invention is to be to overcome the above-mentioned deficiency that existing hydroborate hydrogen supply technology exists, a kind of convenience, controllability and the high method of utilizing the spontaneous hydrogen manufacturing of hydroborate composition of stability are provided, and the present invention realizes on-the-spot small-sized to stablizing hydrogen manufacturing and hydrogen supply on a large scale by the modification to hydroborate.The present invention is achieved through the following technical solutions:
Utilize the method for the spontaneous hydrogen manufacturing of hydroborate composition, it comprises following steps:
(1) hydroborate, activator and weighting agent is dry respectively, pulverize, mix then the hydroborate composition, the weight ratio of described hydroborate and activator is 99:1～5:1, the weight ratio of described activator and weighting agent is 1:1～1:10; Described activator is one or more the mixture in cobalt chloride, nickelous chloride, iron(ic) chloride, Xiao Suangu, the rose vitriol; Described weighting agent is one or more the mixture in carbon dust, carbon nanotube, aluminum oxide, silicon oxide, the zeolite;
(2) the hydroborate composition that step (1) is obtained adds in the entry, can stably produce hydrogen.
In the aforesaid method, pass through to change the proportion of composing of hydroborate composition in the step (2), or the ratio of change hydroborate composition and water is controlled the speed that produces hydrogen; And along with activator ratio in the hydroborate composition increases, hydrogen output also increases.
In the aforesaid method, described hydroborate is one or more the mixture in sodium borohydride, POTASSIUM BOROHYDRIDE, the lithium borohydride.
In the aforesaid method, the weight ratio of hydroborate composition and water is 1:2000～1:10 described in the step (2).
Compared with prior art, the present invention has the following advantages: 1) the hydroborate composition is easy to make, and technology is easy, is fit to scale operation.2) by selecting described component ratio, can control hydrogen-producing speed effectively, reach stable hydrogen supply.3) because hydrogen-producing speed can be regulated by hydroborate and other components in proportions, can realize producing hydrogen to stablizing hydrogen supply on a large scale from trace.4) hydroborate composition energy uniform distribution in the aqueous solution, reaction product is less to spontaneous product hydrogen influence, decomposes fully.5) can realize on-the-spot hydrogen supply and lasting hydrogen supply.The present invention be advantageous in that, use the used device for producing hydrogen of hydroborate composition hydrogen manufacturing simple, less demanding to water, the aqueous solution need not add alkali, and it is easy to change solution.And when extensive hydrogen manufacturing was used, product reclaimed easily, thereby more saves cost.
Description of drawings
Fig. 1 is sodium borohydride and the hydrogen output comparison curves of activator cobalt chloride under the Different Weight ratio in the hydroborate composition.
Embodiment
Below in conjunction with drawings and Examples the present invention is described in further detail.
Embodiment 1
The cobalt chloride that with quality is 1 kilogram is mixed with 1 kilogram of alumina powder, adds 5 kilograms of sodium borohydride uniform mixing then, the sodium borohydride composition.
Embodiment 2
With quality is that 1 kilogram nickelous chloride and 1 kilogram cobalt chloride are mixed with 10 kilograms of silicon oxide powders, adds 99 kilograms of POTASSIUM BOROHYDRIDE uniform mixing then, gets the POTASSIUM BOROHYDRIDE composition.
Embodiment 3
With quality is that 1 kilogram cobalt chloride and 1 kilogram iron(ic) chloride mix with 1 kilogram of carbon dust, adds 20 kilograms of sodium borohydride uniform mixing then, gets the sodium borohydride composition.
Embodiment 4
Rose vitriol and the quality that with quality is 1 kilogram is that 1 kilogram carbon nanotube mixes, then with 80 kilograms of lithium borohydride thorough mixing, the lithium borohydride composition.
Embodiment 5
Xiao Suangu and the quality that with quality is 1 kilogram is that 1 kilogram zeolite mixes, then with 50 kilograms of sodium borohydride thorough mixing, the sodium borohydride composition.
Embodiment 6
The sodium borohydride composition for preparing different cobalt chloride and sodium borohydride ratio (shown in the X-coordinate of Fig. 1) with the method for embodiment 1.Get 5 gram sodium borohydride compositions, add 200 gram water, hydrogen output as shown in Figure 1.Can see, along with the activator ratio increases, the almost proportional increase of hydrogen output.Therefore, can control the speed that produces hydrogen by the proportion of composing that changes the hydroborate composition.
Embodiment 7
Method with embodiment 3 prepares the lithium borohydride composition.Get 1 gram lithium borohydride composition, add 2000 gram water hydrogen manufacturing, hydrogen-producing speed is stable.
Claims (4)
1, utilize the method for the spontaneous hydrogen manufacturing of hydroborate composition, it is characterized in that comprising following steps:
(1) hydroborate, activator and weighting agent is dry respectively, pulverize, mix then the hydroborate composition, the weight ratio of described hydroborate and activator is 99:1～5:1, the weight ratio of described activator and weighting agent is 1:1～1:10; Described activator is one or more the mixture in cobalt chloride, nickelous chloride, iron(ic) chloride, Xiao Suangu, the rose vitriol; Described weighting agent is one or more the mixture in carbon dust, carbon nanotube, aluminum oxide, silicon oxide, the zeolite;
(2) the hydroborate composition that step (1) is obtained adds in the entry, can stably produce hydrogen.
2, method according to claim 1 is characterized in that described hydroborate is one or more the mixture in sodium borohydride, POTASSIUM BOROHYDRIDE, the lithium borohydride.
3, method according to claim 1 is characterized in that the proportion of composing by the described hydroborate composition of change step (1), or the ratio of middle hydroborate composition of change step (2) and water is controlled the speed that produces hydrogen.
4,, it is characterized in that the weight ratio of hydroborate composition described in the step (2) and water is 1:2000～1:10 according to each described method of claim 1～3.
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102029159A (en) * | 2010-11-02 | 2011-04-27 | 天津工业大学 | Catalyst for catalytically hydrolyzing sodium borohydride to prepare hydrogen and preparation method thereof |
| WO2014056386A1 (en) * | 2012-10-12 | 2014-04-17 | Jin Ke | Hydrogen generating composition, reactor, device and hydrogen production method |
| CN104401940A (en) * | 2014-10-23 | 2015-03-11 | 中国计量学院 | Preparation method for aluminium alloy/borohydride hydrogen-production system |
| CN105273864A (en) * | 2014-07-18 | 2016-01-27 | 比亚迪股份有限公司 | Cleaner for alkaline battery and application thereof, and alkaline battery appearance cleaning method |
| CN106495096A (en) * | 2016-11-02 | 2017-03-15 | 北京明德清源科技开发有限公司 | A kind of solid hydrolyzes hydrogen manufacturing material |
| CN106517088A (en) * | 2016-11-15 | 2017-03-22 | 青岛大学 | High-performance lithium borohydride reversible hydrogen production system and hydrogen production method |
| CN107434986A (en) * | 2017-06-28 | 2017-12-05 | 广西启明氢能源有限公司 | Hydrous ethanol reforms fuel combination dedicated liquid activator |
| CN108238584A (en) * | 2016-12-26 | 2018-07-03 | 天津立旋科技有限公司 | A kind of solid sodium borohydride hydrogen production process |
| CN108862191A (en) * | 2018-08-16 | 2018-11-23 | 深圳亚华伟翌科技有限公司 | Sodium borohydride hydrolysis hydrogen production unit |
| CN110713170A (en) * | 2019-10-17 | 2020-01-21 | 浙江高成绿能科技有限公司 | Hydrogen production method by hydrolysis of borohydride by using water vapor |
| CN110963461A (en) * | 2019-12-31 | 2020-04-07 | 世能氢电科技有限公司 | Metal oxide and porous material composite hydrogen storage material and preparation method thereof |
| CN110980636A (en) * | 2019-12-31 | 2020-04-10 | 世能氢电科技有限公司 | Magnesium hydride hydrogen storage composite material containing porous material and preparation method thereof |
| CN114604826A (en) * | 2020-12-09 | 2022-06-10 | 中国科学院上海硅酸盐研究所 | Hydrogen production method based on fine silicon powder and sodium silicate |
| CN116022733A (en) * | 2023-02-24 | 2023-04-28 | 四川卡文智氢新能源有限公司 | Control method for aluminium hydrolysis hydrogen production process |
-
2008
- 2008-11-27 CN CNA2008102194557A patent/CN101428756A/en active Pending
Cited By (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102029159A (en) * | 2010-11-02 | 2011-04-27 | 天津工业大学 | Catalyst for catalytically hydrolyzing sodium borohydride to prepare hydrogen and preparation method thereof |
| CN102029159B (en) * | 2010-11-02 | 2013-06-05 | 天津工业大学 | Catalyst for catalytically hydrolyzing sodium borohydride to prepare hydrogen and preparation method thereof |
| US9663361B2 (en) | 2012-10-12 | 2017-05-30 | Ke Jin | Hydrogen generating composition, reactor, device and hydrogen production method |
| US20150274523A1 (en) * | 2012-10-12 | 2015-10-01 | Spectronik Pte. Ltd. | Hydrogen generating composition, reactor, device and hydrogen production method |
| WO2014056386A1 (en) * | 2012-10-12 | 2014-04-17 | Jin Ke | Hydrogen generating composition, reactor, device and hydrogen production method |
| CN105273864A (en) * | 2014-07-18 | 2016-01-27 | 比亚迪股份有限公司 | Cleaner for alkaline battery and application thereof, and alkaline battery appearance cleaning method |
| CN105273864B (en) * | 2014-07-18 | 2019-03-29 | 比亚迪股份有限公司 | Alkaline battery cleaning agent and its appearance cleaning method of application and alkaline battery |
| CN104401940A (en) * | 2014-10-23 | 2015-03-11 | 中国计量学院 | Preparation method for aluminium alloy/borohydride hydrogen-production system |
| CN106495096B (en) * | 2016-11-02 | 2018-08-03 | 北京明德清源科技开发有限公司 | A kind of solid hydrolysis hydrogen manufacturing material |
| CN106495096A (en) * | 2016-11-02 | 2017-03-15 | 北京明德清源科技开发有限公司 | A kind of solid hydrolyzes hydrogen manufacturing material |
| CN106517088A (en) * | 2016-11-15 | 2017-03-22 | 青岛大学 | High-performance lithium borohydride reversible hydrogen production system and hydrogen production method |
| CN108238584A (en) * | 2016-12-26 | 2018-07-03 | 天津立旋科技有限公司 | A kind of solid sodium borohydride hydrogen production process |
| CN107434986A (en) * | 2017-06-28 | 2017-12-05 | 广西启明氢能源有限公司 | Hydrous ethanol reforms fuel combination dedicated liquid activator |
| CN108862191A (en) * | 2018-08-16 | 2018-11-23 | 深圳亚华伟翌科技有限公司 | Sodium borohydride hydrolysis hydrogen production unit |
| CN110713170A (en) * | 2019-10-17 | 2020-01-21 | 浙江高成绿能科技有限公司 | Hydrogen production method by hydrolysis of borohydride by using water vapor |
| CN110963461A (en) * | 2019-12-31 | 2020-04-07 | 世能氢电科技有限公司 | Metal oxide and porous material composite hydrogen storage material and preparation method thereof |
| CN110980636A (en) * | 2019-12-31 | 2020-04-10 | 世能氢电科技有限公司 | Magnesium hydride hydrogen storage composite material containing porous material and preparation method thereof |
| CN114604826A (en) * | 2020-12-09 | 2022-06-10 | 中国科学院上海硅酸盐研究所 | Hydrogen production method based on fine silicon powder and sodium silicate |
| CN116022733A (en) * | 2023-02-24 | 2023-04-28 | 四川卡文智氢新能源有限公司 | Control method for aluminium hydrolysis hydrogen production process |
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Open date: 20090513 |