CN113929055A - Methane steam reforming hydrogen production coupling hydrogen energy utilization system and process thereof - Google Patents
Methane steam reforming hydrogen production coupling hydrogen energy utilization system and process thereof Download PDFInfo
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 144
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 114
- 239000001257 hydrogen Substances 0.000 title claims abstract description 114
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 111
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 42
- 238000000629 steam reforming Methods 0.000 title claims abstract description 35
- 230000008878 coupling Effects 0.000 title claims abstract description 17
- 238000010168 coupling process Methods 0.000 title claims abstract description 17
- 238000005859 coupling reaction Methods 0.000 title claims abstract description 17
- 238000000034 method Methods 0.000 title claims abstract description 14
- 238000003860 storage Methods 0.000 claims abstract description 95
- 239000007789 gas Substances 0.000 claims abstract description 52
- 239000012528 membrane Substances 0.000 claims abstract description 47
- 230000003197 catalytic effect Effects 0.000 claims abstract description 39
- 238000004146 energy storage Methods 0.000 claims abstract description 15
- 238000010248 power generation Methods 0.000 claims abstract description 15
- 150000003839 salts Chemical class 0.000 claims description 62
- 238000006243 chemical reaction Methods 0.000 claims description 48
- 239000007788 liquid Substances 0.000 claims description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 13
- 230000005540 biological transmission Effects 0.000 claims description 9
- 239000003054 catalyst Substances 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 8
- 238000000926 separation method Methods 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 7
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 6
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 6
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims description 6
- 239000004323 potassium nitrate Substances 0.000 claims description 3
- 235000010333 potassium nitrate Nutrition 0.000 claims description 3
- 239000004317 sodium nitrate Substances 0.000 claims description 3
- 235000010344 sodium nitrate Nutrition 0.000 claims description 3
- 235000010288 sodium nitrite Nutrition 0.000 claims description 3
- 238000001764 infiltration Methods 0.000 claims 2
- 230000008595 infiltration Effects 0.000 claims 2
- 238000004891 communication Methods 0.000 claims 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 10
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 5
- 238000005984 hydrogenation reaction Methods 0.000 description 5
- 239000011833 salt mixture Substances 0.000 description 5
- 238000010276 construction Methods 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 239000000446 fuel Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 230000002441 reversible effect Effects 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000014509 gene expression Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- 239000012466 permeate Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 239000012495 reaction gas Substances 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 238000004088 simulation Methods 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
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- 239000012535 impurity Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000003204 osmotic effect Effects 0.000 description 1
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- 238000000053 physical method Methods 0.000 description 1
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- 230000001737 promoting effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
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- 239000002699 waste material Substances 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
- C01B3/34—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 by reaction of hydrocarbons with gasifying agents
- C01B3/38—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 by reaction of hydrocarbons with gasifying agents using catalysts
- C01B3/382—Multi-step processes
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- H—ELECTRICITY
- H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
- H02S—GENERATION OF ELECTRIC POWER BY CONVERSION OF INFRARED RADIATION, VISIBLE LIGHT OR ULTRAVIOLET LIGHT, e.g. USING PHOTOVOLTAIC [PV] MODULES
- H02S40/00—Components or accessories in combination with PV modules, not provided for in groups H02S10/00 - H02S30/00
- H02S40/40—Thermal components
- H02S40/44—Means to utilise heat energy, e.g. hybrid systems producing warm water and electricity at the same time
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- 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
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- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
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- 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
- C01B2203/0838—Methods of heating the process for making hydrogen or synthesis gas by heat exchange with exothermic reactions, other than by combustion of fuel
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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
- C01B2203/1235—Hydrocarbons
- C01B2203/1241—Natural gas or methane
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention discloses a methane steam reforming hydrogen production coupling hydrogen energy utilization system and a process thereof, which comprises a methane steam reforming hydrogen production module and a photovoltaic power generation energy storage module, wherein the methane steam reforming hydrogen production module comprises a methane gas storage tank, a first heat exchanger and a second heat exchanger, the catalytic bed permeation membrane reactor comprises a catalytic bed permeation membrane reactor, a gas separator and a condensing heat exchanger, wherein the top of the catalytic bed permeation membrane reactor is connected with the gas separator, the bottom of the gas separator is connected with the condensing heat exchanger, the condensing heat exchanger is sequentially connected with a first heat exchanger and a second heat exchanger, the second heat exchanger is connected with the catalytic bed permeation membrane reactor to form a circulation loop, a methane storage tank and a pipeline between the first heat exchanger and the second heat exchanger are connected and converged into a pipeline, the first heat exchanger and the second heat exchanger are circularly connected with a photovoltaic power generation energy storage module, and the photovoltaic power generation energy storage module provides circulating heat exchange. The invention greatly improves the utilization rate of clean energy and realizes the comprehensive utilization of photo-thermal and photovoltaic energy.
Description
Technical Field
The invention belongs to the technical field of solar hydrogen production, and particularly relates to a methane steam reforming hydrogen production coupling hydrogen energy utilization system and a process thereof.
Background
Currently, the human beings establish an economic development mode based on non-renewable energy sources mainly consuming coal, oil and natural gas, which leads to increasingly prominent problems of environmental pollution and greenhouse effect. With the coming of national policies, the development of the research on green energy technologies such as solar energy, wind energy, water energy, biomass energy and the like becomes a topic of high attention in all countries in the world. Hydrogen, as a secondary energy source with extremely high energy density and green cleanness, can be used as a clean energy source for storing waste (wind, light and water) energy sources and promoting the conversion from traditional fossil energy sources to green energy sources, has the energy density (140MJ/kg) 3 times that of petroleum and 4.5 times that of coal, and is regarded as the subversive technical direction of the future energy revolution. With the great improvement of the technical level and the capability of hydrogen production by utilizing renewable energy in China, the technical level of hydrogen energy utilization is continuously improved. The common ones are: hydrogen is used as fuel to be mixed into a natural gas pipeline, so that large-range civil gas transmission combustion is realized; a hydrogen station is built to provide the gas supply demand of the hydrogen fuel automobile; the hydrogen is used in the chemical industry to synthesize the required chemical products, such as methanol fuel and the like.
The involved "manufacturing-storage-transportation-and-handling" integration of hydrogen energy efficient utilization is an important part of the entire industry. The seat 586 is established globally and in the process of building a hydrogen station, and the seat 61 is already established in China and is put into operation 52. In order to encourage the construction of the hydrogenation station, the various governments of China have come out of the hydrogenation station subsidy rules, and the local construction of the hydrogenation station is supported from the aspects of examination and approval, construction, finance and the like of the hydrogenation station. In addition, the development of related technologies of hydrogen energy can be promoted by the addition of related national energy enterprises, a hydrogen energy company is established by China petrochemical industry, the development of the hydrogen energy technology and the construction of an infrastructure network are dedicated, internationally leading hydrogen energy enterprises are introduced as strategic investors, a hydrogen energy industrial chain and a hydrogen energy economic ecological circle are jointly created, and a hydrogen energy manufacturing-storage-transportation-addition integrated supply chain is established.
The hydrogen production technology commonly used in the industry at present is methane steam reforming hydrogen production technology. The preparation of hydrogen is realized by utilizing the radiation energy of solar energy to cause methane and water vapor to generate high-temperature thermochemical reversible reaction. On one hand, the invention ensures the stable hydrogen preparation process, reduces the dependency on fossil energy and electric power, further optimizes and designs the solar methane steam reforming hydrogen production system, and lays a good foundation for improving the hydrogen yield of the system; on the other hand, the prepared hydrogen can be stored by physical and chemical methods, so that the convenience of practical application is improved. In addition, carbon dioxide generated in the reaction process can be collected in a storage tank for other purposes. Finally, the electric energy generated by the photovoltaic power generation of the heat collection type paraboloid structure can be supplied to the power grid, and the energy utilization efficiency is further improved.
Disclosure of Invention
In order to solve the problems, the invention aims to provide a system and a process for utilizing the hydrogen energy in the hydrogen production coupling of methane steam reforming.
In order to achieve the purpose, the following technical scheme is provided:
a system for utilizing coupling hydrogen energy in methane steam reforming hydrogen production comprises a methane steam reforming hydrogen production module and a photovoltaic power generation energy storage module, wherein the photovoltaic power generation energy storage module is connected with the methane steam reforming hydrogen production module and provides heat energy for the methane steam reforming hydrogen production module, the methane steam reforming hydrogen production module converts the heat energy into chemical energy, the methane steam reforming hydrogen production module comprises a methane gas storage tank, a first heat exchanger, a second heat exchanger, a catalytic bed permeation membrane reactor, a gas separator and a condensing heat exchanger, the top of the catalytic bed permeation membrane reactor is connected with the gas separator, the bottom of the gas separator is connected with the condensing heat exchanger, the condensing heat exchanger is sequentially connected with the first heat exchanger and the second heat exchanger, the second heat exchanger is connected with the catalytic bed permeation membrane reactor to form a circulation loop, and the methane gas storage tank is connected with a pipeline between the first heat exchanger and the second heat exchanger to form a pipeline, the first heat exchanger and the second heat exchanger are circularly connected with the photovoltaic power generation energy storage module, and the photovoltaic power generation energy storage module provides circulating heat exchange.
Furthermore, the photovoltaic power generation energy storage module comprises a low-temperature molten salt storage tank, a photovoltaic photo-thermal collector and a high-temperature molten salt liquid storage tank, wherein an inlet of the low-temperature molten salt storage tank is connected with a heat source outlet of the first heat exchanger, an outlet of the low-temperature molten salt storage tank is connected with the photovoltaic photo-thermal collector, the photovoltaic photo-thermal collector is connected with the high-temperature molten salt liquid storage tank, an outlet of the high-temperature molten salt liquid storage tank is connected with a heat source inlet of the second heat exchanger, a heat source outlet of the second heat exchanger is connected with a heat source inlet of the first heat exchanger to form a circulation loop, and solar energy is converted into heat energy.
Furthermore, a liquid storage tank is further arranged on a pipeline between the condensing heat exchanger and the first heat exchanger and used for storing water condensed by the condensing heat exchanger.
Further, the bottom of the catalytic bed permeation membrane reactor is connected with CO2And a side outlet of the gas separator is connected with a hydrogen storage device.
Further, the photovoltaic photo-thermal collector is connected with a transformer, the transformer is connected with a power transmission line, and a second liquid pump is arranged between the first heat exchanger and the low-temperature molten salt storage tank.
Furthermore, a second electromagnetic control valve is arranged on a connecting pipeline of the methane gas storage tank, and a first electromagnetic control valve and a first liquid pump are arranged on a pipeline between the liquid storage tank and the first heat exchanger.
Further, a catalytic bed permeate membrane reactor with CO2And a second stop valve is arranged on a pipeline connected with the gas storage tank, and a first stop valve is arranged on a pipeline connected with the catalytic bed permeation membrane reactor and the gas separator.
A process for utilizing coupling hydrogen energy in methane steam reforming hydrogen production comprises the following steps:
1) the molten salt in the low-temperature molten salt storage tank enters the high-temperature molten salt storage tank after being heated by the photovoltaic photo-thermal collector, the molten salt in the high-temperature molten salt storage tank sequentially passes through the second heat exchanger and the first heat exchanger and serves as a heat medium to heat working media passing through the first heat exchanger and the second heat exchanger, the molten salt flows back to the low-temperature molten salt storage tank after heat exchange, the molten salt in the low-temperature molten salt storage tank is circularly heated, and redundant light energy stored by the photovoltaic photo-thermal collector is input into a power transmission line after being transformed by the transformer;
2) water in the liquid storage tank enters a first heat exchanger to exchange heat with molten salt, methane in a methane storage tank is mixed with unsaturated water vapor formed after heat exchange of the first heat exchanger, the mixture is further heated by a second heat exchanger to form superheated mixed gas, and the superheated mixed gas enters a catalytic bed permeation membrane reactor;
3) the superheated mixed gas of methane and water vapor enters a catalytic bed permeation membrane reactor for chemical reaction, a nickel-based catalyst is placed in the catalytic bed permeation membrane reactor, the product obtained by the reaction enters a gas separator through a hydrogen permeation membrane for separation, the hydrogen obtained by the separation enters a hydrogen storage device for storage, the water vapor obtained by the separation enters a liquid storage tank for circulation after being condensed by a condensing heat exchanger, and CO generated by the reaction in the catalytic bed permeation membrane reactor2Into CO2In a gas storage tank.
Further, the molten salt in the high-temperature molten salt liquid storage tank is a mixture of 53 mass percent of potassium nitrate, 40 mass percent of sodium nitrite and 7 mass percent of sodium nitrate, the outlet temperature is 480-565 ℃, and the temperature of the molten salt in the second heat exchanger is 450-544 ℃.
Further, the mass flow rate of the water vapor entering the first heat exchanger is 0-2.5 kg/h, and the mass flow rate of the methane is 0.3-1.3 kg/h.
The chemical reactions that take place in a catalytic bed permeate membrane reactor are shown below,
wherein, the chemical reaction equation (1) is a main reaction equation, the reaction is a reversible reaction, the forward reaction is an endothermic reaction, the reverse reaction is an exothermic reaction, and the enthalpy of the whole reaction process is changed into 206 kJ/mol. The chemical reaction equation (2) is a side reaction equation, the forward reaction is an exothermic reaction, the reverse reaction is an endothermic reaction, and the enthalpy of the whole reaction process becomes 41 kJ/mol. Since the main reaction is an endothermic reaction and the side reaction is an exothermic reaction, the enthalpy change of the whole chemical reaction process is 165 kJ/mol.
The purpose of the hydrogen in the hydrogen storage device is to transport the hydrogen to a hydrogenation station by a hydrogen transport vehicle; low-temperature liquefaction is carried out through a physical method and stored in a liquefied hydrogen storage tank; hydrogen in a certain proportion is added as clean fuel to be delivered to a civil terminal through a city gas pipeline.
The invention has the beneficial effects that:
1) the ternary molten salt heat storage working medium and the heat regenerator device are used for improving a photo-thermal energy storage system, increasing the reaction temperature of the solar methane steam reforming hydrogen production, ensuring the stability of system energy conversion, and laying a foundation for improving the hydrogen production conversion rate.
2) The temperature condition required by the reaction is obtained through the photo-thermal energy storage circulating system, the utilization rate of clean energy is greatly improved, the environment is protected, the environment is clean and pollution-free, in addition, the parabolic structure integrates the photovoltaic power generation function, the utilization rate of solar radiation energy is further improved, and the photo-thermal and photovoltaic energy comprehensive utilization is realized.
3) Compared with the traditional catalytic bed reactor without the hydrogen permeable membrane, the catalytic bed reactor with the hydrogen permeable membrane further improves the chemical reaction rate, reduces the loss in the energy conversion process of the system, is also beneficial to the separation of reaction products and reduces impurities in hydrogen products.
Drawings
FIG. 1 is a schematic flow diagram of the present invention;
FIG. 2 is a schematic diagram of a catalytic bed hydrogen permeation membrane reactor of the present invention;
FIG. 3 is a graph comparing methane conversion and hydrogen generation according to the present invention.
In the figure: 1-a liquid storage tank; 2-a first liquid pump; 3-a first solenoid control valve; 4-a methane gas storage tank; 5-a second solenoid control valve; 6-a first heat exchanger; 7-a second heat exchanger; 8-catalytic bed permeation membrane reactor; 9-a first stop valve; 10 a gas separator; 11-a condensing heat exchanger; 12-a hydrogen storage means; 13-a photovoltaic photo-thermal collector; 14-a high-temperature molten salt storage tank; 15-a transformer; 16-a power transmission line; 17-a second stop valve; 18-CO2A gas storage tank; 19-a second liquid pump; 20-low temperature molten salt storage tank.
Detailed Description
The invention will be further described with reference to the drawings and examples in the following description, but the scope of the invention is not limited thereto.
As shown in fig. 1, a system for utilizing coupling hydrogen energy for methane steam reforming hydrogen production comprises a liquid storage tank 1, a methane gas storage tank 4, a first heat exchanger 6, a second heat exchanger 7, a catalytic bed permeable membrane reactor 8, a gas separator 10, a condensing heat exchanger 11, a hydrogen storage device 12, a photovoltaic photo-thermal collector 13, a high-temperature molten salt liquid storage tank 14, a transformer 15, a power transmission line 16, a CO2 gas storage tank 18 and a low-temperature molten salt storage tank 20; the top of a catalytic bed permeable membrane reactor 8 is connected with a gas separator 10, the bottom of the gas separator 10 is connected with a condensing heat exchanger 11, the condensing heat exchanger 11 is sequentially connected with a liquid storage tank 1, a first heat exchanger 6 and a second heat exchanger 7, the second heat exchanger 7 is connected with the catalytic bed permeable membrane reactor 8 to form a circulation loop, a methane storage tank 4 is connected with a pipeline between the first heat exchanger 6 and the second heat exchanger 7 to be converged into a pipeline, the first heat exchanger 6 is connected with the second heat exchanger 7 in a circulating manner, the inlet of a low-temperature molten salt storage tank 20 is connected with the first heat exchanger 6, the outlet of the low-temperature molten salt storage tank is connected with a photovoltaic photo-thermal collector 13, the photovoltaic photo-thermal collector 13 is connected with a high-temperature molten salt liquid storage tank 14, the outlet of the high-temperature molten salt liquid storage tank 14 is connected with the second heat exchanger 7 to form a circulation loop, and solar energy is converted into heat energy, the bottom of the catalytic bed osmotic membrane reactor 8 is connected with CO2A gas storage tank 18 is connected with a hydrogen storage device at the side outlet of the gas separator 1012, a photovoltaic photo-thermal collector 13 is connected with a transformer 15, the transformer 15 is connected with a power transmission line 16, a second liquid pump 19 is arranged between a first heat exchanger 6 and a low-temperature molten salt storage tank 20, a second electromagnetic control valve 5 is arranged on a connecting pipeline of a methane storage tank 4, a first electromagnetic control valve 3 and a first liquid pump 2 are arranged on a pipeline between a liquid storage tank 1 and the first heat exchanger 6, and a catalytic bed osmosis membrane reactor 8 and a CO osmosis membrane reactor 8 are arranged on the pipeline2A second stop valve 17 is arranged on a pipeline connected with the gas storage tank 18, and a first stop valve 9 is arranged on a pipeline connected with the catalytic bed permeable membrane reactor 8 and the gas separator 10.
As shown in fig. 2, the catalytic bed permeation membrane reactor 8 mainly comprises a reaction gas inlet, a hydrogen outlet, a hydrogen permeable membrane, a carbon dioxide outlet and a nickel-based catalyst, wherein a high-temperature methane and water vapor mixture enters through the reaction gas inlet and passes through the hydrogen permeable membrane, and a violent chemical reaction occurs on a catalyst bed formed by the nickel-based catalyst to generate hydrogen, carbon dioxide and a small amount of byproducts.
A process for utilizing coupling hydrogen energy in methane steam reforming hydrogen production comprises the following steps:
1) the temperature of the molten salt mixture in the low-temperature molten salt storage tank 20 is 290-400 ℃, the molten salt mixture is heated by the photovoltaic photo-thermal collector 13 and then enters the high-temperature molten salt storage tank 14, the temperature of the molten salt mixture in the high-temperature molten salt storage tank 14 is 550 ℃, the molten salt in the high-temperature molten salt storage tank 14 sequentially passes through the second heat exchanger 7 and the first heat exchanger 6, the molten salt in the high-temperature molten salt storage tank 14 serves as a heat medium to heat working media passing through the first heat exchanger 6 and the second heat exchanger 7, the working media flow back into the low-temperature molten salt storage tank 20 after heat exchange, the molten salt in the low-temperature molten salt storage tank 20 is circularly heated, redundant light energy stored by the photovoltaic photo-thermal collector 13 is transformed by the transformer 15 and then is input into the power transmission line 16, the mass flow rate of the molten salt mixture is 1200-1800 kg/h, and the molten salt mixture is a mixture of potassium nitrate with the mass fraction of 53%, sodium nitrite with the mass fraction of 40% and sodium nitrate with the mass fraction of 7% A compound (I) is provided.
2) The first liquid pump 2 and the first electromagnetic control valve 3 are started, water in the liquid storage tank 1 enters the first heat exchanger 6 to exchange heat with molten salt, methane in the methane storage tank 4 is mixed with unsaturated water vapor formed after heat exchange of the first heat exchanger 6, the mixture is further heated to form superheated mixed gas through the second heat exchanger 7, the superheated mixed gas enters the catalytic bed permeation membrane reactor 8, the mass flow rate of the water vapor in the process is 0.5-2.5 kg/h, the mass flow rate of the methane is 0.3-1.3 kg/h, and in order to guarantee high hydrogen production conversion efficiency, the inlet temperature of the mixture (methane and water vapor) entering the reactor is controlled to be 420-550 ℃.
3) The superheated mixed gas of methane and water vapor enters a catalytic bed permeation membrane reactor 8 for chemical reaction, a nickel-based catalyst is placed in the catalytic bed permeation membrane reactor 8, a product obtained by the reaction enters a gas separator 10 through a hydrogen permeation membrane for separation, hydrogen obtained by the separation enters a hydrogen storage device 12 for storage, the water vapor obtained by the separation enters a liquid storage tank 1 for circulation after being condensed through a condensing heat exchanger 11, and CO generated by the reaction in the catalytic bed permeation membrane reactor 82Into CO2In the gas storage tank 18, the chemical expression of the nickel-based catalyst is Ni (10%) Pt (3%)/CeZr-LaOx, the material of the catalyst bed is SiC foam porous material, and the proper catalyst and reactor material are selected to effectively avoid coke formation in the reactor, thereby improving the conversion efficiency of the chemical reaction.
Conversion of methane XCH4And hydrogen production conversion YH2As important evaluation indexes, the corresponding calculation expressions are as follows:
wherein the content of the first and second substances,
the unit mol is the molar mass of imported methane;
outlet methane molar mass, unit mol;
the unit mol of the hydrogen produced by the hydrogen permeable membrane.
The experimental and simulation result graphs of the methane conversion rate and the hydrogen generation rate of the hydrogen production system along with the change of the molten salt inlet temperature at the second heat exchanger 7 are shown in fig. 3, when the mass flow rate of the water vapor is 2.3kg/h, and the molar mass ratio (S/C) of the water vapor to the carbon contained in the methane is 3.3mol/mol, the methane conversion rate gradually increases along with the gradual increase of the inlet molten salt temperature (from 450 ℃ to 544 ℃), the hydrogen generation rate also gradually increases, and reaches the maximum value at the temperature of 544 ℃, and the methane conversion rate at the moment is 64.8% (experimental value) and 63.37% (simulated value); the hydrogen generation rate was 3.26m3H (experimental value), 3.25m3H (analog value). Through analysis and verification, the consistency of experimental and simulation results is obtained, the correctness of the model is verified, and favorable conditions are provided for the subsequent further parametric study of the methane steam reforming hydrogen production coupling hydrogen energy utilization system.
Claims (10)
1. The utility model provides a methane steam reforming hydrogen production coupling hydrogen energy utilizes system, a serial communication port, including methane steam reforming hydrogen production module and photovoltaic power generation energy storage module, photovoltaic power generation energy storage module is connected with methane steam reforming hydrogen production module, provide heat energy for methane steam reforming hydrogen production module, methane steam reforming hydrogen production module converts heat energy into chemical energy, methane steam reforming hydrogen production module includes methane gas holder (4), first heat exchanger (6), second heat exchanger (7), catalytic bed infiltration membrane reactor (8), gas separator (10) and condensing heat exchanger (11), the top of catalytic bed infiltration membrane reactor (8) is connected with gas separator (10), the bottom of gas separator (10) is connected with condensing heat exchanger (11), condensing heat exchanger (11) connect gradually first heat exchanger (6) and second heat exchanger (7), the second heat exchanger (7) is connected with the catalytic bed permeation membrane reactor (8) to form a circulation loop, the methane storage tank (4) is connected with the pipeline between the first heat exchanger (6) and the second heat exchanger (7) and converged into a pipeline, the first heat exchanger (6) and the second heat exchanger (7) are circularly connected with the photovoltaic power generation energy storage module, and the photovoltaic power generation energy storage module provides circulating heat exchange.
2. The system for utilizing the coupling hydrogen energy for the methane steam reforming hydrogen production according to claim 1, wherein the photovoltaic power generation energy storage module comprises a low-temperature molten salt storage tank (20), a photovoltaic photo-thermal collector (13) and a high-temperature molten salt storage tank (14), an inlet of the low-temperature molten salt storage tank (20) is connected with a heat source outlet of the first heat exchanger (6), an outlet of the low-temperature molten salt storage tank is connected with the photovoltaic photo-thermal collector (13), the photovoltaic photo-thermal collector (13) is connected with the high-temperature molten salt storage tank (14), an outlet of the high-temperature molten salt storage tank (14) is connected with a heat source inlet of the second heat exchanger (7), and a heat source outlet of the second heat exchanger (7) is connected with a heat source inlet of the first heat exchanger (6) to form a circulation loop so as to convert solar energy into heat energy.
3. The system for utilizing the hydrogen energy coupled with the hydrogen production through methane steam reforming as claimed in claim 1, wherein a liquid storage tank (1) is further arranged on a pipeline between the condensing heat exchanger (11) and the first heat exchanger (6), and the liquid storage tank (1) is used for storing water condensed by the condensing heat exchanger (11).
4. The system for hydrogen energy utilization coupling hydrogen production through methane steam reforming as claimed in claim 1, wherein the bottom of the catalytic bed permeable membrane reactor (8) is connected with CO2A gas storage tank (18), and a side outlet of the gas separator (10) is connected with a hydrogen storage device (12).
5. The system for utilizing the hydrogen energy coupled with the hydrogen production through methane steam reforming as claimed in claim 2, wherein the photovoltaic photo-thermal collector (13) is connected with a transformer (15), the transformer (15) is connected with a power transmission line (16), and a second liquid pump (19) is arranged between the first heat exchanger (6) and the low-temperature molten salt storage tank (20).
6. The system for utilizing the hydrogen energy coupled with the hydrogen production through methane steam reforming as set forth in claim 3, characterized in that a second electromagnetic control valve (5) is arranged on a connecting pipeline of the methane gas storage tank (4), and a first electromagnetic control valve (3) and a first liquid pump (2) are arranged on a pipeline between the liquid storage tank (1) and the first heat exchanger (6).
7. The system for hydrogen energy utilization coupling hydrogen production through methane steam reforming as claimed in claim 4, wherein the catalytic bed permeable membrane reactor (8) is connected with CO2A second stop valve (17) is arranged on a pipeline connected with the gas storage tank (18), and a first stop valve (9) is arranged on a pipeline connected with the catalytic bed permeation membrane reactor (8) and the gas separator (10).
8. A process for coupling the production of hydrogen by methane steam reforming with hydrogen energy according to claim 2, comprising the steps of:
1) the molten salt in the low-temperature molten salt storage tank (20) enters the high-temperature molten salt storage tank (14) after being heated by the photovoltaic photo-thermal collector (13), the molten salt in the high-temperature molten salt storage tank (14) sequentially passes through the second heat exchanger (7) and the first heat exchanger (6) and serves as a heat medium to heat working media passing through the first heat exchanger (6) and the second heat exchanger (7), the working media flow back to the low-temperature molten salt storage tank (20) after heat exchange, the molten salt in the low-temperature molten salt storage tank (20) is circularly heated, and redundant light energy stored by the photovoltaic photo-thermal collector (13) is transformed by the transformer (15) and then is input into the power transmission line (16);
2) water in the liquid storage tank (1) enters a first heat exchanger (6) to exchange heat with molten salt, methane in a methane storage tank (4) is mixed with unsaturated water vapor formed after heat exchange of the first heat exchanger (6), the mixture is further heated by a second heat exchanger (7) to form superheated mixed gas, and the superheated mixed gas enters a catalytic bed permeable membrane reactor (8);
3) the superheated mixed gas of methane and water vapor enters a catalytic bed permeation membrane reactor (8) for chemical reaction, a nickel-based catalyst is placed in the catalytic bed permeation membrane reactor (8), and products obtained by the reaction are led throughThe hydrogen-passing permeable membrane enters a gas separator (10) for separation, the separated hydrogen enters a hydrogen storage device (12) for storage, the separated water vapor enters a liquid storage tank (1) for circulation after being condensed by a condensing heat exchanger (11), and CO generated by reaction in a catalytic bed permeable membrane reactor (8)2Into CO2A gas storage tank (18).
9. The process for utilizing the coupling hydrogen energy for hydrogen production by methane steam reforming as claimed in claim 8, wherein the molten salt in the high-temperature molten salt storage tank (14) is a mixture of 53 mass percent potassium nitrate, 40 mass percent sodium nitrite and 7 mass percent sodium nitrate, the outlet temperature is 480-565 ℃, and the temperature of the molten salt in the second heat exchanger (7) is 450-544 ℃.
10. The process for utilizing the hydrogen energy coupling through the hydrogen production by the methane steam reforming as set forth in claim 8, wherein the mass flow rate of the water vapor entering the first heat exchanger (6) is 0.5-2.5 kg/h, and the mass flow rate of the methane is 0.3-1.3 kg/h.
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| US20150037246A1 (en) * | 2012-03-16 | 2015-02-05 | Stamicarbon B.V. Acting Under The Name Of Mt Innovation Center | Method and system for the production of hydrogen |
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| A. GIACONIA ET AL.: "Multi-fuelled solar steam reforming for pure hydrogen production using solar salts as heat transfer fluid", 《ENERGY PROCEDIA》 * |
| ALBERTO GIACONIA ET AL.: "Experimental validation of a pilot membrane reactor for hydrogen production by solar steam reforming of methane at maximum 550℃ using molten salts as heat transfer fluid", 《INTERNATIONAL JOURNAL OF HYDROGEN ENERGY》 * |
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