CN115784148B - Self-heating self-pressurizing efficient ammonia decomposition hydrogen production system and hydrogen production method thereof - Google Patents
Self-heating self-pressurizing efficient ammonia decomposition hydrogen production system and hydrogen production method thereof Download PDFInfo
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- CN115784148B CN115784148B CN202211499628.1A CN202211499628A CN115784148B CN 115784148 B CN115784148 B CN 115784148B CN 202211499628 A CN202211499628 A CN 202211499628A CN 115784148 B CN115784148 B CN 115784148B
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 title claims abstract description 433
- 239000001257 hydrogen Substances 0.000 title claims abstract description 246
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 246
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 229
- 229910021529 ammonia Inorganic materials 0.000 title claims abstract description 180
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 70
- 238000010438 heat treatment Methods 0.000 title claims abstract description 44
- 238000000354 decomposition reaction Methods 0.000 title claims abstract description 22
- 239000012528 membrane Substances 0.000 claims abstract description 63
- 239000007788 liquid Substances 0.000 claims abstract description 55
- 230000003197 catalytic effect Effects 0.000 claims abstract description 52
- 238000003860 storage Methods 0.000 claims abstract description 46
- 239000002994 raw material Substances 0.000 claims abstract description 40
- 229910052751 metal Inorganic materials 0.000 claims abstract description 31
- 239000002184 metal Substances 0.000 claims abstract description 31
- 239000007791 liquid phase Substances 0.000 claims abstract description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 86
- 238000006243 chemical reaction Methods 0.000 claims description 68
- 229910052757 nitrogen Inorganic materials 0.000 claims description 43
- 239000007789 gas Substances 0.000 claims description 37
- 239000012530 fluid Substances 0.000 claims description 29
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 28
- 239000003054 catalyst Substances 0.000 claims description 25
- 230000009471 action Effects 0.000 claims description 21
- 150000002431 hydrogen Chemical class 0.000 claims description 20
- 229910052763 palladium Inorganic materials 0.000 claims description 14
- 239000012495 reaction gas Substances 0.000 claims description 14
- 238000000746 purification Methods 0.000 claims description 13
- 238000000926 separation method Methods 0.000 claims description 13
- 238000003421 catalytic decomposition reaction Methods 0.000 claims description 12
- 238000004064 recycling Methods 0.000 claims description 12
- 238000002485 combustion reaction Methods 0.000 claims description 11
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical group [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 8
- 229910052707 ruthenium Inorganic materials 0.000 claims description 8
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 claims description 7
- 239000000567 combustion gas Substances 0.000 claims description 6
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 5
- 230000000694 effects Effects 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 238000004587 chromatography analysis Methods 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 239000011651 chromium Substances 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 238000005336 cracking Methods 0.000 claims description 3
- 238000005259 measurement Methods 0.000 claims description 3
- 238000004891 communication Methods 0.000 claims description 2
- 238000009499 grossing Methods 0.000 claims 2
- 230000006378 damage Effects 0.000 claims 1
- 229910001873 dinitrogen Inorganic materials 0.000 claims 1
- 239000000446 fuel Substances 0.000 abstract description 12
- 238000004134 energy conservation Methods 0.000 abstract description 5
- 230000009467 reduction Effects 0.000 abstract description 3
- 238000000034 method Methods 0.000 description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 229910052799 carbon Inorganic materials 0.000 description 9
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000005868 electrolysis reaction Methods 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 239000006004 Quartz sand Substances 0.000 description 2
- 238000007084 catalytic combustion reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
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- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
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- 238000007086 side reaction Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 241000282326 Felis catus Species 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000006392 deoxygenation reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
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Classifications
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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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- Hydrogen, Water And Hydrids (AREA)
Abstract
The invention discloses a self-heating self-pressurizing high-efficiency ammonia decomposition hydrogen production system and a hydrogen production method thereof, wherein the system comprises a liquid ammonia raw material tank, a high-pressure flow pump, an ammonia decomposer, a cooler, a gas-liquid separator, a first heat exchanger, a membrane separator and a metal hydrogen storage tank which are sequentially communicated through pipelines and valves, wherein a liquid phase outlet at the bottom of the gas-liquid separator is communicated with the liquid ammonia raw material tank to form a circulation loop; the device also comprises a catalytic combustor, has compact structure, ingenious conception, quick start and stop, silence, no noise, energy conservation and high efficiency, and needs a pressurizing unit, thereby realizing silence, noiseless and movable hydrogen supply; the device can be simplified without external heat supply, energy conservation and emission reduction can be realized, the ammonia raw material is recycled and efficiently utilized in a self-pressurization mode, the hydrogen production rate is greatly improved, and the requirements of the proton exchange membrane fuel cell on practical application indexes such as mass hydrogen storage density, volume hydrogen storage density, hydrogen cost, vibration noise and the like are met.
Description
Technical field:
The invention relates to the technical field of hydrogen energy, in particular to a self-heating self-pressurizing high-efficiency ammonia decomposition hydrogen production system and a hydrogen production method thereof.
The background technology is as follows:
the hydrogen energy has the characteristics of rich reserves, wide sources, high energy density, cyclic utilization, zero carbon emission, no pollutant emission and the like.
The only product of the reaction of hydrogen and oxygen is water, and the efficient energy conversion can be realized by combining the fuel cell technology, the internal combustion engine technology and the gas turbine technology. However, the low volume energy density of hydrogen in the application process and the danger in the transportation process are a great obstacle to commercialization of hydrogen energy application, and the problem of hydrogen utilization cannot be solved by the high-pressure tank, the liquid hydrogen or the solid metal hydrogen storage scheme, and the bottleneck can be solved by a hydrogen storage carrier with high hydrogen content through a method of on-site hydrogen production. At present, the on-site hydrogen production mainly comprises water electrolysis hydrogen production, methanol hydrogen production and ammonia hydrogen production.
The water electrolysis hydrogen production is difficult to popularize due to high cost, electricity is needed, and the water electrolysis hydrogen production is not suitable for mobile site hydrogen production; methanol is a carbon-based hydrogen storage carrier, carbon emission still can be generated when the methanol is used for hydrogen production, the development direction of zero carbon new energy is not met, and the hydrogen purification is complicated and difficult due to the fact that a proton exchange membrane fuel cell is poisoned by a small amount of associated CO; ammonia is a non-carbon-based hydrogen storage carrier, has the advantages of higher hydrogen content (17.65%), higher volume energy density (1.5 times of liquid hydrogen), easy storage and transportation, complete industrial infrastructure, large production scale, low price and the like, is considered as a novel energy carrier with the most potential application prospect, and has strong interest in the field of hydrogen energy in recent years, and ammonia catalytic decomposition hydrogen production is expected to become a main stream for preparing green hydrogen on site, in particular to the field of transportation mobile hydrogen production.
At present, the technology of external heat supply, normal pressure hydrogen production and repression is widely adopted in industrial production and fuel cell automobiles for ammonia hydrogen production. The liquid ammonia is gasified, enters a traditional reactor filled with a catalyst, is externally heated to a higher temperature of 450-700 ℃ to generate gas phase pyrolysis reaction, generates H 2、N2 and a small amount of unreacted NH 3 mixed gas, removes N 2、NH3 and other impurity gases from the mixed gas through a pressure swing adsorption purification system or a membrane separator, obtains high-purity hydrogen, is pressurized by a hydrogen compressor and then is stored in a high-pressure container, and provides hydrogen fuel for a Proton Exchange Membrane (PEMFC) fuel cell or is used for other purposes. Therefore, the ammonia hydrogen production device has the advantages of large volume, slow response, complex and expensive purification unit and large energy consumption, so that the application of the ammonia hydrogen production device is greatly limited.
Therefore, the development of an economical and efficient on-site ammonia hydrogen production system and method with zero carbon emission is still a problem to be solved in the field of hydrogen energy.
The invention comprises the following steps:
The invention aims to provide a self-heating self-pressurizing high-efficiency ammonia decomposition hydrogen production system and a hydrogen production method thereof, the system has compact structure, ingenious conception, quick start and stop, silence and no noise, energy conservation and high efficiency, liquid ammonia enters an ammonia decomposer to undergo decomposition reaction under the action of a high-pressure advection pump to generate hydrogen and nitrogen, self-pressurizing to generate adjustable pressure of 10-50atm, the hydrogen, the nitrogen and unreacted ammonia gas enter a cooler and a gas-liquid separator in sequence under the self-pressurizing pressure difference, the liquid ammonia accumulated at the bottom of the gas-liquid separator is cooled and separated into gas and liquid, the liquid ammonia is returned to a liquid ammonia raw material tank for recycling, crude hydrogen containing the nitrogen and a small amount of ammonia enters a membrane separator after being heated by a first exchanger, purified hydrogen enters a metal hydrogen storage tank without a pressurizing unit, and noiseless mobile hydrogen supply is realized; the hydrogen-containing ammonia nitrogen residual gas enters the catalytic combustor to supply heat, the generated hot gas flow heats the ammonia decomposer and the crude hydrogen containing nitrogen and a small amount of ammonia before entering the membrane separator, and external heat supply is not needed, so that equipment can be simplified, energy conservation and emission reduction can be realized, the ammonia raw material circulation and high-efficiency utilization can be realized through a self-pressurization mode, the hydrogen production rate is greatly improved, the requirements of the proton exchange membrane fuel cell on practical application indexes such as mass hydrogen storage density, volume hydrogen storage density, hydrogen cost, vibration noise and the like are met, and the problems that the ammonia hydrogen production reaction device is large in volume, slow in response, complex and expensive in purification unit and large in required energy consumption are solved.
The invention is realized by the following technical scheme:
The system comprises a liquid ammonia raw material tank, a high-pressure flow pump, an ammonia decomposer, a cooler, a gas-liquid separator, a first heat exchanger, a membrane separator and a metal hydrogen storage tank which are sequentially communicated through a pipeline and a valve, wherein a liquid phase outlet at the bottom of the gas-liquid separator is communicated with the liquid ammonia raw material tank to form a circulation loop; the catalytic burner supplies heat for the ammonia decomposer and the first heat exchanger; the ammonia decomposer is a micro-channel reactor, the structure of the ammonia decomposer is a horizontal-vertical double-side non-intercommunicating internal heat exchange tube pass, wherein the vertical tube pass is a reaction channel, ammonia cracking catalyst particles are filled in the reaction channel to form a catalytic bed, a feed inlet of the reaction channel is arranged at the bottom of the ammonia decomposer, and an air outlet pipe of the reaction channel is arranged at the top end of the reaction channel of the ammonia decomposer; the transverse shell pass is a hot fluid heating channel, a hot fluid inlet and a hot fluid outlet are respectively arranged on two sides of the heating channel, and the hot fluid inlet is communicated with a combustion gas output pipe of the catalytic combustor; liquid ammonia of a liquid ammonia raw material tank enters a reaction channel of an ammonia decomposer from a reaction channel feed inlet at the bottom of the ammonia decomposer under the action of a high-pressure advection pump, and enters a micro-channel reactor reaction channel which is not communicated with each other at two sides of the ammonia decomposer, the liquid ammonia is heated to 150-550 ℃ through heat convection with a transverse shell-side hot fluid heating channel to generate hydrogen and nitrogen through catalytic decomposition reaction, self-pressurization generates adjustable pressure of 10-50atm, the hydrogen, the nitrogen and unreacted ammonia enter a cooler from an air outlet pipe at the top end reaction channel of the ammonia decomposer to be cooled to 15-30 ℃ under the self-pressurization pressure difference, then the liquid ammonia accumulated at the bottom of the gas-liquid separator is separated by a gas-liquid separator, the liquid ammonia is discharged back to the liquid ammonia raw material tank at fixed time under the action of pressure difference or the action of a liquid pump, crude hydrogen containing the nitrogen and a small amount of ammonia is heated to 350-450 ℃ from the top end of the gas-liquid separator by a first heat exchanger and then enters a membrane separator, and most of the hydrogen is purified; purified hydrogen enters a metal hydrogen storage tank without a pressurizing unit, so that silent noiseless movable hydrogen supply is realized; the hydrogen-containing ammonia nitrogen residual gas after hydrogen purification enters a catalytic burner for burning and heating to remove hydrogen and ammonia, and the outlet discharges nitrogen and a small amount of steam for heating an ammonia decomposer and crude hydrogen containing nitrogen and a small amount of ammonia before entering a membrane separator.
The cooler is water-cooled or air-cooled, and the output hydrogen, nitrogen and unreacted ammonia are cooled to normal temperature (15-30 ℃) and are input into the gas-liquid separator.
Preferably, the catalytic burner is also in communication with the metal hydrogen storage tank and receives hydrogen fuel from the metal hydrogen storage tank for initial start-up.
Preferably, the ammonia decomposer and the first heat exchanger are provided with temperature control means.
The ammonia decomposer is connected with the gas-liquid separator through a back pressure valve, and is suitable for conveying hydrogen, nitrogen and unreacted ammonia generated in the ammonia decomposer into the gas-liquid separator for gas-liquid separation, and a bypass valve is arranged at an outlet of the back pressure valve, so that the generated reaction gas is suitable for collecting for flow measurement, component chromatographic analysis and the like.
The gas-liquid separator is sequentially connected with the first heat exchanger and the membrane separator through a control valve, and is suitable for heating the separated gas and then sending the heated gas into the membrane separator for hydrogen separation and purification; the gas-liquid separator is connected with the liquid ammonia raw material tank through the electromagnetic valve and is suitable for recycling the cooled and separated liquid ammonia.
The membrane separator is connected with the metal hydrogen storage pot through a back pressure valve, and is suitable for feeding pure hydrogen into the metal hydrogen storage pot, and a bypass valve is arranged at the air inlet end of the back pressure valve, so that the pure hydrogen is suitable for being fed into other places; the membrane separator residual gas output pipe is connected with the catalytic combustor and is suitable for delivering residual gas into the catalytic combustor; the combustion gas output pipe of the catalytic combustor is respectively connected with a hot fluid inlet of a transverse heating channel of the ammonia decomposer, a first heat exchanger and a bypass valve through three control valves and is respectively applied to heat supply for the ammonia decomposer, heating hydrogen before entering the membrane separator and discharging redundant hot fluid; the metal hydrogen storage pot is connected with the catalytic burner through the control valve, and is suitable for conveying hydrogen of the metal hydrogen storage pot to the catalytic burner to perform a flameless combustion starting system; an air pump is arranged between the metal hydrogen storage tank and the catalytic burner, and is suitable for providing oxygen and deoxidizing catalyst for flameless combustion.
In particular, for the case where the hydrogen production reaction temperature and the membrane separation temperature are similar (350-450 ℃), the ammonia decomposer, the first heat exchanger, the membrane separator, and the catalytic burner may be thermally sealed together to form a compact high temperature zone.
Preferably, in order to realize the effective utilization of heat energy during the system operation, the system further comprises a second heat exchanger, wherein a cold pipe of the second heat exchanger is communicated with the high-pressure advection pump, a heat pipe of the second heat exchanger is communicated with a reaction channel air outlet pipe at the top end of a reaction channel of the ammonia decomposer through a back pressure valve, liquid ammonia of a liquid ammonia raw material tank is continuously fed under the action of the high-pressure advection pump, is gasified and preheated through the second heat exchanger, then enters the ammonia decomposer from a reaction channel feed inlet at the bottom of the ammonia decomposer, hydrogen, nitrogen and unreacted ammonia together enter the second heat exchanger under the self-pressurization pressure difference, exchanges heat with liquid ammonia raw material conveyed under the action of the high-pressure advection pump, and preliminary cools the output hydrogen, nitrogen and unreacted ammonia while preheating the input ammonia, and then enters a cooler for further cooling.
The membrane separator is provided with a palladium membrane tube bundle.
A self-heating self-pressurizing high-efficiency ammonia decomposition hydrogen production method adopts the device and comprises the following steps:
1) Catalytic decomposition of ammonia to produce hydrogen: liquid ammonia of the liquid ammonia raw material tank enters an ammonia decomposer under the action of a high-pressure high-flow pump, and hydrogen and nitrogen of 10-50atm are generated by self-increasing in a reaction channel of a microchannel reactor, which is not communicated with each other at both sides, through heat convection with a transverse shell side hot fluid heating channel, heating to 150-550 ℃ and catalytic decomposition reaction; the active component of the catalyst is ruthenium;
2) And (3) separating and purifying: the hydrogen obtained in the step 1) and the nitrogen are fed into a cooler to be cooled to 15-30 ℃ under the self-pressurization pressure difference together with the unreacted ammonia, then the hydrogen is separated by a gas-liquid separator, the liquid ammonia accumulated at the bottom of the gas-liquid separator is discharged at fixed time under the pressure difference effect or the liquid pump effect and returned to a liquid ammonia raw material tank for recycling, the crude hydrogen containing the nitrogen and a small amount of ammonia is heated to 350-450 ℃ by a first heat exchanger and then fed into a membrane separator, and most of the hydrogen is purified and fed into a metal hydrogen storage tank;
3) And (3) residual gas combustion heat supply: and 2) burning the purified hydrogen-containing ammonia nitrogen residual gas in a catalytic burner to remove hydrogen and ammonia, wherein the generated hot gas is nitrogen and a small amount of steam, and the hot gas is used for heating an ammonia decomposer and crude hydrogen containing nitrogen and a small amount of ammonia before entering a membrane separator.
In particular, at start-up, the catalytic burner uses hydrogen fuel from a metallic hydrogen storage tank for initial use.
In particular, the catalyst in the catalytic combustor is compound chromium, pt/SiO 2.
The equation of the ammonia catalytic decomposition hydrogen production method is as follows: 2NH 3→3H2+2N2ΔH＝+45.9KJ mol–1 (weak endothermic reversible reaction)
The catalytic decomposition of ammonia to produce hydrogen is a weak endothermic reaction, the thermal energy is consumed for producing hydrogen by decomposing ammonia, and ammonia is not inflammable although being a fuel, but the hydrogen-containing ammonia gas is easy to burn. The hydrogen-containing residual gas after hydrogen purification is used for burning and supplying heat, so that an external heating system can be eliminated, equipment can be simplified, and energy conservation and emission reduction can be realized. The ammonia hydrogen production is usually carried out under normal pressure, various pressure-needed scenes are pressurized by a hydrogen compressor, the hydrogen compressor is expensive and consumes energy (1 kg of hydrogen is compressed to 70 megapascal energy consumption-6 kWh and 1.3 kg of carbon emission is produced), and the self-pressurizing ammonia hydrogen production does not need a hydrogen compression system, so that the effects of simplifying equipment, saving energy and reducing emission are achieved. The ammonia catalytic decomposition is a volume-increasing reaction, and increasing the hydrogen production pressure reduces the ammonia conversion rate, but the hydrogen production rate is greatly improved.
The beneficial effects of the invention are as follows:
1) The system has compact structure, realizes raw material circulation and heat recycling, has zero carbon and zero pollution, and is efficient and energy-saving;
2) The use of the microchannel reactor improves heat and mass transfer, increases the hydrogen production rate and shortens the response time;
3) The self-pressurizing gas-liquid separation realizes the recycling of raw material ammonia, and the hydrogen production rate is greatly improved without pursuing high conversion rate;
4) The palladium membrane separation not only obtains pure hydrogen, but also obtains combustible hydrogen-containing ammonia nitrogen mixed gas which only contains nitrogen after combustion;
5) The hydrogen-containing residual ammonia flameless catalytic combustion simplifies the heating unit, reduces the energy consumption of the system and improves the safety of the system;
6) The integration of the heat-insulating sealing high-temperature area ensures that the system is more compact, safer and saves energy.
In a word, the hydrogen production system has compact structure, quick start and stop, silence and no noise, realizes raw material circulation and heat recycling, has zero carbon and zero pollution, does not generate carbon dioxide emission and poisoning carbon monoxide of the proton exchange membrane battery, and is environment-friendly, energy-saving and efficient; the method realizes the recycling and high-efficiency utilization of the ammonia raw material in a self-pressurization mode, greatly improves the hydrogen production rate, meets the requirements of the proton exchange membrane fuel cell on practical application indexes such as mass hydrogen storage density, volume hydrogen storage density, hydrogen cost, vibration noise and the like, and overcomes a series of problems caused by excessively pursuing the nearly complete conversion of ammonia.
Description of the drawings:
FIG. 1 is a schematic diagram of a self-heating self-pressurizing efficient ammonia decomposition hydrogen production system of the present invention;
The device comprises a liquid ammonia raw material tank 1, a high-pressure flow-flattening pump 2, a second heat exchanger 3, a back pressure valve 4, an ammonia decomposer 5, a back pressure valve 6, a bypass valve 7, a cooler 8, a gas-liquid separator 9, an electromagnetic valve 10, a control valve 11, a first heat exchanger 12, a membrane separator 13, a palladium membrane tube bundle 14, a catalytic combustor 15, a deoxidizing catalyst 16, a three-way control valve 17, a bypass valve 18, a back pressure valve 19, a bypass valve 20, a metal hydrogen storage valve 21, a control valve 22, an air pump 23 and an adiabatic high-temperature zone.
The specific embodiment is as follows:
the following is a further illustration of the invention and is not a limitation of the invention.
Referring to fig. 1, the preferred self-heating self-pressurizing ammonia decomposition hydrogen production system of the invention comprises a liquid ammonia raw material tank 1, a high-pressure flow pump 2, an ammonia decomposer 4, a second heat exchanger 3, a cooler 7, a gas-liquid separator 8, a first heat exchanger 11, a membrane separator 12 and a metal hydrogen storage tank 20, wherein a liquid phase outlet at the bottom of the gas-liquid separator 8 is communicated with the liquid ammonia raw material tank 1 to form a circulation loop; further comprising a catalytic burner 14, the catalytic burner 14 supplying heat to the ammonia decomposer 4 and the first heat exchanger 11; the working pump pressure of the high-pressure advection pump 2 is 10-100atm, the high-pressure advection pump 2 is connected with the liquid ammonia raw material tank 1, and is suitable for feeding ammonia of the liquid ammonia raw material tank 1 into the ammonia decomposer 4; the pressure bearing of each component of the system is not less than 50atm, and the zone pressure and start-stop of the system are set by the respective control valves. The ammonia decomposer 4 is a micro-channel reactor, and has a structure of a horizontal-vertical double-side non-intercommunicating internal heat exchange tube pass, wherein the vertical tube pass is a reaction channel, ammonia cracking catalyst particles are filled in the reaction channel to form a catalytic bed, a feed inlet of the reaction channel is arranged at the bottom of the ammonia decomposer 4, and an air outlet pipe of the reaction channel is arranged at the top end of the reaction channel of the ammonia decomposer 4; the transverse shell pass is a hot fluid heating channel, two sides of the heating channel are respectively provided with a hot fluid inlet and a hot fluid outlet, and the hot fluid inlet is communicated with a combustion gas output pipe of the catalytic combustor 14; the outlet of the ammonia decomposer 4 is connected with the inlet of the gas-liquid separator 8 through a back pressure valve 5 and a reaction gas conveying pipe, and is suitable for conveying the reaction gas of hydrogen, nitrogen and unreacted ammonia generated in the ammonia decomposer 4 into the gas-liquid separator 8 for gas-liquid separation, and the outlet of the back pressure valve 5 is provided with a bypass valve 6, so that the generated reaction gas is suitable for collecting, measuring the flow, performing component chromatographic analysis and the like. The ammonia decomposer 4 is sequentially connected with the second heat exchanger 3, the cooler 7 and the gas-liquid separator 8 through the back pressure valve 5, and is suitable for cooling hydrogen, nitrogen and unreacted ammonia generated in the ammonia decomposer 4 and then conveying the cooled hydrogen, nitrogen and unreacted ammonia into the gas-liquid separator 8 for gas-liquid separation, and a bypass valve 6 is arranged at an outlet of the back pressure valve 5, and is suitable for collecting generated reaction gas for flow measurement, component chromatographic analysis and the like.
The gas-liquid separator 8 is sequentially connected with a first heat exchanger 11 and a membrane separator 12 through a control valve 10, and is suitable for heating the separated gas and then sending the heated gas into the membrane separator 12 for hydrogen separation and purification; the gas-liquid separator 8 is connected with the liquid ammonia raw material tank 1 through an electromagnetic valve 9, and is suitable for recycling the cooled and separated liquid ammonia.
The membrane separator 12 is connected with the metal hydrogen storage pot 20 through a back pressure valve 18, and is suitable for feeding pure hydrogen into the metal hydrogen storage pot 20, and a bypass valve 19 is arranged at the air inlet end of the back pressure valve 18, and is suitable for feeding pure hydrogen into other places; the residual gas output pipe of the membrane separator 12 is connected with the catalytic combustor 14 and is suitable for sending residual gas into the catalytic combustor 14; the combustion gas output pipe of the catalytic combustor 14 is respectively connected with a hot fluid inlet of a transverse heating channel of the ammonia decomposer 4, the first heat exchanger 11 and the bypass valve 17 through a three-way control valve 16 and is respectively used for supplying heat to the ammonia decomposer, heating hydrogen entering the membrane separator 12 and discharging redundant hot fluid; the metal hydrogen storage pot 20 is connected with the catalytic burner 14 through a control valve 21, and is suitable for conveying the hydrogen of the metal hydrogen storage pot 20 to the catalytic burner 14 to perform a flameless combustion starting system; an air pump 22 is provided intermediate the metal hydrogen storage tank 20 and the catalytic burner 14 and is adapted to provide oxygen and deoxygenation catalyst 15 for flameless combustion.
The method comprises the steps that liquid ammonia of a liquid ammonia raw material tank 1 is gasified and preheated through a second heat exchanger 3 under the action of a high-pressure flow pump 2, enters a reaction channel of a microchannel reactor which is not communicated with each other at two sides of the ammonia decomposer 4 from a reaction channel feed inlet at the bottom of the ammonia decomposer 4, is heated and heated to 150-550 ℃ through convection heat exchange with a transverse shell-side hot fluid heating channel to generate hydrogen and nitrogen, self-supercharging is carried out to generate adjustable pressure of 10-50atm, the hydrogen, the nitrogen and unreacted ammonia are together with the ammonia, enter the second heat exchanger 3 from a reaction channel air outlet pipe at the top end of the reaction channel of the ammonia decomposer 4 under the self-supercharging pressure difference, are subjected to heat exchange with liquid ammonia raw materials conveyed under the action of the high-pressure flow pump 2, the input ammonia is preheated, meanwhile, the output hydrogen and the nitrogen are cooled and the unreacted ammonia are further cooled down to 15-30 ℃ through a cooler 7, then separated through a gas-liquid separator 8, the liquid ammonia accumulated at the bottom of the gas-liquid separator 8 is discharged at fixed time under the action of pressure difference or the action of the liquid ammonia is returned to the raw material tank 1 for recycling, and the crude hydrogen containing the nitrogen and a small amount of ammonia is fed into a membrane separator from the top end of the first heat exchanger 11-350 to a high-350, and then enters a membrane separator 12 for purification part; purified hydrogen enters the metal hydrogen storage tank 20 without a pressurizing unit, so that silent noiseless mobile hydrogen supply is realized; the hydrogen-containing ammonia nitrogen residual gas after hydrogen purification enters a catalytic combustor 14 to be combusted for heating and removing hydrogen and ammonia, and the outlet discharges nitrogen and a small amount of water vapor for heating an ammonia decomposer and crude hydrogen containing nitrogen and a small amount of ammonia before entering a membrane separator.
Principle of operation of ammonia decomposer 4: the ammonia decomposer is a micro-channel reactor, the structure of the ammonia decomposer is that the ammonia decomposer is of a transverse-vertical double-channel non-intercommunicating internal heat exchange type, a catalyst is filled in a vertical side reaction channel, and the temperature of a reaction chamber is 150-550 ℃; ammonia is fed from the bottom of the vertical side reaction channel and is heated by the transverse side hot fluid to generate catalytic decomposition reaction, a temperature control device is arranged in the reaction channel, the top end of the reaction channel is connected with a reaction gas conveying pipe, and the reaction gas conveying pipe is connected with a second heat exchanger through a back pressure valve; the liquid ammonia is output by a high-pressure flow pump, preheated and gasified by a second heat exchanger, the preheated ammonia is continuously input from the bottom of the reaction channel and heated by a transverse side hot fluid, when the temperature reaches 150-550 ℃, ammonia catalytic decomposition reaction occurs, self-pressurization generates reaction gas containing hydrogen, nitrogen and ammonia up to 50bar, and overflows from an air outlet pipe at the top of the reaction channel, thus the multi-component multi-reaction gas-solid catalytic reaction system.
The principle of operation of the membrane separator 12: the membrane separator adopts a commercial palladium membrane separation device, the temperature of the membrane separator 12 is about 400 ℃ during operation, hydrogen molecules are dissociated into hydrogen atoms on one side of the palladium membrane under the action of pressure difference and dissolved in palladium and diffused to the other side of the palladium membrane, then the hydrogen atoms are combined into molecules, so that hydrogen gas penetrates through the palladium membrane 13, other gases such as nitrogen, ammonia and the like cannot penetrate through the palladium membrane 13, and part of hydrogen which does not penetrate through the palladium membrane is discharged from the tail end of the gas flow together, thereby achieving the purpose of separating and purifying the hydrogen.
Principle of operation of the catalytic combustor 14: the catalytic burner adopts commercial known products, the catalytic burner 14 is filled with a deoxidizing catalyst 15, the deoxidizing catalyst 15 can be compound chromium, pt/SiO 2 or other deoxidizing catalysts, and the catalytic burner is suitable for flameless combustion and heat release of hydrogen ammonia in the residual gas and oxygen from the air pump 22 and flameless combustion of hydrogen from the hydrogen storage.
Example 1:
Taking ruthenium-based ammonia decomposition catalyst as an example, the active component ruthenium of the catalyst is 5%, the catalyst contains an auxiliary agent and a carrier, and the working temperature is 350-550 ℃. 20 g (60-120 meshes) of ruthenium-based catalyst and equal volume of SiO 2 quartz sand (60-120 meshes) particles are uniformly mixed and filled in a reaction channel of the stainless steel microchannel ammonia decomposer 4, and quartz glass fibers are filled at two ends of a catalytic layer for fixation and leakage prevention. The hydrogen from the metal hydrogen storage bottle 20 and the air input from the air pump 22 are mixed (the mixture gas contains 2-3% hydrogen), burned in the catalytic burner 14, and the hot fluid preheats the ammonia decomposer 4 and the first heat exchanger 11 to 400 ℃. The method comprises the steps that liquid ammonia in a liquid ammonia raw material tank 1 is continuously fed through a high-pressure flow pump 2 at a mass airspeed WHSV=150 mL gcat -1min-1 (flow speed 3000mL min -1), is gasified and preheated through a heat exchanger 3, is input into an ammonia decomposer from a bottom reaction channel feed pipe, exchanges heat with a hot fluid of a transverse heating channel in a convection way, achieves 400 ℃ to produce hydrogen through ammonia decomposition reaction, the preset pressure of a back pressure valve is 1atm, and when the inside of the reactor is self-pressurized to the preset pressure of the back pressure valve, the produced mixed reaction gas is output from the back pressure valve, is connected with a gas chromatograph through a bypass valve 6 to analyze the composition of the mixed reaction gas, and parameters such as ammonia conversion rate, hydrogen production rate and the like are calculated:
ammonia conversion X NH3 (%) = [ total input NH 3 -total output NH 3)/total input NH 3 ]
Hydrogen production rate V (mmol gcat -1·min-1) = (ammonia flow rate/22.4) ×conversion NH3) ×1.5/catalyst mass
Hydrogen is produced at normal pressure and is not suitable for subsequent separation and purification.
Example 2:
Taking ruthenium-based ammonia decomposition catalyst as an example, the catalyst has a ruthenium dispersity of 5% and a working temperature of 250-550 ℃. 20 g (60-120 meshes) of ruthenium-based catalyst and equal volume of SiO 2 quartz sand (60-120 meshes) particles are uniformly mixed and filled in a reaction channel of the stainless steel microchannel ammonia decomposer 4, and quartz glass fibers are filled at two ends of a catalytic layer for fixation and leakage prevention. The hydrogen from the hydrogen storage bottle 20 and the air input from the air pump 22 are mixed (the mixture gas contains 2-3% hydrogen), burned in the catalytic burner 14, and the hot fluid preheats the ammonia decomposer 4 and the first heat exchanger 11 to 400 ℃. The method comprises the steps that liquid ammonia in a liquid ammonia raw material tank 1 is continuously fed through a high-pressure flow pump 2 at a mass airspeed WHSV=150 mL gcat -1min-1 (flow speed 3000mLmin -1), is gasified and preheated through a heat exchanger 3, is input into an ammonia decomposer from a bottom reaction channel feed pipe, exchanges heat with a heat fluid convection of a transverse heating channel, reaches 400 ℃ to produce hydrogen through ammonia decomposition reaction, the preset pressure of a back pressure valve 5 is 10atm, when the pressure in the reactor is increased to the preset pressure of the back pressure valve, the generated mixed reaction gas is output from the back pressure valve, is connected with a gas chromatograph through a bypass valve 6 to analyze the composition of the mixed reaction gas, and parameters such as ammonia conversion rate, hydrogen production rate and the like are calculated:
ammonia conversion X NH3 (%) = [ total input NH 3 -total output NH 3)/total input NH 3 ]
Hydrogen production rate V (mmol·gcat -1·min-1) = (ammonia flow rate/22.4) conversion NH3 x 1.5/catalyst mass.
The mixed reaction gas output from the back pressure valve enters the heat exchanger 3 to exchange heat and pre-cool under the action of pressure difference, then enters the cooler 7 to cool to 15-30 ℃, ammonia gas reaches liquefaction under the pressure of 10atm in the temperature range, the gas-liquid mixed fluid enters the gas-liquid separator, and the separated and accumulated liquid ammonia is continuously returned to the raw material tank 1 for recycling through the electromagnetic valve 9 under the induction of the liquid level meter.
The crude hydrogen gas (hydrogen-nitrogen volume ratio is 4:1, ammonia volume percentage is < 7%) enriched at the upper end of the gas-liquid separator enters the membrane separator (working temperature is 350-450 ℃) after being heated to 400 ℃ by the heater 11 under the action of pressure difference, and the working pressure difference (1-5 atm) of the membrane separator can be regulated by the control valve 16. The treatment process setting of the hydrogen can be calculated according to the specific composition and flow rate (m 3h-1) of crude hydrogen, commercial palladium membrane parameters such as hydrogen permeation quantity (m 3 m-2h-1atm-1), working pressure difference (atm), palladium membrane selectivity and the like. The hydrogen recovery rate of palladium membrane separation is generally in the range of 85-95%. The purified hydrogen finally enters a metal hydrogen storage tank (working pressure 10-50 atm).
The residual gas (containing 5-15% of hydrogen by volume) is mixed with air input from an air pump 22 (diluted to contain 1-3% of hydrogen) and enters a catalytic combustor 14, flameless catalytic combustion is carried out under the action of a deoxidizing catalyst 15, the generated hot air flow heats the ammonia decomposer 4 and the hydrogen before entering a membrane separator, the ammonia decomposer and the heater are provided with a temperature control system, and the residual hot air flow can be discharged from a bypass valve 17.
Example 3:
the same procedure as in example 2 was followed except that the back pressure valve 5 was set to 20 atm.
Example 4:
The same procedure as in example 2 was followed except that the back pressure valve 5 was set to 40 atm.
Example 5:
the procedure of example 1 was repeated except that the hydrogen production temperature was set to 550 ℃.
Example 6:
The procedure of example 2 was repeated except that the hydrogen production temperature was set to 550 ℃.
Example 7:
The procedure of example 6 was repeated except that the back pressure valve 5 was set to 20 atm.
Example 8:
The procedure of example 6 was repeated except that the back pressure valve 5 was set to 40 atm.
The ammonia conversion X (%) and hydrogen production rate V (mmol. G cat -1·min-1) of examples 1 to 8 are shown in Table 1.
As can be readily seen from table 1, both the ammonia conversion X (%) and the hydrogen production rate V increased with increasing hydrogen production temperature, with activation temperatures (x=50%) below 400 ℃, approaching complete conversion at 550 ℃ at atmospheric pressure. Increasing hydrogen production pressure reduces ammonia conversion, but reduces the ammonia conversion to a smaller extent at high temperatures; conversely, increasing hydrogen production pressure will greatly increase the hydrogen production rate, with a greatly increased hydrogen production rate at temperatures at which ammonia conversion is nearly complete.
Therefore, through the design of recycling the ammonia raw material, the hydrogen production pressure is increased to greatly improve the hydrogen production rate, and the high-efficiency ammonia decomposition hydrogen production can be realized. The requirements of the proton exchange membrane fuel cell on practical application indexes such as mass hydrogen storage density, volume hydrogen storage density, hydrogen cost, vibration noise and the like are met.
The foregoing description of the specific embodiments of the present invention has been presented in conjunction with fig. 1, but it should not be construed as limiting the scope of the invention, and it should be appreciated by those skilled in the art that various equivalent structures or equivalent processes may be modified without the need for inventive effort or applied to other related technical fields while remaining within the scope of the invention.
TABLE 1
| Examples | XNH3 | V |
| Example 1 | 60.1 | 6.58 |
| Example 2 | 21.1 | 19.7 |
| Example 3 | 17.2 | 30.7 |
| Example 4 | 13.2 | 51.5 |
| Example 5 | 99.0 | 10.0 |
| Example 6 | 92.7 | 88.3 |
| Example 7 | 86.9 | 166.7 |
| Example 8 | 82.7 | 316.3 |
Claims (9)
1. The self-heating self-pressurizing high-efficiency ammonia decomposition hydrogen production system is characterized by comprising a liquid ammonia raw material tank, a high-pressure flow smoothing pump, an ammonia decomposer, a cooler, a gas-liquid separator, a first heat exchanger, a membrane separator and a metal hydrogen storage tank which are sequentially communicated through pipelines and valves, wherein a liquid phase outlet at the bottom of the gas-liquid separator is communicated with the liquid ammonia raw material tank to form a circulation loop, the self-heating self-pressurizing high-efficiency ammonia decomposition hydrogen production system also comprises a second heat exchanger, a cold pipe of the second heat exchanger is communicated with the high-pressure flow smoothing pump, a heat pipe of the second heat exchanger is communicated with a reaction channel air outlet pipe at the top end of a reaction channel of the ammonia decomposer through a back pressure valve, and a residual air output pipe of the membrane separator is connected with a catalytic combustor to send residual air into the catalytic combustor; continuously feeding liquid ammonia of a liquid ammonia raw material tank under the action of a high-pressure horizontal flow pump, gasifying and preheating through a second heat exchanger, then entering the ammonia decomposer from a reaction channel feed inlet at the bottom of the ammonia decomposer, enabling hydrogen, nitrogen and unreacted ammonia to enter the second heat exchanger together under the self-pressurizing pressure difference, performing heat exchange with liquid ammonia raw materials conveyed under the action of the high-pressure horizontal flow pump, preheating input liquid ammonia, simultaneously primarily cooling output hydrogen, nitrogen and unreacted ammonia, and then entering a cooler for further cooling; the catalytic burner supplies heat for the ammonia decomposer and the first heat exchanger; the ammonia decomposer is a micro-channel reactor, the structure of the ammonia decomposer is a horizontal-vertical double-side non-intercommunicating internal heat exchange tube pass, wherein the vertical tube pass is a reaction channel, ammonia cracking catalyst particles are filled in the reaction channel to form a catalytic bed, a feed inlet of the reaction channel is arranged at the bottom of the ammonia decomposer, and an air outlet pipe of the reaction channel is arranged at the top end of the reaction channel of the ammonia decomposer; the transverse shell pass is a hot fluid heating channel, a hot fluid inlet and a hot fluid outlet are respectively arranged on two sides of the heating channel, and the hot fluid inlet is communicated with a combustion gas output pipe of the catalytic combustor; liquid ammonia of a liquid ammonia raw material tank enters a reaction channel of an ammonia decomposer from a reaction channel feed inlet at the bottom of the ammonia decomposer under the action of a high-pressure advection pump, and enters a micro-channel reactor reaction channel which is not communicated with each other at two sides of the ammonia decomposer, the liquid ammonia is heated to 150-550 ℃ through heat convection with a transverse shell-side hot fluid heating channel to generate hydrogen and nitrogen through catalytic decomposition reaction, self-pressurization generates adjustable pressure of 10-50 atm, the hydrogen, the nitrogen and unreacted ammonia enter a cooler from an air outlet pipe at the top end reaction channel of the ammonia decomposer to be cooled to 15-30 ℃ under the self-pressurization pressure difference, then the liquid ammonia accumulated at the bottom of the gas-liquid separator is separated by a gas-liquid separator, the liquid ammonia is discharged back to the liquid ammonia raw material tank at fixed time under the action of pressure difference or the action of a liquid pump, crude hydrogen containing the nitrogen and a small amount of ammonia is heated to 350-450 ℃ from the top end of the gas-liquid separator by a first heat exchanger and then enters a membrane separator, and most of the hydrogen is purified; the purified hydrogen enters a metal hydrogen storage tank without a pressurizing unit; the hydrogen-containing ammonia nitrogen residual gas after hydrogen purification enters a catalytic burner for burning and heating, and is used for heating an ammonia decomposer and crude hydrogen containing nitrogen and a small amount of ammonia before entering a membrane separator.
2. An efficient ammonia decomposition hydrogen production system according to claim 1 wherein the cooler is of a water-cooled type or an air-cooled type, and the output hydrogen and nitrogen and unreacted ammonia are cooled to 15-30 ℃ and fed into a gas-liquid separator.
3. An efficient ammonia destruction hydrogen production system as recited in claim 1 wherein the catalytic burner is also in communication with the metal hydrogen storage tank; the ammonia decomposer and the first heat exchanger are provided with temperature control equipment.
4. The high-efficiency ammonia-decomposing hydrogen production system as claimed in claim 1, wherein the ammonia decomposer is connected with the gas-liquid separator through a back pressure valve, and hydrogen gas, nitrogen gas and unreacted ammonia gas generated in the ammonia decomposer are conveyed into the gas-liquid separator for gas-liquid separation.
5. An efficient ammonia decomposition hydrogen production system as claimed in claim 4 wherein the outlet of the back pressure valve is provided with a bypass valve for collecting the generated reaction gas for flow measurement and component chromatographic analysis.
6. The high-efficiency ammonia decomposition hydrogen production system according to claim 1, wherein the gas-liquid separator is sequentially connected with the first heat exchanger and the membrane separator through a control valve, and the separated gas is heated and then is sent into the membrane separator for hydrogen separation and purification; the gas-liquid separator is connected with the liquid ammonia raw material tank through an electromagnetic valve, and the cooled and separated liquid ammonia is recovered and recycled.
7. The high-efficiency ammonia decomposition hydrogen production system according to claim 1, wherein the membrane separator is provided with a palladium membrane tube bundle, and is connected with the metal hydrogen storage tank through a back pressure valve, and the air inlet end of the back pressure valve is provided with a bypass valve; the combustion gas output pipe of the catalytic combustor is respectively connected with the hot fluid inlet of the transverse heating channel of the ammonia decomposer, the first heat exchanger and the bypass valve through three paths of control valves; the metal hydrogen storage tank is connected with the catalytic burner through the control valve, and the hydrogen of the metal hydrogen storage tank is conveyed to the catalytic burner to perform a flameless combustion starting system; an air pump is arranged between the metal hydrogen storage tank and the catalytic burner.
8. An efficient ammonia decomposing hydrogen production system as claimed in claim 1 wherein the ammonia decomposer, first heat exchanger, membrane separator, catalytic burner are thermally sealed together to form a compact high temperature zone.
9. A self-heating self-pressurizing efficient ammonia decomposition hydrogen production method, characterized in that the self-heating self-pressurizing efficient ammonia decomposition hydrogen production system as claimed in claim 1 is adopted, comprising the following steps:
1) Catalytic decomposition of ammonia to produce hydrogen: liquid ammonia of a liquid ammonia raw material tank enters an ammonia decomposer under the action of a high-pressure high-flow pump, and hydrogen and nitrogen which are 10-50 atm are generated by self-increasing through heat convection with a transverse shell side hot fluid heating channel and heating to 150-550 ℃ to perform catalytic decomposition reaction in a microchannel reactor reaction channel which is not communicated with the two sides; the active component of the catalyst is ruthenium;
2) And (3) separating and purifying: the hydrogen obtained in the step 1) and the nitrogen are fed into a cooler to be cooled to 15-30 ℃ under the self-pressurization pressure difference together with the unreacted ammonia, then the hydrogen is separated by a gas-liquid separator, the liquid ammonia accumulated at the bottom of the gas-liquid separator is discharged at fixed time under the pressure difference effect or the liquid pump effect and returned to a liquid ammonia raw material tank for recycling, the crude hydrogen containing the nitrogen and a small amount of ammonia is heated to 350-450 ℃ by a first heat exchanger and then fed into a membrane separator, and most of the hydrogen is purified and fed into a metal hydrogen storage tank;
3) And (3) residual gas combustion heat supply: the purified hydrogen-containing ammonia nitrogen residual gas in the step 2) enters a catalytic combustor to burn and remove hydrogen and ammonia, and the generated hot gas is nitrogen and a small amount of steam and is used for heating an ammonia decomposer and crude hydrogen containing nitrogen and a small amount of ammonia before entering a membrane separator; the catalyst in the catalytic burner is compound chromium and Pt/SiO 2.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20110121821A (en) * | 2010-05-03 | 2011-11-09 | 한국지질자원연구원 | A micro-channel reactor for ammonia decomposition and ammonia decomposition method using the same |
| CN105152133A (en) * | 2015-09-06 | 2015-12-16 | 中国船舶重工集团公司第七一二研究所 | Online high-purity hydrogen preparation system for fuel cell and control method of online high-purity hydrogen preparation system |
| JP2018134628A (en) * | 2017-02-21 | 2018-08-30 | 新日鐵住金株式会社 | Catalyst structure for producing hydrogen from ammonia, method for manufacturing catalyst structure and method for producing hydrogen |
| CN111377403A (en) * | 2020-04-23 | 2020-07-07 | 广东大昆科技有限公司 | Quiet compact movable methanol low-temperature liquid-phase reforming hydrogen production system |
| CN115092884A (en) * | 2022-07-14 | 2022-09-23 | 招商局海洋装备研究院有限公司 | Self-heating ammonia decomposition hydrogen production device and hydrogen production method thereof |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20110121821A (en) * | 2010-05-03 | 2011-11-09 | 한국지질자원연구원 | A micro-channel reactor for ammonia decomposition and ammonia decomposition method using the same |
| CN105152133A (en) * | 2015-09-06 | 2015-12-16 | 中国船舶重工集团公司第七一二研究所 | Online high-purity hydrogen preparation system for fuel cell and control method of online high-purity hydrogen preparation system |
| JP2018134628A (en) * | 2017-02-21 | 2018-08-30 | 新日鐵住金株式会社 | Catalyst structure for producing hydrogen from ammonia, method for manufacturing catalyst structure and method for producing hydrogen |
| CN111377403A (en) * | 2020-04-23 | 2020-07-07 | 广东大昆科技有限公司 | Quiet compact movable methanol low-temperature liquid-phase reforming hydrogen production system |
| CN115092884A (en) * | 2022-07-14 | 2022-09-23 | 招商局海洋装备研究院有限公司 | Self-heating ammonia decomposition hydrogen production device and hydrogen production method thereof |
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