CN201046911Y - Hydrogen production plant of chemical hydride hydrogen-storage material system - Google Patents
Hydrogen production plant of chemical hydride hydrogen-storage material system Download PDFInfo
- Publication number
- CN201046911Y CN201046911Y CNU200620168833XU CN200620168833U CN201046911Y CN 201046911 Y CN201046911 Y CN 201046911Y CN U200620168833X U CNU200620168833X U CN U200620168833XU CN 200620168833 U CN200620168833 U CN 200620168833U CN 201046911 Y CN201046911 Y CN 201046911Y
- Authority
- CN
- China
- Prior art keywords
- hydrogen
- reactor
- catalyst
- hydrogen production
- storage
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 124
- 239000001257 hydrogen Substances 0.000 title claims abstract description 124
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 120
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 48
- 239000000126 substance Substances 0.000 title claims abstract description 24
- 150000004678 hydrides Chemical class 0.000 title claims abstract description 21
- 239000011232 storage material Substances 0.000 title claims abstract description 15
- 238000003860 storage Methods 0.000 claims abstract description 31
- 239000000463 material Substances 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000003054 catalyst Substances 0.000 claims description 35
- 238000005516 engineering process Methods 0.000 abstract description 5
- 238000000034 method Methods 0.000 abstract description 5
- 239000003513 alkali Substances 0.000 abstract description 4
- 229910052783 alkali metal Inorganic materials 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 3
- 230000004044 response Effects 0.000 abstract description 2
- 239000012190 activator Substances 0.000 abstract 1
- -1 hydrogen alkali metal Chemical class 0.000 abstract 1
- 229910052751 metal Inorganic materials 0.000 abstract 1
- 239000002184 metal Substances 0.000 abstract 1
- 239000002689 soil Substances 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 45
- 238000006460 hydrolysis reaction Methods 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 14
- 230000007062 hydrolysis Effects 0.000 description 11
- 239000002994 raw material Substances 0.000 description 11
- 239000012279 sodium borohydride Substances 0.000 description 8
- 229910000033 sodium borohydride Inorganic materials 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 238000010998 test method Methods 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 239000012448 Lithium borohydride Substances 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 230000002441 reversible effect Effects 0.000 description 5
- 238000011161 development Methods 0.000 description 4
- 230000018109 developmental process Effects 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 150000001340 alkali metals Chemical class 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000003957 anion exchange resin Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
Images
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
- Catalysts (AREA)
Abstract
The utility model relates to a hydrogen storage material system and hydrogen manufacture technology of chemical hydride, in particular to a hydrogen manufacture device for the hydrogen storage material system of hydrogen alkali metal or alkali soil metal hydroboron. The utility model is used for storing hydrogen effectively and safely and supplying hydrogen instantly. The device consists of a material storage device, a water tank, a material mixer, a pump, a reactor, a buffer and a collector. The material storage device is communicated with the material mixer through a pipeline. The water tank is communicated with the material mixer through a pipeline and the material mixer is communicated with the reactor through a pipeline. The reactor is provided with an activator inside. The reactor is respectively connected with the buffer and the collector. The hydrogen manufacture device of chemical hydride provided by the utility model has the advantages of fast response time and hydrogen supply speed. The utility model can automatically adjust the hydrogen manufacture process according to the hydrogen demand of a terminal and provides a practical hydrogen storage technology and device for vehicle hydrogen storage and various movable powers.
Description
Technical Field
The utility model relates to a chemical hydride hydrogen storage material system and a hydrogen production technology, in particular to a hydrogen production device of an alkali metal or alkaline earth metal borohydride hydrogen storage material system.
Background
The development of a high-performance hydrogen storage system for providing hydrogen sources for hydrogen fuel cell vehicles and various military and civil mobile power supplies is a key link of hydrogen energy application. Among various hydrogen storage modes, the material-based hydrogen storage is remarkably superior to high-pressure gas cylinders and low-temperature liquid hydrogen in the aspects of safety and hydrogen storage density, and is acknowledged as the most promising development prospect. However, after years of research, no reversible hydrogen storage material can meet the comprehensive requirements of a vehicle-mounted hydrogen storage system in terms of weight/volume hydrogen storage density, operating temperature, hydrogen absorption/desorption rate and the like, so that development of a non-reversible system becomes a research hotspot in the field of the current hydrogen storage materials.
Unlike a reversible system which utilizes a solid-gas reaction to realize reversible hydrogen charging/discharging, a non-reversible hydrogen storage material produces hydrogen through a catalytic hydrolysis (or solid-gas) reaction, and hydride regeneration is completed through a chemical process, so the system is also called as chemical hydride. Because two links of hydrogen discharge and hydrogen charging are separated, the chemical hydrogen storage greatly reduces the technical difficulty of developing a practical hydrogen storage system, and has application feasibility at the present stage.
A typical hydrogen production reaction by hydrolysis of a chemical hydride can be represented by the formula (1):
wherein M represents an alkali metal or an alkaline earth metal, and X is 1 or 2. The chemical hydrogen storage has the advantages that: high hydrogen storage capacity, hydrogen production at room temperature, controllable hydrogen generation rate and safe operation. At present, various foreign companies have introduced a chemical hydrogen storage prototype device, and the design principle is as follows: adding NaOH alkali liquor stabilizer into chemical hydride aqueous solution to improve the storage stability of the chemical hydride aqueous solution, injecting reaction liquid into a reaction chamber in a continuous flow mode to contact with a catalyst when hydrogen is required to be produced, and separating, collecting and applying the hydrogen produced by catalytic hydrolysis and a liquid phase. The device of the mode is simple and has high safety, but has the following defects:
(1) the addition of the alkali liquor stabilizer can slow down the hydrolysis reaction rate and reduce the hydrogen production amount of the system;
(2) the addition of alkali liquor can destroy the catalyst/carrier structure, reduce the load firmness and cause the loss of the catalyst;
(3) hydrolysis products are difficult to effectively remove in time in the continuous hydrolysis reaction process, the catalyst surface is covered, so that the catalytic activity is reduced, the hydrolysis reaction is incomplete, and the actual hydrogen storage capacity of the system is reduced;
(4) the continuous feeding results in the hydrogen storage system not responding quickly to the change in the hydrogen demand of the terminal.
These disadvantages severely limit the practical application of chemical hydride hydrogen storage technology. The development of practical chemical hydrogen technology requires fundamental changes in system configuration and device design.
SUMMERY OF THE UTILITY MODEL
The utility model aims to provide a novel hydrogen production device of a chemical hydride hydrogen storage system, which is used for high-efficiency and safe hydrogen storage and instant hydrogen supply.
The technical scheme of the utility model is that:
a hydrogen generation assembly for a chemical hydride hydrogen storage material system comprising: the reactor comprises a material storage device, a water tank, a mixer, a pump, a reactor, a buffer and a collector, wherein the material storage device and the water tank are respectively communicated with the mixer through pipelines, the mixer is communicated with the reactor through a pipeline, a catalyst is arranged in the reactor, and the reactor is respectively connected with the buffer and the collector.
Chemical hydride and water are respectively stored before reaction, and are respectively and quantitatively fed when hydrogen production is required, and the powder of the chemical hydride and the water are uniformly mixed in a mixer in a short time through stirring, are supplied to a reactor through a pump, and undergo hydrolysis reaction in areaction chamber with a preset catalyst to prepare the hydrogen. After the reaction is finished, the reaction product aqueous solution in the reaction chamber is completely discharged to a collector, then the next feeding hydrogen production is carried out according to the hydrogen use requirement, and the whole process can be automatically finished through signal acquisition and program control.
The utility model has the advantages that:
1. the utility model provides a chemical hydride hydrogen plant has characteristics such as response time is fast, hydrogen supply speed is fast to can be according to the hydrogen demand automatically regulated hydrogen manufacturing process at terminal, provide the hydrogen storage technique and the device of practicality for on-vehicle hydrogen storage and various portable power source.
Drawings
FIG. 1 is a graph showing the effect of NaOH concentration on the hydrogen production and hydrogen production rate of a system.
FIG. 2 influence of catalyst amount on hydrogen production and hydrogen production rate of the system.
FIG. 3 NaBH at a catalyst loading of 0.3 g (5% wt. -%)4Concentration versus system hydrogen production and productionThe influence of the hydrogen rate.
FIG. 4 shows the effect of the number of hydrolysis cycles and the catalyst washing treatment on the amount of hydrogen produced by the system when 10% NaOH was added.
FIG. 5 shows the effect of the number of hydrolysis cycles and the catalyst washing treatment on the amount of hydrogen produced by the system without adding NaOH.
FIG. 6LiBH4Influence of concentration on the amount of hydrogen produced by the system.
FIG. 7 shows Co supported on activated carbon support2NaBH at room temperature when B powder is used as catalyst4A graph of the relationship between the amount of hydrogen produced by hydrolysis and the reaction time.
FIG. 8 is a schematic diagram of a chemical hydride hydrolysis hydrogen production plant. In the figure, 1, a material storage device; 2. a water tank; 3. a valve; 4. a mixer; 5. a valve; 6. a pump; 7. a catalyst; 8. a reactor; 9. a pressure gauge; 10. a safety valve; 11. a buffer; 12. a collector; 13. and (4) a valve.
Detailed Description
As shown in fig. 8, the hydrogen production apparatus of the present invention comprises a material storage device 1, a water tank 2, a material mixer 4, a pump 6, a reactor 8, a buffer 11 and a collector 12; the storage device 1 is sent to the mixer 4 through the pipeline provided with the valve 3, the water tank 2 is communicated with the mixer 4 through the pipeline provided with the valve 5, after the raw materials (chemical hydride) are fully stirred and uniformly mixed in the mixer 4, the raw materials are sent to the reactor 8 through the pump 6, the catalyst 7 is arranged in the reactor 8, the reactor 8 is respectively connected with the buffer 11 and the collector 12, the buffer 11 is provided with the pressure gauge 9 and the safety valve 10, the outlet of the collector 12 is provided with the valve 3, wherein the buffer has the function of improving the hydrogen supply capacity of the system, the instant hydrogen supply is realized, and the hydrogen pressure fluctuation is reduced. Chemical hydride and water are respectively stored before reaction, and are respectively quantitatively fed when hydrogen production is required, the quantitative range of powder provided by a material storage device is 0.01-1 g/s, the quantitative range of water quantity is 0.05-5 ml/s, the hydrogen production rate range is 0.003-3 l/s, the chemical hydride powder and the water are uniformly mixed in a mixer within a period of several seconds to 1 minute by stirring, and are provided to a reactor by a pump, and the hydrolysis reaction is carried out in a reaction chamber with a preset catalyst to prepare the hydrogen; after the reaction is finished, the reaction product aqueous solution in the reaction chamber is completely discharged to a collector, and then the hydrogen production is carried out by feeding for the next time according to the requirement. The hydrogen production period is 10-20 minutes; the hydrogen production interval time is 10 seconds to 5 minutes.
The present invention is described in detail below by way of examples, with reference to amounts, purities and concentrations by weight.
Comparative example 1
With NaBH4、H2O, NaOH is used as reaction raw material, Ru as catalyst and 717 anion exchange resin as catalyst carrier, wherein NaBH4The purity is 96%, the grain diameter is about 0.1 mm, and the dosage is 0.5 g; h2O adopts to remove5 ml of ionized water; the purity of NaOH is 98 percent; the catalyst loading rate on the carrier is about 5 wt%, the particle size is about 0.45 mm, the catalyst adopts stainless steel net as a packaging body, and the mesh of the stainless steel net is about 0.33 mm. NaBH4The concentration is 20%, the NaOH concentration is 0, 5%, 10% and 20%, the catalyst dosage is 0.3 g, and the catalyst accounts for about 5% of the total weight of the hydrogen storage material system. The hydrogen production rate and the hydrogen production quantity of the material are tested by adopting a volume method, and experimental tests are carried out at 23℃ and 1atm pressure.
FIG. 1 shows the effect of NaOH usage on hydrogen production rate and hydrogen production capacity of the system. As the amount of NaOH is increased, the hydrogen production rate and the hydrogen discharge amount are both reduced.
Example 1
No NaOH was used as the raw material, and the other raw materials, the test method and the test conditions were the same as those in comparative example 1. The dosage of the catalyst is 0.1 to 0.5 g and accounts for 2 to 9 percent of the total weight of the hydrogen storage material system.
FIG. 2 shows the effect of catalyst usage on the hydrogen production and hydrogen production rate of the system. With the increase of the catalyst dosage, the hydrogen production quantity and the hydrogen production rate are both improved.
Example 2
The raw materials, the test methods and the test conditions were the same as those in example 1. NaBH4The concentration of the aqueous solution is as follows: NaBH4∶H2O is 1: 1-1: 10. The amount of the catalyst is 0.3 g and accounts for 5 percent of the total weight of the hydrogen storage material system.
FIG. 3 shows NaBH4The influence of the concentration on the hydrogen production amount and the hydrogen production rate of the system. With NaBH4The concentration is increased, the hydrogen production quantity and the hydrogen production rate of the system are firstly increased, the optimum is reached when the hydrogen production quantity and the hydrogen production rate reach 1: 5, and NaBH is continuously increased4The concentration results in a decrease in the hydrogen production rate.
Comparative example 2
The raw materials, the test method and the test conditions were the same as those of comparative example 1, and the NaOH concentration was 10%. FIG. 4 shows the effect of the number of hydrolysis cycles and the catalyst washing treatment on the amount of hydrogen produced by the system when 10% NaOH was added. For a material system added with 10% of NaOH stabilizer, the hydrogen production quantity gradually attenuates along with the increase of the cycle number, and the catalyst cleaning treatment can slow down the hydrogen production quantity attenuation to a certain extent.
Example 3
The raw materials, the test methods and the test conditions were the same as those in example 1. FIG. 5 shows the effect of the number of hydrolysis cycles and the catalyst washing treatment on the amount of hydrogen produced by the system without the addition of NaOH. For a material system without NaOH, the hydrogen production amount is generally stable along with the increase of the cycle number, and the stability of the hydrogen discharge amount can be further improved by cleaning the catalyst.
Example 4
With LiBH4、H2O as a reaction raw material, LiBH4Purity 96%, particle size about 0.1 mm, added in 0.2 g. The catalyst/support and the test method and test conditions were the same as in comparative example 1. FIG. 6 shows LiBH4Influence of concentration on the amount of hydrogen produced by the system. With LiBH4The concentration is increased, and the hydrogen production amount of the system is firstlyIncrease, reaching the maximum when reaching 40%, continue to increase LiBH4The concentration results in a reduction in the amount of hydrogen produced.
Example 5
With NaBH4、H2O is used as a reaction raw material, andthe raw material conditions and the addition amount are the same as those of comparative example 1. The catalyst is Co supported on an active carbon carrier2B powder, Co2The particle diameter of the B powder is about 1-5 microns, and the loading rate of the catalyst on the carrier is 10 weight percent. The catalyst was used in an amount of 0.3 grams and accounted for about 5% of the total weight of the hydrogen storage material system. The catalyst is packed in stainless steel net with mesh of 0.1 mm. The test method and test conditions were the same as in comparative example 1. FIG. 7 shows Co supported on activated carbon support2NaBH at room temperature when B powder is used as catalyst4A graph of the relationship between the amount of hydrogen produced by hydrolysis and the reaction time.
Claims (1)
1. The hydrogen production device of the chemical hydride hydrogen storage material system is characterized in that: the device consists of a material storage device (1), a water tank (2), a material mixer (4), a pump (6), a reactor (8), a buffer (11) and a collector (12); the material storage device (1) is communicated with the material mixer (4) through a pipeline, the water tank (2) is communicated with the material mixer (4) through a pipeline, the material mixer (4) is communicated with the reactor (8) through a pipeline, the reactor (8) is internally provided with a catalyst (7), and the reactor (8) is respectively connected with the buffer (11) and the collector (12).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNU200620168833XU CN201046911Y (en) | 2006-12-31 | 2006-12-31 | Hydrogen production plant of chemical hydride hydrogen-storage material system |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNU200620168833XU CN201046911Y (en) | 2006-12-31 | 2006-12-31 | Hydrogen production plant of chemical hydride hydrogen-storage material system |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN201046911Y true CN201046911Y (en) | 2008-04-16 |
Family
ID=39299486
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNU200620168833XU Expired - Fee Related CN201046911Y (en) | 2006-12-31 | 2006-12-31 | Hydrogen production plant of chemical hydride hydrogen-storage material system |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN201046911Y (en) |
-
2006
- 2006-12-31 CN CNU200620168833XU patent/CN201046911Y/en not_active Expired - Fee Related
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101100285A (en) | Chemical hydride hydrogen storing material system, hydrogen preparing method and hydrogen preparing device | |
| CN201161926Y (en) | Movable chemical hydrogen production plant | |
| JP4572384B2 (en) | Hydrogen generation method | |
| Gislon et al. | Hydrogen production from solid sodium borohydride | |
| CN101829564B (en) | Preparation method of Ru/C catalyst for preparing hydrogen by sodium borohydride hydrolysis | |
| CN103420335B (en) | Composition, reactor and device for producing hydrogen and hydrogen production method | |
| CN201842638U (en) | Automatic-control gas generating device | |
| CN101632929B (en) | Hydrogen production catalyst with high-temperature methyl alcohol water vapour and preparation method thereof | |
| CN101841048A (en) | Method for generating hydrogen through lithium borohydride-porous carbon hydrolysis and reaction system | |
| Pozio et al. | Apparatus for the production of hydrogen from sodium borohydride in alkaline solution | |
| CN104148084A (en) | Preparation of nano porous quaternary alloy catalyst and application thereof in production of hydrogen by virtue of ammonia borane hydrolysis | |
| CN114517304B (en) | Preparation method of NiFe-LDH metal nanosheet material electrocatalyst with PdCu alloy particle loading | |
| CN104399468A (en) | Nickel-based catalyst, and preparation method and application thereof | |
| Min et al. | Hydrogen generation by hydrolysis of solid sodium borohydride for portable PEMFC applications | |
| Oronzio et al. | New reactor design for catalytic sodium borohydride hydrolysis | |
| CN101786603A (en) | Device for preparing hydrogen through hydrolysis | |
| CN104383927B (en) | The Catalysts and its preparation method of a kind of methane and CO 2 reformation preparing synthetic gas | |
| CN201046911Y (en) | Hydrogen production plant of chemical hydride hydrogen-storage material system | |
| CN111974383A (en) | Coconut shell activated carbon supported platinum catalyst and preparation method and application thereof | |
| CN111359636A (en) | Mo-S/NF hydrogen evolution material and preparation method and application thereof | |
| CN1438169A (en) | Hydrogen preparation method and apparatus | |
| CN201154897Y (en) | Simple portable hydrogen generator | |
| TWI405717B (en) | Method of producing hydrogen by mixing sea water and metal borohydrides | |
| CN112429702B (en) | Continuous hydrogen production system and solid fuel | |
| CN111137857A (en) | Composite material for preparing hydrogen by solid hydrolysis and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20080416 Termination date: 20111231 |