CN112047301A - Self-adaptive solar thermal drive methanol liquid-phase reforming hydrogen production device and method - Google Patents
Self-adaptive solar thermal drive methanol liquid-phase reforming hydrogen production device and method Download PDFInfo
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 330
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 167
- 239000001257 hydrogen Substances 0.000 title claims abstract description 167
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 167
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 105
- 238000002407 reforming Methods 0.000 title claims abstract description 75
- 239000007791 liquid phase Substances 0.000 title claims abstract description 71
- 238000000034 method Methods 0.000 title description 5
- 238000006243 chemical reaction Methods 0.000 claims abstract description 49
- 239000003054 catalyst Substances 0.000 claims abstract description 36
- 238000003860 storage Methods 0.000 claims abstract description 24
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 230000005484 gravity Effects 0.000 claims abstract description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 24
- 238000010438 heat treatment Methods 0.000 claims description 24
- 239000000243 solution Substances 0.000 claims description 17
- 239000007864 aqueous solution Substances 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 10
- 238000001179 sorption measurement Methods 0.000 claims description 10
- 229920001661 Chitosan Polymers 0.000 claims description 8
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 8
- 230000003044 adaptive effect Effects 0.000 claims description 7
- 239000012752 auxiliary agent Substances 0.000 claims description 6
- 230000003197 catalytic effect Effects 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 238000013461 design Methods 0.000 abstract description 3
- 229910000510 noble metal Inorganic materials 0.000 description 7
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 5
- 239000000446 fuel Substances 0.000 description 5
- 238000011056 performance test Methods 0.000 description 4
- 238000011161 development Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 238000001651 catalytic steam reforming of methanol Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000010248 power generation Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 150000004681 metal hydrides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000006057 reforming reaction Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
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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
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/323—Catalytic reaction of gaseous or liquid organic compounds other than hydrocarbons with gasifying agents
- C01B3/326—Catalytic reaction of gaseous or liquid organic compounds other than hydrocarbons with gasifying agents characterised by the catalyst
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/72—Copper
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/084—Decomposition of carbon-containing compounds into carbon
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/088—Decomposition of a metal salt
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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
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
- C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
- C01B2203/0233—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a steam reforming step
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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
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/06—Integration with other chemical processes
- C01B2203/066—Integration with other chemical processes with fuel cells
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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
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/08—Methods of heating or cooling
- C01B2203/0805—Methods of heating the process for making hydrogen or synthesis gas
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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
- 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
- C01B2203/1076—Copper or zinc-based catalysts
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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
- C01B2203/1082—Composition of support materials
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- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/12—Feeding the process for making hydrogen or synthesis gas
- C01B2203/1205—Composition of the feed
- C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
- C01B2203/1217—Alcohols
- C01B2203/1223—Methanol
Abstract
The invention discloses a self-adaptive solar heat-driven methanol liquid-phase reforming hydrogen production device and a self-adaptive solar heat-driven methanol liquid-phase reforming hydrogen production method, which realize the pressure balance of a hydrogen production reactor and a head tank through the innovative design that a methanol liquid-phase reforming hydrogen production reaction pipe filled with a Cu @ C catalyst is arranged in a solar vacuum heat collecting pipe, the hydrogen production reactor is communicated with a closed head tank, ensure that a methanol water solution in the head tank automatically feeds to the hydrogen production reactor under the action of gravity, the hydrogen production rate is self-adaptively adjusted along with the solar energy fluctuation, realize self-adaptive intelligent control, conveniently, safely, intelligently, efficiently and continuously utilize solar heat to drive methanol liquid-phase reforming hydrogen production, hydrogen storage and hydrogen utilization under a field environment, are used for a hydrogen source of a PEFC, do not need to be manually operated, and solve the problem that the field environment.
Description
The technical field is as follows:
the invention relates to the technical field of hydrogen energy, in particular to a self-adaptive solar heat-driven methanol liquid-phase reforming hydrogen production device and method.
Background art:
the hydrogen energy is a recognized clean energy with the most development potential in the 21 st century, industries such as hydrogen fuel cell distributed power stations, field communication base station hydrogen fuel cell standby power supplies and the like are developing, industrial development plans are made everywhere, and billions of market-scale hydrogen energy economy is created.
How to conveniently, safely and efficiently produce, store and use hydrogen in a field environment becomes one of the most challenging technologies. The existing hydrogen storage technologies, such as 35-70MPa gaseous high-pressure hydrogen storage, ultralow temperature liquid hydrogen storage, metal hydride hydrogen storage, porous medium hydrogen storage, organic liquid hydrogen storage and the like, have the problems of overhigh pressure, difficult heat preservation at ultralow temperature, lower hydrogen storage density, higher dehydrogenation temperature and the like, and are difficult to popularize and apply in scale.
Methanol (hydrogen content 12.5 wt%) is used as a hydrogen carrier, is considered as the most promising liquid sunlight fuel, and has the advantages of large industrial production scale, low price, easy obtainment and the like. The existing methanol reforming hydrogen production technology mainly comprises methanol steam reforming hydrogen production and methanol pyrolysis hydrogen production.
The hydrogen production by methanol steam reforming needs to vaporize methanol and brine-free water into steam, and then the steam phase reforming reaction is carried out at the higher temperature of 250-350 ℃ to generate H2、CO、CO2And the mixed gas has large volume of a reaction device, large energy consumption for vaporizing methanol and water, and CO concentration in the generated gas far exceeds the tolerance limit of the PEMFC, so that a complex and expensive hydrogen purification unit is required to be added, and the application of the mixed gas is greatly limited. The high-temperature cracking of methanol for hydrogen production also has the problems, and is difficult to popularize and apply.
The hydrogen production by methanol liquid phase reforming is a new hydrogen production technology which is just reported in recent years, and methanol-water is converted into high-pressure hydrogen containing only trace CO by a one-step method in a single reactor at the low temperature of 190 ℃ and under the action of noble metal catalysts such as platinum and the like. Chinese patent application CN201610462928.0 discloses a preparation method of a catalyst for methanol reforming hydrogen production at 190 ℃ by using a Pt/alpha-MoC-x supported monatomic dispersion catalyst with platinum loading capacity of 0.2-2%. But the preparation process is complex, the cost is high, and the limitation is large in practical application.
However, the high cost and low reserves of precious metals limit the industrial application. The direction of using non-noble metal to replace noble metal platinum catalyst for water phase reforming hydrogen production has great practical significance. The nickel catalyst in non-noble metal has considerable attention due to the hydrogen production performance, but often generates more alkanes, reduces the hydrogen purity and is often doped with other metals; the development of other non-noble metal catalysts (such as copper-based catalysts) has very important significance in realizing high-efficiency hydrogen production and hydrogen purification.
The commercial CuZnAl catalyst shows better activity, stability and H2 selectivity in the hydrogen production reaction by reforming methanol steam. But is rapidly deactivated by the corrosive action of high-temperature liquid water in the hydrogen production reaction by methanol liquid-phase reforming.
Therefore, the commercial CuZnAl catalyst has poor performance in the reaction of producing hydrogen by methanol liquid phase reforming, and cannot replace a noble metal catalyst, so that the technical problem to be solved by the technical personnel in the field is urgently needed.
Meanwhile, how to safely and efficiently produce, store and use hydrogen in an unattended environment becomes one of the most challenging technologies.
The invention content is as follows:
the invention aims to provide a self-adaptive solar heat-driven methanol liquid-phase reforming hydrogen production device and a self-adaptive solar heat-driven methanol liquid-phase reforming hydrogen production method, which realize the pressure balance of a hydrogen production reactor and a head tank through the innovative design that a methanol liquid-phase reforming hydrogen production reaction pipe filled with a Cu @ C catalyst is arranged in a solar vacuum heat collecting pipe, the hydrogen production reactor is communicated with a closed head tank, ensure that the methanol water solution in the head tank automatically feeds to the hydrogen production reactor under the action of gravity, the hydrogen production rate is self-adaptively adjusted along with the fluctuation of solar energy, realize self-adaptive intelligent control, conveniently, safely, intelligently, efficiently and continuously drive the methanol liquid-phase reforming hydrogen production, the hydrogen storage and the hydrogen utilization by using solar heat under the field environment, are used for the hydrogen source of a PEMFC, do not need to be attended, solve the problem that the field environment cannot be attended to continuously and intelligently produce hydrogen or the solar, and the temperature of the hydrogen production reactor fluctuates with the temperature, so that the hydrogen production rate fluctuates with the temperature, the raw material consumption fluctuates with the temperature, and the feeding quantity cannot be automatically adjusted to produce hydrogen for the power generation of the PEMFC fuel cell.
The invention is realized by the following technical scheme:
a self-adaptive solar thermal drive methanol liquid phase reforming hydrogen production device comprises a methanol/water storage tank, a supply pump, a closed elevated tank, a methanol liquid phase reforming hydrogen production reaction tube and an adsorption type high-pressure hydrogen tank which are sequentially communicated, wherein a Cu @ C catalyst is filled in the methanol liquid phase reforming hydrogen production reaction tube and is arranged in a solar vacuum heat collecting tube, the methanol/water storage tank is communicated with the closed elevated tank through the supply pump and a one-way valve to provide a methanol water solution for the closed elevated tank, the closed elevated tank is communicated with a methanol liquid phase reforming hydrogen production reaction tube core feeding guide pipe, in addition, the methanol liquid phase reforming hydrogen production reaction tube is also provided with a hydrogen outlet, and the hydrogen outlet is communicated with the adsorption type high-pressure hydrogen tank through the closed elevated tank and the one-way valve; a methanol water solution is continuously fed into a closed elevated tank through a supply pump, the methanol water solution in the closed elevated tank automatically flows to an axis feeding guide pipe of a methanol liquid phase reforming hydrogen production reaction pipe from top to bottom under the action of gravity, the methanol water solution enters a catalytic particle bed filled with a Cu @ C catalyst after being turned back at the bottom of the methanol liquid phase reforming hydrogen production reaction pipe, a solar vacuum heat collecting pipe collects solar heat energy and heats the methanol liquid phase reforming hydrogen production reaction pipe arranged in the solar vacuum heat collecting pipe, methanol liquid phase reforming hydrogen production reaction and conversion reaction are carried out at the temperature of 150 plus materials and 210 ℃, high-pressure hydrogen (the content of CO is less than 100ppm) with the pressure of 4.0-7.0MPa is generated through self pressurization, and the high-pressure hydrogen flows through the elevated tank and enters an adsorption type high-pressure hydrogen storage tank under the action of pressure.
Preferably, the solar vacuum heat collecting tube is obliquely arranged to better utilize solar energy.
Preferably, the closed head tank is provided with a liquid level control meter, the supply pump is stopped when the head tank reaches a certain liquid level, and the supply pump is started when the head tank is lower than the certain liquid level.
The methanol liquid phase reforming hydrogen production reaction pipe is communicated with the elevated tank to realize pressure balance, and the methanol aqueous solution in the elevated tank is ensured to automatically feed the methanol liquid phase reforming hydrogen production reaction pipe under the action of gravity. The hydrogen production rate is adaptively adjusted along with the fluctuation of solar energy, and adaptive intelligent control is realized.
The invention also provides a self-adaptive solar thermal drive methanol liquid-phase reforming hydrogen production method, which utilizes the device and comprises the following steps: the methanol aqueous solution continuously feeds to a closed elevated tank through a supply pump, the methanol aqueous solution in the closed elevated tank automatically flows to an axis feeding guide pipe of a methanol liquid phase reforming hydrogen production reaction pipe from top to bottom under the action of gravity, the methanol aqueous solution returns at the bottom of the methanol liquid phase reforming hydrogen production reaction pipe and then enters a catalytic particle bed filled with a Cu @ C catalyst, a solar vacuum heat collecting pipe collects solar heat energy and heats the methanol liquid phase reforming hydrogen production reaction pipe arranged in the solar vacuum heat collecting pipe, methanol liquid phase reforming hydrogen production reaction and conversion reaction are carried out at the temperature of 150 plus materials and 210 ℃, high-pressure hydrogen with 4.0-7.0MPa and CO content less than 100ppm is generated by self-pressurization, and the high-pressure hydrogen flows through the closed elevated tank and then enters an adsorption type high-pressure hydrogen storage tank under the action of pressure difference for a hydrogen source of a.
Preferably, the concentration of the aqueous methanol solution is 40 wt% to 60 wt%.
The preparation method of the copper-based catalyst Cu @ C for low-temperature liquid-phase methanol reforming hydrogen production comprises the following steps: copper nitrate is used as a Cu source, acetic acid is used as an auxiliary agent, chitosan is used as a carbon source, and the copper nitrate and the chitosan are mixed according to a molar ratio of 1: 1-3: 1, then adding acetic acid, fully stirring, heating to dry by a program, and then carrying out high-temperature heat treatment at the temperature of 400-900 ℃ under the protection of nitrogen to obtain the Cu @ C catalyst.
Preferably, the temperature programming drying part is heated from normal temperature to 60 ℃ at the speed of 5 ℃/min, is kept at the constant temperature of 60 ℃ for 5 hours, is heated from 60 ℃ to 80 ℃ at the speed of 5 ℃/min, is kept at the constant temperature of 80 ℃ for 3 hours, is heated from 80 ℃ to 110 ℃ at the speed of 5 ℃/min, and is kept at the constant temperature of 110 ℃ for 3-5 hours.
The invention has the following beneficial effects:
1) the innovative design that a methanol liquid phase reforming hydrogen production reaction tube filled with Cu @ C catalyst is arranged in a solar vacuum heat collecting tube, a hydrogen production reactor is communicated with a closed head tank is adopted, the pressure balance between the hydrogen production reactor and the head tank is realized, the methanol aqueous solution in the head tank is automatically fed into the hydrogen production reactor under the action of gravity, the hydrogen production rate is self-adaptively adjusted along with the fluctuation of solar energy, the self-adaptive intelligent control is realized, the methanol liquid phase reforming hydrogen production, the hydrogen storage and the hydrogen utilization are conveniently, safely, intelligently, efficiently and continuously driven by solar energy under the field environment, the hydrogen source for the PEMFC is used for the hydrogen source, the unattended operation is not needed, the excellent stability and the self-adaptive capability are shown, the problem that the continuous and intelligent hydrogen production cannot be realized under the unattended field environment is solved, or the heat collecting temperature of a glass vacuum tube fluctuates along with the fluctuation of the temperature of the, the hydrogen production rate and the raw material consumption fluctuate along with the fluctuation, and the feeding quantity can not be automatically adjusted to stably produce hydrogen for the power generation of the PEMFC fuel cell.
2) The catalyst is cheap, easy to obtain and high-efficiency, and shows good activity, stability and H2And (4) selectivity.
Description of the drawings:
fig. 1 is a schematic structural diagram of an adaptive solar thermally driven methanol liquid-phase reforming hydrogen production device of the present invention.
The specific implementation mode is as follows:
the following is a further description of the invention and is not intended to be limiting.
The device comprises a methanol/water storage tank, a replenishing pump, a closed elevated tank, a methanol liquid phase reforming hydrogen production reaction pipe and an adsorption type high-pressure hydrogen tank which are sequentially communicated, wherein a Cu @ C catalyst is filled in the methanol liquid phase reforming hydrogen production reaction pipe and is arranged in a solar vacuum heat collecting pipe, the methanol/water storage tank is communicated with the closed elevated tank through the replenishing pump and a one-way valve to provide a methanol water solution for the closed elevated tank, the closed elevated tank is communicated with a methanol liquid phase reforming hydrogen production reaction pipe core feeding guide pipe, in addition, the methanol liquid phase reforming hydrogen production reaction pipe is also provided with a hydrogen outlet, and the hydrogen outlet is communicated with the adsorption type high-pressure hydrogen tank through the closed elevated tank and the one-way valve; a methanol water solution is continuously fed into a closed elevated tank through a supply pump, the methanol water solution in the closed elevated tank automatically flows to an axis feeding guide pipe of a methanol liquid phase reforming hydrogen production reaction pipe from top to bottom under the action of gravity, the methanol water solution enters a catalytic particle bed filled with a Cu @ C catalyst after being turned back at the bottom of the methanol liquid phase reforming hydrogen production reaction pipe, a solar vacuum heat collecting pipe collects solar heat energy and heats the methanol liquid phase reforming hydrogen production reaction pipe arranged in the solar vacuum heat collecting pipe, methanol liquid phase reforming hydrogen production reaction and conversion reaction are carried out at the temperature of 150 plus materials and 210 ℃, high-pressure hydrogen (the content of CO is less than 100ppm) with the pressure of 4.0-7.0MPa is generated through self pressurization, and the high-pressure hydrogen flows through the elevated tank and enters an adsorption type high-pressure hydrogen storage tank under the action of pressure.
Example 1:
methanol and desalted water are mixed to prepare a methanol solution with the concentration of 60 wt%, and the methanol solution is added into a methanol/water storage tank. Copper nitrate and chitosan are mixed according to a molar ratio of 1: 1 to prepare an aqueous solution, adding 5 wt% of acetic acid as an auxiliary agent, fully stirring for 3 hours, and then heating and drying by a program, specifically heating from the normal temperature to 60 ℃ at a speed of 5 ℃/min, keeping the temperature at 60 ℃ for 5 hours, then continuously heating to 80 ℃ at a speed of 5 ℃/min, keeping the temperature at 80 ℃ for 3 hours, and then continuously heating to 110 ℃ at a speed of 5 ℃/min, and keeping the temperature for 3 hours. And then carrying out high-temperature heat treatment at 400 ℃ under the protection of nitrogen to obtain the Cu @ C-400 catalyst. The prepared Cu @ C-400 catalyst is filled into a methanol liquid phase reforming hydrogen production reaction tube, and the hydrogen production reaction tube is internally arranged in a solar vacuum heat collecting tube. The system is integrally connected according to the figure 1, and the performance test of field solar thermal drive methanol liquid phase reforming hydrogen production is carried out. The results are as follows:
example 2
Reference example 1 was repeated, except that the catalyst was prepared by a different method. The preparation method of the catalyst comprises the following steps: copper nitrate and chitosan are mixed according to a molar ratio of 2: 1 proportion to prepare aqueous solution, then adding 10 percent acetic acid as an auxiliary agent, fully stirring for 3 hours, and then heating and drying by a program, specifically heating from normal temperature to 60 ℃ at the speed of 5 ℃/min, keeping the temperature at 60 ℃ for 5 hours, then continuously heating to 80 ℃ at the speed of 5 ℃/min, keeping the temperature at 80 ℃ for 3 hours, and then continuously heating to 110 ℃ at the speed of 5 ℃/min, and keeping the temperature for 5 hours. Then carrying out high-temperature heat treatment at 600 ℃ under the protection of nitrogen to obtain the Cu @ C-600 catalyst. The prepared Cu @ C-600 catalyst is filled into a methanol liquid phase reforming hydrogen production reaction tube, and the hydrogen production reaction tube is internally arranged in a solar vacuum heat collecting tube. The system is integrally connected, and the performance test of field solar thermal drive methanol liquid phase reforming hydrogen production is carried out. The results are as follows:
example 3
Methanol and desalted water are mixed to prepare a methanol solution with the concentration of 40 wt%, and the methanol solution is added into a methanol/water storage tank. Copper nitrate and chitosan are mixed according to a molar ratio of 3: 1 to prepare an aqueous solution, adding 15 wt% of acetic acid as an auxiliary agent, fully stirring for 3 hours, and then heating and drying by a program, specifically heating from the normal temperature to 60 ℃ at a speed of 5 ℃/min, keeping the temperature at 60 ℃ for 5 hours, then continuously heating to 80 ℃ at a speed of 5 ℃/min, keeping the temperature at 80 ℃ for 3 hours, and then continuously heating to 110 ℃ at a speed of 5 ℃/min, and keeping the temperature for 5 hours. And then carrying out high-temperature heat treatment at 700 ℃ under the protection of nitrogen to obtain the Cu @ C-700 catalyst. The prepared Cu @ C-700 catalyst is filled into a methanol liquid phase reforming hydrogen production reaction tube, and the hydrogen production reaction tube is internally arranged in a solar vacuum heat collecting tube. The system is integrally connected, and the performance test of field solar thermal drive methanol liquid phase reforming hydrogen production is carried out. The results are as follows:
example 4
Methanol and desalted water are mixed to prepare a methanol solution with the concentration of 60 wt%, and the methanol solution is added into a methanol/water storage tank. Copper nitrate and chitosan are mixed according to a molar ratio of 2: 1 to prepare an aqueous solution, adding 10 wt% of acetic acid as an auxiliary agent, fully stirring for 3 hours, and then heating and drying by a program, specifically heating from the normal temperature to 60 ℃ at a speed of 5 ℃/min, keeping the temperature at 60 ℃ for 5 hours, then continuously heating to 80 ℃ at a speed of 5 ℃/min, keeping the temperature at 80 ℃ for 3 hours, and then continuously heating to 110 ℃ at a speed of 5 ℃/min, and keeping the temperature for 5 hours. And then carrying out high-temperature heat treatment at 900 ℃ under the protection of nitrogen to obtain the Cu @ C-900 catalyst. The prepared Cu @ C-900 catalyst is filled into a methanol liquid phase reforming hydrogen production reaction tube, and the hydrogen production reaction tube is internally arranged in a solar vacuum heat collecting tube. The system is integrally connected, and the performance test of field solar thermal drive methanol liquid phase reforming hydrogen production is carried out. The results are as follows:
from the above results, it can be concluded that: under the driving of fluctuating solar energy, the hydrogen production system has self-adaptive hydrogen production rate H at different temperatures2The selectivity reaches about 99 percent, and the CO content is lower than the lower detection limit of an instrument. The system provided by the invention shows excellent stability and self-adaptive capacity through rigorous inspection of complex solar fluctuation working conditions, and proves that the technical problems of unattended, convenient, safe and efficient hydrogen production, hydrogen storage and hydrogen production by using hydrogen and high-efficiency catalytic methanol liquid-phase reforming of cheap and easily-available non-noble metal catalyst in a field environment are solved.
Claims (7)
1. A self-adaptive solar thermal drive methanol liquid phase reforming hydrogen production device is characterized by comprising a methanol/water storage tank, a supply pump, a closed elevated tank, a methanol liquid phase reforming hydrogen production reaction pipe and an adsorption type high-pressure hydrogen tank which are sequentially communicated, wherein a Cu @ C catalyst is filled in the methanol liquid phase reforming hydrogen production reaction pipe and is arranged in a solar vacuum heat collecting pipe, the methanol/water storage tank is communicated with the closed elevated tank through the supply pump and a one-way valve to provide a methanol water solution for the closed elevated tank, the closed elevated tank is communicated with a methanol liquid phase reforming hydrogen production reaction pipe core feeding guide pipe, in addition, the methanol liquid phase reforming hydrogen production reaction pipe is also provided with a hydrogen outlet, and the hydrogen outlet is communicated with the adsorption type high-pressure hydrogen tank through the closed elevated tank and the one-way valve; the methanol aqueous solution continuously feeds to a closed elevated tank through a supply pump, the methanol aqueous solution in the closed elevated tank automatically flows to an axis feeding guide pipe of a methanol liquid phase reforming hydrogen production reaction pipe from top to bottom under the action of gravity, the methanol aqueous solution returns at the bottom of the methanol liquid phase reforming hydrogen production reaction pipe and then enters a catalytic particle bed filled with a Cu @ C catalyst, a solar vacuum heat collecting pipe collects solar heat energy and heats the methanol liquid phase reforming hydrogen production reaction pipe arranged in the solar vacuum heat collecting pipe, methanol liquid phase reforming hydrogen production reaction and conversion reaction are carried out at the temperature of 150-.
2. The adaptive solar thermally driven methanol liquid-phase reforming hydrogen production device according to claim 1, wherein the solar vacuum heat collecting tube is placed obliquely.
3. The self-adaptive solar thermal drive methanol liquid-phase reforming hydrogen production device according to claim 1 or 2, characterized in that the closed elevated tank is provided with a liquid level control meter, the supply pump is stopped when the elevated tank reaches a certain liquid level, and the supply pump is started when the elevated tank is lower than the certain liquid level.
4. An adaptive solar heat-driven methanol liquid-phase reforming hydrogen production method, which is characterized by utilizing the device of any one of claims 1 to 3 and comprising the following steps: the methanol aqueous solution continuously feeds to a closed elevated tank through a supply pump, the methanol aqueous solution in the closed elevated tank automatically flows to an axis feeding guide pipe of a methanol liquid phase reforming hydrogen production reaction pipe from top to bottom under the action of gravity, the methanol aqueous solution returns at the bottom of the methanol liquid phase reforming hydrogen production reaction pipe and then enters a catalytic particle bed filled with a Cu @ C catalyst, a solar vacuum heat collecting pipe collects solar heat energy and heats the methanol liquid phase reforming hydrogen production reaction pipe arranged in the solar vacuum heat collecting pipe, methanol liquid phase reforming hydrogen production reaction and conversion reaction are carried out at the temperature of 150 plus materials and 210 ℃, high-pressure hydrogen with 4.0-7.0MPa and CO content less than 100ppm is generated by self-pressurization, and the high-pressure hydrogen flows through the closed elevated tank and then enters an adsorption type high-pressure hydrogen storage tank under the action of pressure difference for a hydrogen source of a.
5. The adaptive solar thermally driven methanol liquid-phase reforming hydrogen production method according to claim 4, wherein the concentration of the methanol aqueous solution is 40 wt% to 60 wt%.
6. The adaptive solar thermal drive methanol liquid-phase reforming hydrogen production method according to claim 4, characterized in that the preparation method of the copper-based catalyst Cu @ C for low-temperature liquid-phase reforming hydrogen production of methanol comprises the following steps: copper nitrate is used as a Cu source, acetic acid is used as an auxiliary agent, chitosan is used as a carbon source, and the copper nitrate and the chitosan are mixed according to a molar ratio of 1: 1-3: 1, then adding acetic acid, fully stirring, heating to dry by a program, and then carrying out high-temperature heat treatment at the temperature of 400-900 ℃ under the protection of nitrogen to obtain the Cu @ C catalyst.
7. The adaptive solar thermal drive methanol liquid-phase reforming hydrogen production method according to claim 6, wherein the temperature programming drying part is used for raising the temperature from normal temperature to 60 ℃ at a rate of 5 ℃/min, keeping the temperature at 60 ℃ for 5 hours, raising the temperature from 60 ℃ to 80 ℃ at a rate of 5 ℃/min, keeping the temperature at 80 ℃ for 3 hours, raising the temperature from 80 ℃ to 110 ℃ at a rate of 5 ℃/min, and keeping the temperature at 110 ℃ for 3-5 hours.
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