CN104787721A - Hydrolysis hydrogen production agent - Google Patents
Hydrolysis hydrogen production agent Download PDFInfo
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- CN104787721A CN104787721A CN201510176845.0A CN201510176845A CN104787721A CN 104787721 A CN104787721 A CN 104787721A CN 201510176845 A CN201510176845 A CN 201510176845A CN 104787721 A CN104787721 A CN 104787721A
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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 hydrolysis hydrogen production agent which at least comprises borohydride, metal catalysts and acid catalysts, wherein the metal catalysts comprise one or more of CoCl2, Co-B, FeCl2, NiC12 and CuCl2; the acid catalysts comprise one or more of citric acid, oxalic acid and phosphoric acid. The metal catalysts and the acid catalysts, namely two different types of catalysts, are mixed, a reaction between the catalyst mixture and borohydride is performed according to a certain formula, and water absorbents and a leavening agent are added into the formula, so that the catalyst mixture has the characteristics of being porous in appearance, large in specific surface area, high in catalytic activity and the like, the service life of the catalyst mixture is greatly prolonged, and the hydrogen yield and the hydrogen production rate are comprehensively improved; the defects in the borohydride-based hydrolysis hydrogen production rate and yield are overcome; besides, according to the formula for hydrogen production, the energy density of a portable hydrogen fuel battery can be enhanced, and the application prospect in the portable hydrogen production field is very wide.
Description
Technical field
The invention belongs to Hydrogen Energy and fuel cell field, be specifically related to a kind of hydrolytic hydrogen production agent.
Background technology
Unmanned plane can be executed the task under uninteresting, dirty and dangerous environment, except except military field is in widespread attention, all has purposes extremely widely at civil areas such as disaster prevention monitoring, power communication system overhaul, oceanographic surveys.Relatively large unmanned plane adopts burning type engine, uses conventional fuel oil to drive; Small-sized unmanned plane uses electric motor mostly, is generally driven by lithium ion battery.Based on differing materials system, current lithium ion battery technology specific energy is limited, between 150 Wh/kg to 250 Wh/kg scopes, cannot meet the development trend demand of modern unmanned plane miniaturization, long voyage, therefore, the power supply with high-energy-density is studied significant.
As the power-supply system with high-energy-density, the application of Proton Exchange Membrane Fuel Cells on unmanned plane is more and more subject to the attention of various countries.But fuel cell system specific energy is mainly limited by hydrogen storage system, though existing high-pressure hydrogen storing, liquid technology such as storage hydrogen, solid alloy Chu Qing etc. respectively have relative merits, be all difficult to the requirement meeting long voyage unmanned plane high-energy-density.The fuel cell unmanned plane of forefront adopts borohydride hydrolytic hydrogen supply, and in such borohydride hydrogen making-Proton Exchange Membrane Fuel Cells (B-H-PEMFC) power-supply system, preparing hydrogen by sodium borohydride hydrolysis reaction is:
According to above-mentioned reaction, 1g NaBH
4can produce hydrogen 0.211g, hydrogen manufacturing amount can reach 7.4 wt%.If calculated with fuel cell voltage 0.7V, B-H-PEMFC Systems Theory specific energy can reach 2770 Wh/kg.Visible, B-H-PEMFC system has very high specific energy, and actual unmanned plane B-H-PEMFC system specific energy can reach 500 ~ 1300 Wh/kg, is 2.5 to 7 times of lithium ion battery.
In actual preparing hydrogen by sodium borohydride hydrolysis system, usually adopt NaBH
4solution is hydrolyzed and produces hydrogen under the effect of catalyzer.In this hydrogen generating system, NaBH
4solution delivers to reactor hydrolysis by micropump, and product is through gas-liquid separation, and raffinate enters waste liquid tank, and hydrogen enters fuel cell power generation.In hydrogen generating system, for avoiding the NaBO of low solubility
2.xH
2o crystallization impacts catalyzer or destroys, can not the too high NaBH of working concentration
4solution, so recommend NaBH in document
4the optimum concn of solution is about 15 wt%.But the excessive water in solution reduces system specific energy.
In order to improve specific energy, the amount reducing water in hydrolysis reaction is even more important.Therefore, NaBH
4the repercussion study of solid and a small amount of water comes into one's own, and comprises water vapor or liquid water.Prosini etc. utilize porous mass to make water permeation to NaBH
4there is hydrolysis reaction in solid, find that namely water have hydrogen to produce after entering solid, water and NaBH
4mol ratio when being approximately 6, NaBH
4react completely.The research such as Liu shows, water and NaBH
4mol ratio lower than for 4 time, adopt CoCl
2make catalyzer and can make NaBH
4transformation efficiency reaches 90%, and hydrogen manufacturing amount can reach 6.7wt%, but our experiments show that, works as NaBH
4when reacting with a small amount of water, speed is slow.Therefore, the catalyst method of researching and developing a kind of borohydride hydrolytic hydrogen production of fast hydrogen making becomes this technical field technical barrier urgently to be resolved hurrily.
Summary of the invention
The object of the invention is to provide the formula of borohydride hydrolytic hydrogen production of a kind of high hydrogen production rate, stable performance and fast hydrogen making, overcomes the defect that existing borohydride hydrolytic hydrogen production hydrogen output is low and speed of reaction is slow.
Technical scheme of the present invention is: a kind of hydrolytic hydrogen production agent, at least comprises hydroborate, metal catalyst, acid catalyst; Described metal catalyst is CoCl
2, Co-B, FeCl
2, NiCl
2, CuCl
2in one or more; Described acid catalyst is one or more in citric acid, oxalic acid, phosphoric acid.
Further, the mass ratio of hydroborate and metal catalyst is 5 ~ 12 ︰ 1, and the mass ratio of hydroborate and acid catalyst is 5 ~ 12 ︰ 1.
Most preferably, sodium borohydride: cobalt chloride: citric acid=0.25 ︰ 0.03 ︰ 0.04.
Further, also comprise water-retaining agent and raising agent, the mass ratio of hydroborate and water-retaining agent and raising agent is 5 ~ 15 ︰ 1, and wherein the mass ratio of water-retaining agent and raising agent is 1 ~ 5 ︰ 1.
Further, described water-retaining agent is one or more in calcium chloride, gac, absorbent cotton or silica gel.
Further, described raising agent is gac.
The present invention compared with prior art tool has the following advantages:
Formula of the present invention can reach very high unit mass and produce hydrogen density, and unit mass hydrogen output reaches as high as 700mL/g.
Formula of the present invention can reach the hydrogen production conversion rate of more than 90% when water yield abundance.
Formula of the present invention service discharge lower than amounts of reactants than time speed of response also very fast, as shown in Figure 1, when amount of water is 0.25ml, reach 350mL/g at about 3min hydrogen output.
Formula of the present invention adopts metal catalyst and acid catalyst mixture as catalyzer hydrogen manufacturing, and cost reduces compared with traditional precious metals pt catalyzer.
Formula of the present invention can reduce hydrogen manufacturing formulation weight as the onboard hydrogen source of hydrogen fuel cell, owing to only carrying pressed powder, is not made into the lower borohydride solution of concentration, and then improves the system energy densities of fuel cell.
Formula of the present invention is solid mixture, compares with hydroborate liquid mixture, and be easy to carry movement.
Formula of the present invention is solid mixture, does not need the borohydride solution carrying lower concentration, therefore can save the volumetric spaces of carrying superfluous water, and then improves the volume energy density of fuel cell.
Add water-retaining agent in formula of the present invention, the water that fuel battery negative pole side produces can be adsorbed onto anode side, be beneficial to borohydride hydrolytic hydrogen production.
Accompanying drawing explanation
Fig. 1, Fig. 2 and Fig. 3 are that the unit mass of different ratio in experimental example 1 produces hydrogen figure;
Fig. 4 is that the unit mass of embodiment 2 produces hydrogen figure;
Fig. 5 is that the unit mass of contrast experiment 1 produces hydrogen figure;
Fig. 6 is that the unit mass of contrast experiment 2 produces hydrogen figure.
Embodiment
Experimental example 1
After the mixed powder of the citric acid of 0.25g SODIUM BOROHYDRIDE POWDER, 0.05g cobalt chloride, different mass is fully mixed in 50mL round-bottomed flask, react with the entry needle of 1mL the distilled water of 0.25mL, 0.5mL, 0.75mL being added in round-bottomed flask, the hydrogen airway produced is drawn through sebific duct and guides to long-pending full water back-off in the 1L graduated cylinder of large beaker, thus record certain hour interval collected produce the amount of hydrogen.Reaction is 18 DEG C in room temperature, NaBH
4consumption 0.25g, water intake mode carries out under selecting the condition of disposable injection.Unit mass hydrogen output Vm(mL/g) and time t(min) as Suo Shi accompanying drawing 1 ~ Fig. 3 (represent amount of water with W in legend, N represents citric acid, and C represents cobalt chloride).
Experimental example 2
After the mixed powder of the citric acid of 0.25g SODIUM BOROHYDRIDE POWDER, 0.03g cobalt chloride, different mass is fully mixed in 50mL round-bottomed flask, react with the entry needle of 1mL 0.5mL distilled water being added in round-bottomed flask, the hydrogen airway produced is drawn through sebific duct and guides to long-pending full water back-off in the 1L graduated cylinder of large beaker, thus record certain hour interval collected produce the amount of hydrogen.Reaction is 18 DEG C in room temperature, NaBH
4consumption 0.25g, water intake mode carries out under selecting the condition of disposable injection.Unit mass hydrogen output Vm(mL/g) and time t(min) as shown in Figure 4 (represent amount of water with W in legend, N represents citric acid, and C represents cobalt chloride).
From above-mentioned two experimental examples, the optimal proportion obtained is sodium borohydride: cobalt chloride: citric acid=0.25 ︰ 0.03 ︰ 0.04, unit mass hydrogen output is about 700mL/g.
Contrast experiment 1
After 0.25g SODIUM BOROHYDRIDE POWDER and 0.05g, 0.10g, 0.15g, 0.20g and 0.25g citric acid powder Homogeneous phase mixing, react with the entry needle of 1mL 0.5mL distilled water being added in round-bottomed flask, the hydrogen airway produced is drawn through sebific duct and guides to long-pending full water back-off in the 1L graduated cylinder of large beaker, thus record certain hour interval collected produce the amount of hydrogen.Reaction is 18 DEG C in room temperature, and NaBH4 consumption 0.25g, water intake mode carries out under selecting the condition of disposable injection.Unit mass hydrogen output Vm(mL/g) and time t(min) as shown in Figure 5 (represent amount of water with W in legend, N represents citric acid).
Contrast experiment 2
By 0.25g SODIUM BOROHYDRIDE POWDER respectively with the cobalt chloride powder Homogeneous phase mixing of 0.03g, 0.04g, 0.05g, 0.06g, 0.07g after, react with the entry needle of 1mL 0.5mL distilled water being added in round-bottomed flask, the hydrogen airway produced is drawn through sebific duct and guides to long-pending full water back-off in the 1L graduated cylinder of large beaker, thus record certain hour interval collected produce the amount of hydrogen.Reaction is 18 DEG C in room temperature, NaBH
4consumption 0.25g, water intake mode carries out under selecting the condition of disposable injection.Unit mass hydrogen output Vm(mL/g) and time t(min) as shown in Figure 6 (represent amount of water with W in legend, N represents citric acid).
Comparative analysis
Drawn by Fig. 5: when making catalyzer with citric acid, hydrogen production reaction is very rapid, but its unit mass hydrogen output is no more than 500mL/g.
Drawn by Fig. 6: when only making catalyzer by cobalt chloride, hydrogen production reaction speed comparatively spent mixed catalyst is slow.
Drawn by Fig. 4: if its unit mass hydrogen output can reach 700mL/g when cobalt chloride and citric acid being mixed by a certain percentage the catalyzer reacted as sodium borohydride and water, the hydrogen production reaction time drops to 3-4min.
Therefore the mixed catalyst that the present invention uses is faster than the hydrogen production reaction speed being used alone cobalt chloride or citric acid, unit mass hydrogen output is high.
The above embodiment only have expressed the embodiment of the application, and it describes comparatively concrete and detailed, but therefore can not be interpreted as the restriction to the application's protection domain.It should be pointed out that for the person of ordinary skill of the art, under the prerequisite not departing from technical scheme design, can also make some distortion and improvement, these all belong to the protection domain of the application.
Claims (6)
1. a hydrolytic hydrogen production agent, is characterized in that, at least comprises hydroborate, metal catalyst, acid catalyst; Described metal catalyst is CoCl
2, Co-B, FeCl
2, NiCl
2, CuCl
2in one or more; Described acid catalyst is one or more in citric acid, oxalic acid, phosphoric acid.
2. a kind of hydrolytic hydrogen production agent according to claim 1, is characterized in that, the mass ratio of hydroborate and metal catalyst is 5 ~ 12 ︰ 1, and the mass ratio of hydroborate and acid catalyst is 5 ~ 12 ︰ 1.
3. a kind of hydrolytic hydrogen production agent according to claim 1, is characterized in that, sodium borohydride: cobalt chloride: citric acid=0.25 ︰ 0.03 ︰ 0.04.
4. a kind of hydrolytic hydrogen production agent according to claim 1, is characterized in that, also comprise water-retaining agent and raising agent, and the mass ratio of hydroborate and water-retaining agent and raising agent is 5 ~ 15 ︰ 1, and wherein the mass ratio of water-retaining agent and raising agent is 1 ~ 5 ︰ 1.
5. a kind of hydrolytic hydrogen production agent according to claim 4, is characterized in that, described water-retaining agent is one or more in calcium chloride, gac, absorbent cotton or silica gel.
6. a kind of hydrolytic hydrogen production agent according to claim 4, is characterized in that, described raising agent is gac.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510176845.0A CN104787721A (en) | 2015-04-15 | 2015-04-15 | Hydrolysis hydrogen production agent |
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|---|---|---|---|
| CN201510176845.0A CN104787721A (en) | 2015-04-15 | 2015-04-15 | Hydrolysis hydrogen production agent |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106495095A (en) * | 2016-11-02 | 2017-03-15 | 北京明德清源科技开发有限公司 | A kind of composite hydrolysis hydrogen manufacturing material and hydrogen production process |
| RU2689587C1 (en) * | 2018-04-09 | 2019-05-28 | Федеральное государственное бюджетное учреждение науки "Федеральный исследовательский центр "Институт катализа им. Г.К. Борескова Сибирского отделения Российской академии наук" (Институт катализа СО РАН, ИК СО РАН) | Hydrogen production composition, method of its preparation and hydrogen production process |
| 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 |
| CN111137857A (en) * | 2020-02-26 | 2020-05-12 | 江苏集萃分子工程研究院有限公司 | Composite material for preparing hydrogen by solid hydrolysis and preparation method thereof |
| CN111348621A (en) * | 2020-04-21 | 2020-06-30 | 杭州氢源素生物科技有限公司 | Hydrolysable hydrogen production material using hydrogen-containing compound |
| CN111777037A (en) * | 2020-06-19 | 2020-10-16 | 浙江高成绿能科技有限公司 | Fuel for producing hydrogen by adding water and preparation process thereof |
| CN112599798A (en) * | 2020-12-16 | 2021-04-02 | 北京大学 | NaBH4Sponge and preparation method thereof |
-
2015
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106495095A (en) * | 2016-11-02 | 2017-03-15 | 北京明德清源科技开发有限公司 | A kind of composite hydrolysis hydrogen manufacturing material and hydrogen production process |
| CN106495095B (en) * | 2016-11-02 | 2018-08-03 | 北京明德清源科技开发有限公司 | A kind of composite hydrolysis hydrogen manufacturing material and hydrogen production process |
| RU2689587C1 (en) * | 2018-04-09 | 2019-05-28 | Федеральное государственное бюджетное учреждение науки "Федеральный исследовательский центр "Институт катализа им. Г.К. Борескова Сибирского отделения Российской академии наук" (Институт катализа СО РАН, ИК СО РАН) | Hydrogen production composition, method of its preparation and hydrogen production process |
| 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 |
| CN111137857A (en) * | 2020-02-26 | 2020-05-12 | 江苏集萃分子工程研究院有限公司 | Composite material for preparing hydrogen by solid hydrolysis and preparation method thereof |
| CN111348621A (en) * | 2020-04-21 | 2020-06-30 | 杭州氢源素生物科技有限公司 | Hydrolysable hydrogen production material using hydrogen-containing compound |
| CN111348621B (en) * | 2020-04-21 | 2021-09-24 | 杭州氢源素生物科技有限公司 | Hydrolysable hydrogen production material using hydrogen-containing compound |
| WO2021213029A1 (en) * | 2020-04-21 | 2021-10-28 | 杭州氢源素生物科技有限公司 | Hydrolyzable hydrogen production material using hydrogen-containing compound |
| CN111777037A (en) * | 2020-06-19 | 2020-10-16 | 浙江高成绿能科技有限公司 | Fuel for producing hydrogen by adding water and preparation process thereof |
| CN112599798A (en) * | 2020-12-16 | 2021-04-02 | 北京大学 | NaBH4Sponge and preparation method thereof |
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Effective date of registration: 20170309 Address after: 610000 Sichuan City, Chengdu Province, No. two North Ring Road, No. 111 Applicant after: Southwest Jiaotong University Address before: 610000 Chengdu science and Technology Industrial Park, hi tech Zone, hi tech Zone, Sichuan,, China A-242 Applicant before: Chengdu Ruidingte Science and Technology Co., Ltd. |
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