CN113277468A - Integrated kilowatt-level fuel cell sodium borohydride hydrolysis hydrogen production device - Google Patents
Integrated kilowatt-level fuel cell sodium borohydride hydrolysis hydrogen production device Download PDFInfo
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- CN113277468A CN113277468A CN202010890574.6A CN202010890574A CN113277468A CN 113277468 A CN113277468 A CN 113277468A CN 202010890574 A CN202010890574 A CN 202010890574A CN 113277468 A CN113277468 A CN 113277468A
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- sodium borohydride
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- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 128
- 239000001257 hydrogen Substances 0.000 title claims abstract description 128
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 125
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 66
- 239000012279 sodium borohydride Substances 0.000 title claims abstract description 41
- 229910000033 sodium borohydride Inorganic materials 0.000 title claims abstract description 40
- 239000000446 fuel Substances 0.000 title claims abstract description 36
- 238000006460 hydrolysis reaction Methods 0.000 title claims abstract description 27
- 230000007062 hydrolysis Effects 0.000 title claims abstract description 23
- 239000007788 liquid Substances 0.000 claims abstract description 138
- 239000003054 catalyst Substances 0.000 claims abstract description 82
- 239000002699 waste material Substances 0.000 claims abstract description 52
- 239000002994 raw material Substances 0.000 claims abstract description 50
- 238000006243 chemical reaction Methods 0.000 claims abstract description 47
- 238000000746 purification Methods 0.000 claims abstract description 14
- 238000000926 separation method Methods 0.000 claims abstract description 11
- 238000003860 storage Methods 0.000 claims description 47
- 239000003513 alkali Substances 0.000 claims description 35
- 238000001035 drying Methods 0.000 claims description 24
- 229910052723 transition metal Inorganic materials 0.000 claims description 22
- 239000000243 solution Substances 0.000 claims description 19
- 229910000510 noble metal Inorganic materials 0.000 claims description 18
- 239000007787 solid Substances 0.000 claims description 16
- -1 transition metal salt Chemical class 0.000 claims description 14
- 239000000498 cooling water Substances 0.000 claims description 12
- 239000002274 desiccant Substances 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 150000003624 transition metals Chemical class 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 238000011068 loading method Methods 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- 238000005470 impregnation Methods 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910052755 nonmetal Inorganic materials 0.000 claims description 3
- 239000012266 salt solution Substances 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 2
- 230000007704 transition Effects 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 9
- 208000012839 conversion disease Diseases 0.000 abstract description 4
- 230000010354 integration Effects 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000002808 molecular sieve Substances 0.000 description 6
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 150000002431 hydrogen Chemical class 0.000 description 5
- 239000000741 silica gel Substances 0.000 description 5
- 229910002027 silica gel Inorganic materials 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 3
- 239000004327 boric acid Substances 0.000 description 3
- 239000011964 heteropoly acid Substances 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 229910010276 inorganic hydride Inorganic materials 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000002407 reforming Methods 0.000 description 2
- 239000013589 supplement Substances 0.000 description 2
- 229910001428 transition metal ion Inorganic materials 0.000 description 2
- 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 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 229910020674 Co—B Inorganic materials 0.000 description 1
- 229910003252 NaBO2 Inorganic materials 0.000 description 1
- 229910000102 alkali metal hydride Inorganic materials 0.000 description 1
- 150000008046 alkali metal hydrides Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical compound [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003729 cation exchange resin Substances 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
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- 230000005494 condensation Effects 0.000 description 1
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- 238000013461 design Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000002637 fluid replacement therapy Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
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- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
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- 238000010248 power generation Methods 0.000 description 1
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- 229920002554 vinyl polymer Polymers 0.000 description 1
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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/32—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of manganese, technetium or rhenium
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
- C01B3/065—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents from a hydride
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
- H01M8/0606—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants
- H01M8/065—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants by dissolution of metals or alloys; by dehydriding metallic substances
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1005—Arrangement or shape of catalyst
- C01B2203/1029—Catalysts in the form of a foam
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- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
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- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1047—Group VIII metal catalysts
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- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
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- C01B2203/1052—Nickel or cobalt catalysts
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- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1047—Group VIII metal catalysts
- C01B2203/1052—Nickel or cobalt catalysts
- C01B2203/1058—Nickel catalysts
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- 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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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention provides an integrated kilowatt-level fuel cell sodium borohydride hydrolysis hydrogen production device which comprises an outer shell, wherein a waste liquid area, a reaction area and a separation and purification area are sequentially arranged in the outer shell from bottom to top; the reaction zone is provided with a catalyst lifting basket, a raw material liquid inlet is arranged on the outer shell corresponding to the reaction zone, and the raw material liquid inlet is provided with a feeding pipe extending downwards to the bottom of the catalyst lifting basket; an annular baffle is arranged between the reaction zone and the separation and purification zone. The device has high integration level, can realize continuous hydrogen production, and does not need to stop in the supply and discharge processes; the raw material liquid is fully contacted with the catalyst, and the reaction conversion rate is high; the prepared hydrogen is fully purified and can be directly supplied to a fuel cell for use.
Description
Technical Field
The invention belongs to the technical field of hydrogen preparation, and particularly provides a continuous-operation integrated kilowatt-level fuel cell sodium borohydride hydrolysis hydrogen production device.
Background
The proton exchange membrane fuel cell is a power generation device which directly converts chemical energy stored in fuel into electric energy through electrochemical reaction, has the advantages of high energy density, high energy conversion efficiency, environmental friendliness and the like, and is a preferred power source for new energy automobiles, mobile electronic equipment, unmanned aerial vehicles, communication base stations and the like. To realize the scale application of fuel cells, high-density storage and rapid and safe supply of pure hydrogen are important problems to be solved urgently at present.
At present, the supply of hydrogen fuel mainly comprises two modes of physical hydrogen storage and chemical hydrogen production. The physical hydrogen storage method mainly comprises high-pressure gaseous hydrogen storage and low-temperature liquid hydrogen storage. Wherein, the high-pressure gaseous hydrogen storage is convenient to use and has wide application range, but the volume energy density is low; the low-temperature liquid hydrogen storage has high energy density, but the system is complex and the cost is high. The chemical hydrogen production mainly comprises hydrocarbon steam conversion hydrogen production, methanol reforming hydrogen production, water electrolysis hydrogen production and inorganic hydride hydrolysis hydrogen production. The hydrogen production by hydrocarbon steam conversion method and methanol reforming method is widely applied in industry, but the prepared hydrogen contains a certain amount of CO impurities and can be used only after being purified, and the two methods have complicated hydrogen production equipment and are difficult to miniaturize; the purity of hydrogen obtained by hydrogen production through water electrolysis is very high, but the hydrogen production cost is high, the power consumption is large, and large-scale popularization cannot be realized temporarily; the hydrolysis of inorganic hydride to produce hydrogen is used as a small-sized hydrogen production method, and is very suitable for being applied to portable low-power fuel cells.
The inorganic hydride mainly comprises alkali metal hydride, alkaline earth metal hydride, borohydride and aluminum hydride, wherein, the hydrogen production by hydrolysis of sodium borohydride is the current relatively hot on-site hydrogen production technology, and the advantages mainly comprise: (1) the hydrogen production efficiency is high. The hydrogen content of sodium borohydride is up to 10.8 wt%, and hydrogen is completely released under the catalytic action of the catalyst, which can reach over 90%. (2) The purity of the hydrogen is higher. The hydrogen generated by the hydrolysis of sodium borohydride does not contain CO, and complex purification treatment is not needed. (3) The reaction condition is mild, and the speed is controllable. The hydrolysis reaction of sodium borohydride can be carried out at room temperature, and the hydrogen production rate can be conveniently controlled by controlling the concentration and the feeding flow of the sodium borohydride solution. (4) The safety is high. The sodium borohydride is stable in nature in dry air, convenient to store and transport, and the alkaline solution is very stable and can not undergo self-hydrolysis.
At present, in the published documents of sodium borohydride hydrogen production reaction devices (such as CN103253631A, CN106744678B, CN203238030U, CN203402923U, CN203741035U, etc.), part of reaction raw material liquid in the devices passes through the catalyst coated on the bed layer from top to bottom or from bottom to top, so that the contact time between the raw material liquid and the catalyst is short and insufficient, and incomplete reaction or low hydrogen production rate is easily caused. Part of the hydrogen production devices are fed intermittently, and hydrogen cannot be produced continuously. In addition, NaOH and NaBO can be entrained in hydrogen generated by hydrolysis reaction of sodium borohydride2If alkaline impurities enter the fuel cell, the performance and the service life of the cell are greatly influenced, so that hydrogen prepared by hydrolyzing sodium borohydride can be supplied to the fuel cell only after being sufficiently purified, and the problem is not solved in the prior art.
Disclosure of Invention
The invention aims to provide an integrated kilowatt-level fuel cell sodium borohydride hydrolysis hydrogen production device, which has high integration level, can realize continuous hydrogen production, and does not need to stop in the supply and discharge processes; the raw material liquid is fully contacted with the catalyst, and the reaction conversion rate is high; the prepared hydrogen is fully purified and can be directly supplied to a fuel cell for use.
The invention is realized by the following steps:
an integrated kilowatt-level fuel cell sodium borohydride hydrolysis hydrogen production device comprises an outer shell, wherein a waste liquid area, a reaction area and a separation and purification area are sequentially arranged inside the outer shell from bottom to top; the reaction zone comprises a reactor, a catalyst lifting basket is arranged in the reactor, a raw material liquid inlet is arranged on an outer shell corresponding to the reaction zone, and a feeding pipe extending downwards to the bottom of the catalyst lifting basket is arranged on the raw material liquid inlet; an annular baffle is arranged between the reaction zone and the separation and purification zone.
Specifically, the reaction zone is provided with a first temperature display table for measuring the reaction temperature; the catalyst lifting basket is used for containing a catalyst and comprises a solid bottom surface, a solid side wall arranged around the solid bottom surface, a mesh side wall arranged above the solid side wall, a mesh cover arranged on the inner side of the mesh side wall and a mesh hanging lug arranged above the mesh side wall; the catalyst lifting basket is fixed in the outer shell of the reaction area through mesh hangers.
The device further comprises a raw material liquid storage tank, wherein the raw material liquid storage tank is communicated with the feeding pipe through a feeding pump; the raw material liquid storage tank is provided with a first high/low liquid level indicator, and the inlet pipe is provided with a one-way valve.
Further, the catalyst of the present invention may be one or more of a supported noble metal catalyst, a supported non-noble metal catalyst or a supported non-metal catalyst, preferably, the catalyst is a supported non-noble metal catalyst, and more preferably, the catalyst is a sponge supported non-noble metal catalyst.
Further, the sponge-supported non-noble metal catalyst is prepared by the following steps:
1) transition metal salt impregnation loading
Soaking sponge with surface oxygen-containing groups into aqueous solution of transition metal salt to prepare transition metal salt-loaded sponge;
2) preparation of sponge-supported catalyst
Immersing the sponge loaded with the transition metal salt prepared in the step 1) into NaBH4In the solution, reducing the transition metal salt into transition metal or boride of transition metal to obtain the sponge carrier catalyst, wherein NaBH4The mass percentage of the solution is 0.5-20%.
The transition metal salt solution is selected from one or more of nitrate or chloride aqueous solutions of Co, Ni, Fe and Mn.
Specifically speaking, the top of the raw material liquid storage tank is provided with an emptying valve and a raw material liquid inlet, and the raw material liquid inlet is provided with a first electromagnetic valve interlocked with a first high/low liquid level indicator.
Further, the separation purification area comprises a condenser and a drying and alkali removal tank, the condenser comprises a plurality of heat exchange tubes arranged in parallel, and hydrogen generated by reaction in the reaction area is cooled through the heat exchange tubes; cooling water cavities are arranged among the heat exchange tubes and between the heat exchange tubes and the outer shell, and a liquid inlet and a liquid outlet are formed in the outer shell corresponding to the condenser; and a second temperature display table for measuring the temperature of the cooled gas is arranged between the condenser and the drying and alkali removing tank.
Specifically, mesh baffles are arranged on the upper part and the lower part of each drying and alkali removing tank, and a drying agent and an alkali removing agent are filled between the two mesh baffles; a hydrogen outlet is arranged on the outer shell above the drying and alkali removing agent.
Further, the waste liquid district includes the waste liquid storage tank, waste liquid storage tank bottom is equipped with heat exchange coil, heat exchange coil one end links to each other with the liquid outlet on the condenser shell body, and the other end extends the shell body that the waste liquid district corresponds.
Specifically, a waste liquid outlet is formed in the bottom of the waste liquid area, a second high-low liquid level indicator is arranged in the waste liquid area, and a second electromagnetic valve linked with the second high-low liquid level indicator is arranged on the waste liquid outlet; the waste liquid area is provided with a third temperature display meter for measuring the temperature of the cooled waste liquid; and the waste liquid area is provided with a pressure display meter and a pressure relief pipe, and the pressure relief pipe is provided with a safety valve interlocked with the pressure display meter.
The invention has the beneficial effects that:
(1) the hydrogen production device has high integration level. The reactor, the condenser, the drying alkali removal tank and the waste liquid storage tank are designed into a whole, so that the volume and the weight of the device are greatly reduced, and the hydrogen storage density of the device is obviously improved.
(2) The hydrogen production device has high automation degree. Through the interlocking of high-low liquid level indicator and solenoid valve, can the automatic control feed liquor's fluid replacement and the emission of waste liquid, supply and discharge process need not to shut down, and hydrogen manufacturing can go on in succession.
(3) The hydrogen production device has short hydrogen production response time, stable hydrogen production rate and sufficient reaction. The raw material liquid gradually rises from the bottom of the catalyst lifting basket after entering the reactor, and is discharged out of the catalyst lifting basket after reaching the side wall of the mesh, the retention time of the raw material liquid is sufficient, the raw material liquid can fully contact and react with the catalyst, and the reaction conversion rate can reach more than 85%.
(4) The hydrogen production rate of the hydrogen production device is adjustable. The hydrogen production rate can be very conveniently controlled by changing the concentration of sodium borohydride in the raw material liquid and the feeding rate of the feeding pump, and the method is suitable for fuel cells with different powers from tens of watts to thousands of watts.
(5) The hydrogen prepared by the hydrogen production device has high purity. The condenser has the functions of condensation and gas-liquid separation, and can separate most of water vapor carried in hydrogen, NaOH and NaBO2When the alkaline impurities are removed, the drying agent and the alkaline removing agent in the drying alkaline removing tank can further dry and remove the alkaline to purify the hydrogen, and the purified hydrogen can be directly supplied to the fuel cell for use.
(6) The hydrogen production device is safe to use. The temperature of the reaction zone, the temperature of the cooled hydrogen and the temperature of the cooled waste liquid can be monitored in real time through the temperature display meter, and the reaction condition can be mastered at any time. The device is provided with a safety valve, and when the pressure of the system reaches a high limit, the safety valve automatically opens the relief pressure to prevent the system from generating accidents due to overpressure.
(7) In addition, the sponge with oxygen-containing groups on the surface is preferably selected, so that transition metal ions can be directly adsorbed, the transition metal and the sponge carrier form stronger connection through chemical bonding, and the falling of active sites in the reaction process is effectively inhibited.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are required to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.
FIG. 1 is a schematic diagram of an integrated kilowatt-scale fuel cell sodium borohydride hydrolysis hydrogen production plant of the present invention;
fig. 2 is a schematic diagram of the structure of the catalyst carrier of the present invention.
Icon:
1-raw material liquid storage tank, 2-feeding pump, 3-one-way valve, 4-1 high/low liquid level indicator, 5-1 electromagnetic valve, 6-emptying valve, 7-reactor, 8-catalyst basket, 9-feeding pipe, 10-ring baffle, 11-1 temperature indicator, 12-condenser, 13-2 temperature indicator, 14-drying alkali removal tank, 15-mesh baffle, 16-flange, 17-waste liquid storage tank, 18-2 high/low liquid level indicator, 19-2 electromagnetic valve, 20-heat exchange coil, 21-3 temperature indicator, 22-pressure indicator, 23-safety valve, 24-cooling water inlet, 25-cooling water outlet, 26-solid bottom surface, 27-solid side wall, 28-mesh side wall, 29-mesh cover, 30-mesh hangers.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions of the embodiments of the present invention will be described clearly and completely with reference to the accompanying drawings of the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all embodiments of the present invention. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
Thus, the following detailed description of the embodiments of the present invention, presented in the figures, is not intended to limit the scope of the invention, as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
In the description of the present invention, it is to be understood that the terms indicating an orientation or positional relationship are based on the orientation or positional relationship shown in the drawings only for the convenience of describing the present invention and simplifying the description, and do not indicate or imply that the device or element referred to must have a specific orientation, be constructed and operated in a specific orientation, and thus, should not be construed as limiting the present invention.
In the present invention, unless otherwise expressly stated or limited, the terms "mounted," "connected," "secured," and the like are to be construed broadly and can, for example, be fixedly connected, detachably connected, or integrally formed; can be mechanically or electrically connected; either directly or indirectly through intervening media, either internally or in any other relationship. The specific meanings of the above terms in the present invention can be understood by those skilled in the art according to specific situations.
In the description of the present invention, it should be noted that the terms "center", "upper", "lower", "left", "right", "vertical", "horizontal", "inner", "outer", etc. indicate orientations or positional relationships based on the orientations or positional relationships shown in the drawings or the orientations or positional relationships that the products of the present invention are conventionally placed in use, and are only used for convenience in describing the present invention and simplifying the description, but do not indicate or imply that the devices or elements referred to must have a specific orientation, be constructed and operated in a specific orientation, and thus, should not be construed as limiting the present invention. Furthermore, the terms "first," "second," "third," and the like are used solely to distinguish one from another and are not to be construed as indicating or implying relative importance.
Furthermore, the terms "horizontal", "vertical", "overhang" and the like do not imply that the components are required to be absolutely horizontal or overhang, but may be slightly inclined. For example, "horizontal" merely means that the direction is more horizontal than "vertical" and does not mean that the structure must be perfectly horizontal, but may be slightly inclined.
In the present invention, unless otherwise expressly stated or limited, the first feature may be present on or under the second feature in direct contact with the first and second feature, or may be present in the first and second feature not in direct contact but in contact with another feature between them. Also, the first feature being above, on or above the second feature includes the first feature being directly above and obliquely above the second feature, or merely means that the first feature is at a higher level than the second feature. A first feature that underlies, and underlies a second feature includes a first feature that is directly under and obliquely under a second feature, or simply means that the first feature is at a lesser level than the second feature.
The purpose of this embodiment is in order to provide an integrated form kilowatt-level fuel cell sodium borohydride hydrogen plant that hydrolysises, including shell body and raw materials liquid storage tank 1, inside waste liquid district, reaction zone and the separation purification zone of establishing in proper order from up down of shell body. Referring to fig. 1, the waste liquid zone is a waste liquid storage tank 17, the reaction zone is a reactor 7, and the separation and purification zone comprises a condenser 12 and a drying and alkali removal tank 14. That is, essentially, the apparatus is composed of a raw material liquid storage tank 1, a feed pump 2, a reactor 7, a condenser 12, a dry alkali removal tank 14, a waste liquid storage tank 17, and other accessories.
In detail, the raw material liquid storage tank is connected with a feed pump through a pipeline, the feed pump is connected into the reactor through an inlet pipe 9, and an annular baffle plate 10 is welded on the inlet pipe. A one-way valve 3 is arranged on a pipeline between the feeding pump and the reactor to prevent the backflow of the fluid. Be provided with 1 high/low liquid level indicator 4 in the raw materials liquid storage tank, 1 high/low liquid level indicator interlocks with 1 solenoid valve 5, can carry into the raw materials liquid storage tank with the raw materials liquid automatically. The stock solution storage tank top design atmospheric valve 6 prevents jar interior negative pressure.
The reactor 7, the condenser 12, the drying and alkali removing tank 14 and the waste liquid storage tank 17 are designed into a whole, and share one outer shell. Wherein the top ends of the reactor and the dry caustic removal tank are sealed with a flange 16. A catalyst basket 8 is provided in the reactor.
Referring to fig. 2, the catalyst basket 8 is fixed inside the reactor and used for containing the catalyst, and the catalyst basket 8 can be directly taken out of the reactor, so that the catalyst can be conveniently replaced. The raw material liquid enters the reactor and reacts with the catalyst in the catalyst basket 8 to generate hydrogen, and the hydrogen enters the tube pass of the condenser 12 from the top of the reactor. A temperature display table No. 1 was inserted into the reactor 7 to indicate the temperature of the reaction zone. The feeding pipe extends into the bottom of the catalyst lifting basket in the reactor; the catalyst can be one or more of a supported noble metal catalyst, a supported non-noble metal catalyst or a supported non-metal catalyst. Further, the catalyst carrier 8 comprises a solid bottom surface 26, a solid side wall 27, a mesh side wall 28, a mesh cover 29 and a mesh lug 30, wherein the solid bottom surface 26 and the solid side wall 27 enable reaction liquid to have enough residence time in the catalyst carrier 8 to fully react with the catalyst, the mesh side wall enables raw material liquid after full reaction to overflow from the mesh and enter a waste liquid storage tank, the mesh cover is used for fixing the catalyst and simultaneously enabling hydrogen generated by reaction to pass through, and the mesh lug is used for fixing the catalyst carrier in the reactor. The raw material liquid is a mixed solution of sodium borohydride and sodium hydroxide, and the solution is alkaline and can inhibit the self-hydrolysis reaction of the sodium borohydride.
The condenser 12 cools the water vapor and the solution droplets carried in the hydrogen gas into a liquid phase state by external cooling water, and the cooled hydrogen gas enters a drying and alkali removing tank. A No. 2 temperature display table 13 is connected between the condenser 12 and the drying and alkali removing tank 14 and used for indicating the temperature of the cooled gas. External cooling water enters from a cooling water inlet 24, sequentially passes through the condenser and the heat exchange coil at the bottom of the waste liquid storage tank, and then flows out from a cooling water outlet 25.
The drying and alkali removing tank 14 is filled with a drying agent and an alkali removing agent for further drying and alkali removing purification treatment of the cooled hydrogen. The upper end and the lower end of the drying and alkali removing tank 14 are both provided with mesh baffles 15 for fixing a drying agent and an alkali removing agent; the top of the drying and alkali removing tank is provided with a pure hydrogen outlet for a fuel cell. The drying agent in the drying and alkali removing tank 14 can be one or a mixture of more of molecular sieve, sponge, anhydrous calcium chloride, allochroic silica gel, cotton, activated carbon and the like; the alkali remover can be one or a mixture of more of molecular sieve, heteropoly acid, boric acid, cation exchange resin and the like; the drying agent is arranged before the alkali remover or the drying agent is arranged before and after the alkali remover.
A No. 2 high/low liquid level indicator 18 is arranged in the waste liquid storage tank, and the No. 2 high/low liquid level indicator is interlocked with a No. 2 electromagnetic valve 19 and can automatically discharge waste liquid. The bottom of the waste liquid storage tank is provided with a heat exchange coil 20, and waste liquid heat is carried away by external cooling water. A No. 3 temperature display table 21 is connected into the waste liquid storage tank and used for indicating the temperature of the cooled waste liquid. A pressure display meter 22 is connected into the waste liquid storage tank and is interlocked with a safety valve 23, and when the pressure in the waste liquid storage tank reaches a high limit, the safety valve automatically opens the pressure of a discharge system.
In addition, each part of the hydrogen production apparatus of this embodiment is made of an alkali corrosion resistant material, such as stainless steel or polytetrafluoroethylene.
When in use, the flow is as follows:
before hydrogen production, raw material liquid is supplemented into a raw material liquid storage tank 1 from the outside, when the liquid level of the raw material liquid reaches the high liquid level of a No. 1 high/low liquid level indicator 4, a No. 1 electromagnetic valve 5 is closed, and liquid supplement is stopped; the catalyst in the catalyst basket 8 and the drying agent and the alkali removing agent in the drying alkali removing tank 14 are filled, and the flange is screwed down.
When the device is used for producing hydrogen, external cooling water is opened, enters from a cooling water inlet 24, sequentially passes through the condenser 12 and the heat exchange coil 20, and flows out from a cooling water outlet 25; the flow rate of the feed pump 2 is set and then started. The feed pump carries the raw materials liquid in the raw materials liquid storage tank to catalyst basket 8 bottom in reactor 7, and the raw materials liquid takes place the reaction after contacting with the catalyst and begins to produce hydrogen, and solid bottom surface 26 and solid lateral wall 27 of catalyst basket make the reaction liquid have enough dwell time fully to react in the catalyst basket, and when the raw materials liquid level reached the mesh lateral wall 28 of catalyst basket, the raw materials liquid after the full reaction spills over from the mesh and gets into waste liquid storage tank 17. The hydrogen generated by the reaction passes through the mesh cover 29 of the catalyst basket and enters the tube side of the condenser 12 to be cooled, the water vapor and solution fog drops carried in the hydrogen are cooled to be in a liquid phase state, the water vapor and solution fog drops cooled to be in the liquid phase drop from the condenser onto the annular baffle plate 10, and then the hydrogen passes through the meshes of the mesh hangers 30 to enter the waste liquid storage tank. And the cooled hydrogen enters a drying and alkali removing tank for further drying and alkali removing purification treatment, and the purified hydrogen is used for the fuel cell.
When the liquid level of the raw material liquid in the raw material liquid storage tank is reduced to the low liquid level of the No. 1 high/low liquid level indicator, the No. 1 electromagnetic valve is opened to supplement the liquid. When the liquid level of the waste liquid in the waste liquid storage tank reaches the high liquid level of the No. 2 high/low liquid level indicator 18, the No. 2 electromagnetic valve 19 is opened, and the waste liquid in the waste liquid storage tank is discharged outwards. When the liquid level of the waste liquid is reduced to the low liquid level of the No. 2 high/low liquid level indicator, the No. 2 electromagnetic valve is closed, and the liquid discharge is stopped.
When the pressure display meter 22 detects that the pressure in the waste liquid storage tank reaches a high limit, the safety valve 23 automatically opens the relief pressure to prevent the system from generating danger due to overpressure.
In order to better verify the use effect of the hydrogen production device in the embodiment, the following experiments are specifically performed:
example 1
According to the assembly device shown in the figure 1, the whole device is made of stainless steel, the raw material solution is 5 wt% of sodium borohydride +2 wt% of sodium hydroxide solution, the catalyst is a supported non-noble metal catalyst, the drying agent and the alkali remover are allochroic silica gel and a molecular sieve respectively, the allochroic silica gel is placed in front of the molecular sieve, and the flow rate of the feeding pump is set to be 60 mL/min.
Tests show that the hydrogen production rate is stable after feeding for 1.5 min, the hydrogen production rate is 6.4L/min, and hydrogen can be continuously supplied to a fuel cell with the power of 500W. After the hydrogen is continuously and stably produced for 150 min, the conversion rate of the sodium borohydride hydrogen production is calculated to be 91%, hydrogen produced by the device is introduced into a certain amount of deionized water, the pH value of the deionized water is not changed, and the prepared hydrogen is fully purified.
Example 2
According to the assembly device shown in the figure 1, the whole device is made of stainless steel, the raw material solution is 10 wt% of sodium borohydride +4 wt% of sodium hydroxide solution, the catalyst is a supported non-noble metal catalyst, the drying agent and the alkali removing agent are respectively molecular sieves and boric acid, the molecular sieves are arranged before and after the boric acid, and the flow rate of the feeding pump is set to be 52 mL/min.
Tests show that the hydrogen production rate is stable after feeding for 2.5 min, the hydrogen production rate is 11.9L/min, and hydrogen can be continuously supplied to a fuel cell with the power of 1000W. After 120 min of continuous and stable hydrogen production, the conversion rate of hydrogen production by sodium borohydride is calculated to be 88%, hydrogen produced by the device is introduced into a certain amount of deionized water, the pH value of the deionized water is not changed, and the prepared hydrogen is fully purified.
Example 3
According to the assembly device shown in the figure 1, the whole device is made of stainless steel, the raw material solution is 15 wt% of sodium borohydride and 5 wt% of sodium hydroxide solution, the catalyst is a supported non-noble metal catalyst, the drying agent and the alkali remover are allochroic silica gel and heteropoly acid respectively, the allochroic silica gel is placed in front of and behind the heteropoly acid, and the flow rate of the feeding pump is set to be 60 mL/min.
Tests show that the hydrogen production rate is stable after feeding for 4.5 min, the hydrogen production rate is 20.8L/min, and hydrogen can be continuously supplied to a fuel cell with the power of 2000W. After 120 min of continuous and stable hydrogen production, the conversion rate of sodium borohydride hydrogen production is calculated to be 85%, hydrogen produced by the device is introduced into a certain amount of deionized water, the pH value of the deionized water is not changed, and the prepared hydrogen is fully purified.
Therefore, the hydrogen production devices of the embodiments 1 to 3 can solve the technical problems of incomplete reaction, low hydrogen production rate, discontinuous hydrogen production and incomplete hydrogen purification of the existing sodium borohydride hydrolysis hydrogen production device. The integration level is high, hydrogen can be continuously produced, and the supply and discharge processes do not need to be stopped; the raw material liquid is fully contacted with the catalyst, and the reaction conversion rate is high; the prepared hydrogen is fully purified and can be directly supplied to a fuel cell for use.
Example 4
The rest of the example 1 is the same as the supported non-noble metal catalyst selected as the supported non-noble metal catalyst with low cost and high activity. The catalyst is a sponge-supported non-noble metal catalyst and is prepared by the following steps: 1) and (3) carrying out immersion loading on transition metal salt: impregnation of sponge polyvinyl formal (PVF) sponge with surface oxygen-containing groups to transition metal salt CoCl2Will be fully absorbed with CoCl2Putting the PVF sponge of the aqueous solution into an oven for drying to prepare the CoCl loaded with the transition metal salt2The sponge of (1); 2) preparation of sponge supported catalyst:loading transition metal salt CoCl prepared in the step 1)2The sponge is immersed in NaBH with the mass percentage of 5 percent4Reducing in the solution to prepare the PVF sponge supported Co-B catalyst.
Tests have found that it is possible to supply hydrogen continuously to a fuel cell with a power of 1000W. After the hydrogen is continuously and stably produced for 150 min, the conversion rate of the sodium borohydride hydrogen production is calculated to be 89.5%, the hydrogen produced by the device is introduced into a certain amount of deionized water, the pH value of the deionized water is not changed, and the prepared hydrogen is fully purified.
Wherein, the transition metal salt solution can also be one or more of nitrate or chloride aqueous solutions of Ni, Fe and Mn.
The surface of the PVF sponge is provided with an oxygen-containing group which can directly adsorb transition metal ions, so that the transition metal and the sponge carrier form stronger connection through chemical bonding, and the falling of an active site in the reaction process is effectively inhibited.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The utility model provides an integrated form kilowatt-level fuel cell sodium borohydride hydrogen plant that hydrolysises which characterized in that: the device comprises an outer shell, wherein a waste liquid zone, a reaction zone and a separation and purification zone are sequentially arranged in the outer shell from bottom to top; the reaction zone comprises a reactor (7), a catalyst basket (8) is arranged in the reactor, a raw material liquid inlet is arranged on an outer shell corresponding to the reaction zone, and a feeding pipe (9) extending downwards to the bottom of the catalyst basket is arranged on the raw material liquid inlet; an annular baffle (10) is arranged between the reaction zone and the separation and purification zone.
2. The integrated kilowatt-grade fuel cell sodium borohydride hydrolysis hydrogen production device according to claim 1, characterized in that: the reaction zone is provided with a first temperature display table (11) for measuring the reaction temperature; the catalyst lifting basket (8) is used for containing a catalyst and comprises a solid bottom surface (26), a solid side wall (27) arranged around the solid bottom surface, a mesh side wall (28) arranged above the solid side wall, a mesh cover (29) arranged on the inner side of the mesh side wall and a mesh hanging lug (30) arranged above the mesh side wall; the catalyst lifting basket (8) is fixed in the outer shell of the reaction zone through mesh lugs.
3. The integrated kilowatt-grade fuel cell sodium borohydride hydrolysis hydrogen production device according to claim 1 or 2, characterized in that: the device also comprises a raw material liquid storage tank (1), wherein the raw material liquid storage tank is communicated with a feeding pipe (9) through a feeding pump (2); the raw material liquid storage tank is provided with a first high/low liquid level indicator (4), and the inlet pipe is provided with a one-way valve (3).
4. The integrated kilowatt-grade fuel cell sodium borohydride hydrolysis hydrogen production device according to claim 2, characterized in that: the catalyst is selected from one or more of a supported noble metal catalyst, a supported non-noble metal catalyst or a supported non-metal catalyst, preferably, the catalyst is a supported non-noble metal catalyst, and more preferably, the catalyst is a sponge supported non-noble metal catalyst.
5. The integrated kilowatt-grade fuel cell sodium borohydride hydrolysis hydrogen production device according to claim 4, characterized in that: the sponge-supported non-noble metal catalyst is prepared by the following steps:
1) transition metal salt impregnation loading
Soaking sponge with surface oxygen-containing groups into aqueous solution of transition metal salt to prepare transition metal salt-loaded sponge;
2) preparation of sponge-supported catalyst
Immersing the sponge loaded with the transition metal salt prepared in the step 1) into NaBH4In solution, reduction of transition metal salts to transition metals or boronization of transition metalsPreparing a sponge carrier catalyst in which NaBH is added4The mass percentage content of the solution is 0.5-20%;
the transition metal salt solution is selected from one or more of nitrate or chloride aqueous solutions of Co, Ni, Fe and Mn.
6. The integrated kilowatt-grade fuel cell sodium borohydride hydrolysis hydrogen production device according to claim 3, characterized in that: the top of the raw material liquid storage tank is provided with an emptying valve (6) and a raw material liquid inlet, and the raw material liquid inlet is provided with a first electromagnetic valve (5) interlocked with a first high/low liquid level indicator.
7. The integrated kilowatt-grade fuel cell sodium borohydride hydrolysis hydrogen production device according to claim 6, characterized in that: the separation and purification area comprises a condenser (12) and a drying and alkali removal tank (14), the condenser comprises a plurality of heat exchange tubes arranged in parallel, and hydrogen generated by reaction in the reaction area is cooled through the heat exchange tubes; cooling water cavities are arranged among the heat exchange tubes and between the heat exchange tubes and the outer shell, and a liquid inlet and a liquid outlet are formed in the outer shell corresponding to the condenser; and a second temperature display table (13) for measuring the temperature of the cooled gas is arranged between the condenser and the drying and alkali removing tank.
8. The integrated kilowatt-grade fuel cell sodium borohydride hydrolysis hydrogen production device according to claim 7, characterized in that: mesh baffles are arranged on the upper part and the lower part of the drying and alkali removing tank (14), and a drying agent and an alkali removing agent are filled between the two mesh baffles; a hydrogen outlet is arranged on the outer shell above the drying and alkali removing agent.
9. The integrated kilowatt-level fuel cell sodium borohydride hydrolysis hydrogen production device according to any one of claims 6-8, characterized in that: the waste liquid district includes waste liquid storage tank (17), waste liquid storage tank bottom is equipped with heat transfer coil (20), heat transfer coil one end links to each other with the liquid outlet on the condenser shell body, and the other end extends the shell body that the waste liquid district corresponds.
10. The integrated kilowatt-grade fuel cell sodium borohydride hydrolysis hydrogen production device according to claim 9, characterized in that: a waste liquid outlet is formed in the bottom of the waste liquid area, a second high-low liquid level indicator (18) is arranged in the waste liquid area, and a second electromagnetic valve (19) linked with the second high-low liquid level indicator is arranged on the waste liquid outlet; the waste liquid area is provided with a third temperature display meter (21) for measuring the temperature of the cooled waste liquid; the waste liquid area is provided with a pressure display meter (22) and a pressure relief pipe, and the pressure relief pipe is provided with a safety valve (23) interlocked with the pressure display meter.
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