CN109573945A - The vapor separation of flue gas and reclamation set and method in a kind of methane reforming hydrogen manufacturing burner - Google Patents

The vapor separation of flue gas and reclamation set and method in a kind of methane reforming hydrogen manufacturing burner Download PDF

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Publication number
CN109573945A
CN109573945A CN201811536992.4A CN201811536992A CN109573945A CN 109573945 A CN109573945 A CN 109573945A CN 201811536992 A CN201811536992 A CN 201811536992A CN 109573945 A CN109573945 A CN 109573945A
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vapor
gas
methane
flue gas
pipe
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CN109573945B (en
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黎华玲
宋文吉
冯自平
韩颖
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Guangzhou Institute of Energy Conversion of CAS
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Guangzhou Institute of Energy Conversion of CAS
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    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32Production 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
    • C01B3/34Production 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
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02Processes for making hydrogen or synthesis gas
    • C01B2203/0205Processes for making hydrogen or synthesis gas containing a reforming step
    • C01B2203/0227Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
    • C01B2203/0233Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a steam reforming step
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/08Methods of heating or cooling
    • C01B2203/0805Methods of heating the process for making hydrogen or synthesis gas
    • C01B2203/0811Methods of heating the process for making hydrogen or synthesis gas by combustion of fuel
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/08Methods of heating or cooling
    • C01B2203/0872Methods of cooling
    • C01B2203/0883Methods of cooling by indirect heat exchange
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/12Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1205Composition of the feed
    • C01B2203/1211Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
    • C01B2203/1235Hydrocarbons
    • C01B2203/1241Natural gas or methane
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/12Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1258Pre-treatment of the feed
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/10Process efficiency
    • Y02P20/129Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Inorganic Chemistry (AREA)
  • Hydrogen, Water And Hydrids (AREA)

Abstract

The vapor separation of the invention discloses a kind of suitable for methane reforming hydrogen manufacturing burner flue gas and reclamation set and method, it separates, is back in methane-steam reforming by the waste heat high efficiente callback of flue gas, then by vapor, realize that waste heat efficiently utilizes, flue gas vapor reuse.

Description

In a kind of methane reforming hydrogen manufacturing burner the vapor separation of flue gas and reclamation set and Method
Technical field:
The vapor separation of the present invention relates to a kind of suitable for methane reforming hydrogen manufacturing burner flue gas and reclamation set and Method.
Background technique:
Increasingly depleted and environmental pollution now with petroleum resources is got worse, and develops and utilizes cleaning, cheap Fuel source is by common concern.Hydrogen is a kind of ideal clean energy resource, and comburant only has H2O, to environment without any dirt Dye.Therefore, hydrogen is widely applied in various aspects such as space flight, urban transportation, fuel cells.Methane source is abundant, is the head of hydrogen manufacturing Select raw material.Hydrogen production from methane vapor reforming process for making hydrogen produces hydrogen rate height, and hydrogen purity is high, is the effective way for solving hydrogen source.First Alkane steam reforming reaction isNeed to use methane and it is pure remove metal ion vapor, usually Reaction temperature will can be only achieved enough equilibrium conversions at 800 DEG C or more.This heat of reaction is fired by the methane in burner It burns and provides, the reaction equation of methyl hydride combustion isPure water of the band containing high heat in the flue gas of burning Vapor gas etc., there is no the methods that open high efficiente callback utilizes at present.
Summary of the invention:
It the vapor separation of the object of the present invention is to provide a kind of suitable for methane reforming hydrogen manufacturing burner flue gas and returns With device and method, separates, be back in methane reforming reaction, more than realization by the waste heat high efficiente callback of flue gas, then by vapor It is hot efficiently to utilize, flue gas vapor reuse.
The present invention is achieved by the following technical programs:
A kind of vapor separation of the flue gas suitable for methane reforming hydrogen manufacturing burner and reclamation set, the device include Improved hydrogen production from methane vapor reforming reaction unit, the reaction unit inner wall are equipped with heat-insulating material, reaction unit top Equipped with raw material tracheae, water inlet pipe, reaction unit top is preheating chamber, and preheating chamber center is equipped with casing, and casing center is equipped with thermoelectricity Even, casing outer wall of inner tube spiral wound has a fuel gas pipe, and casing outer tube outer wall is wound with air intake duct, casing inner and outer pipes it Between cavity formed smoke discharge tube;Described fuel gas pipe one end, which is stretched out, is connected to gas source at the top of reaction unit, other end connection is pre- The combustion chamber of hot cell lower end;Described air intake duct one end, which is stretched out, is connected to air at the top of reaction unit, the other end is connected to preheating chamber The combustion chamber of lower end;The smoke discharge tube is sequentially communicated surge tank, gas compressor, gas separator, condenser, liquid water Holding vessel, water pump, most followed by the top of reaction unit water inlet pipe is connected to, and forms a circulation loop;Described gas separator one end Also it is connected to N2Collecting tank;The condenser is also connected to CO2Collecting tank;The reaction unit lower central is combustion chamber, and methane water steams Gas reformation hydrogen production reaction chamber is distributed in combustion chamber surrounding, and hydrogen production from methane vapor reforming reaction chamber is respectively with raw material tracheae, water inlet Pipe connection;Hydrogen production from methane vapor reforming reaction chamber is additionally provided with product gas escape pipe, and fuel gas enters via fuel gas pipe, air Enter via air intake duct, by the preheating of preheating chamber, reaches combustion chamber and burn, the flue gas after burning is arranged by flue gas Outlet pipe discharge.
The gas separator is equipped with the one of which of hollow fiber separating film, molecular sieve, acticarbon, utilizes nitrogen Gas and vapor, the permeability of carbon dioxide, the difference of molecular diameter realize the separation of row nitrogen and vapor, carbon dioxide.
The coolant liquid of the condenser condenser pipe is pure deionized water.
A kind of vapor separation of the flue gas suitable for methane reforming hydrogen manufacturing burner and reuse method, this method is using upper State device, comprising the following steps:
1) methane fuel gas enters via fuel gas pipe, and air enters via air intake duct, by preheating chamber, reaches combustion It burns room to burn, and releases heat and be supplied to hydrogen production from methane vapor reforming reaction chamber progress hydrogen production from methane vapor reforming Reaction obtains hydrogen, and flue gas flows away by preheating indoor smoke discharge tube road after burning, while flue gas is carried out by preheating chamber Waste heat is passed to the methane fuel gas and air for being wrapped in tube wall inside and outside casing by heat exchange, is controlled heat transfer boundary condition, is made flue-gas temperature It is reduced to 100-150 DEG C, flue gas conveys gas into gas separator after surge tank, using gas compressor, by nitrogen With vapor and carbon dioxide separation, nitrogen is collected after separation;
2) passing through condenser through step 1) vapor obtained after separation and carbon dioxide, vapor is condensed into liquid, with Atmospheric carbon dioxide separation, is collected, then is delivered into water inlet pipe at the top of reaction unit through water pump and carried out methane vapor reforming React hydrogen manufacturing;
3) carbon dioxide after the separation of step 2) condenser is collected.
Particularly, in Water in Condenser condenser pipe after the heat exchange of pure vapor, the temperature of water rises, and is also used for methane water Steam reforming reaction.
Due to the vapor after the application fuel combustion in flue gas be it is pure, without any metal impurities, be by chance used for The vapor of methane-steam reforming requires the pure water for removing metal ion, therefore, by the vapor in flue gas through excessive It is used for methane-steam reforming from rear, reduces the metal impurities step of removing again of water.By using in condenser pipe The heat exchange of pure vapor after, the temperature of water rises, and becomes steam in methane-steam reforming, reducing water heating Heat consumption amount.
Beneficial effects of the present invention are as follows:
The present invention is ingenious in design, separates by the waste heat high efficiente callback of flue gas, then by vapor, is back to methane vapor weight In whole reaction, realize that waste heat efficiently utilizes, flue gas vapor reuse.
Detailed description of the invention:
Fig. 1 is the structural schematic diagram of one embodiment of the present of invention;
Fig. 2 is the cross-section structure perspective view of Fig. 1 middle sleeve;Wherein, 1, fuel gas pipe, 2, air intake duct, 3, unstripped gas Pipe, 4, surge tank, 5, gas separator, 6, condenser, 7, CO2Separating pipe, 8, H2O separating pipe, 9, liquid water store tank, 10, CO2Collecting tank, 11, N2Collecting tank, 12, N2Separating pipe, 13, hydrogen production from methane vapor reforming reaction chamber, 14, combustion chamber, 15, production Product gas escape pipe, 16, casing, 17, water inlet pipe, 18, heat-insulating material, 19, water pump, 20, water pipe, 21, gas compressor, 22, cigarette Gas discharge pipe.
Specific embodiment:
It is to further explanation of the invention, rather than limiting the invention below.
Embodiment 1:
A kind of vapor separation of flue gas suitable for methane reforming hydrogen manufacturing burner and reclamation set as shown in Figure 1, should Device includes improved hydrogen production from methane vapor reforming reaction unit, and the reaction unit inner wall is equipped with heat-insulating material 18, this is anti- It answers and is equipped with raw material tracheae 3, water inlet pipe 17 at the top of device, reaction unit top is preheating chamber, and preheating chamber center is equipped with the (ginseng of casing 16 See Fig. 2), the center of casing 16 is equipped with thermocouple, and 16 outer wall of inner tube spiral wound of casing has a fuel gas pipe 1, outside 16 outer tube of casing Wall is wound with air intake duct 2, and the cavity between 16 inner and outer pipes of casing forms smoke discharge tube 22;Described 1 one end of fuel gas pipe It stretches out and is connected to gas source at the top of reaction unit, the other end is connected to the combustion chamber 14 of preheating chamber lower end;It stretches described 2 one end of air intake duct Air is connected at the top of reaction unit out, the other end is connected to the combustion chamber 14 of preheating chamber lower end;The smoke discharge tube 22 successively connects Logical surge tank 4, gas compressor 21, gas separator 5, condenser 6, liquid water store tank 9, water pump 19, most followed by reaction fills Top set portion water inlet pipe 17 is connected to, and forms a circulation loop;Described 5 one end of gas separator is also connected to N2Collecting tank 11;It is described Condenser 6 is also connected to CO2Collecting tank 10;The reaction unit lower central is combustion chamber 14, and hydrogen production from methane vapor reforming is anti- Room 13 is answered to be distributed in 14 surrounding of combustion chamber, hydrogen production from methane vapor reforming reaction chamber 13 connects with raw material tracheae 3, water inlet pipe 17 respectively It is logical;Hydrogen production from methane vapor reforming reaction chamber 13 is additionally provided with product gas escape pipe 15, and fuel gas enters via fuel gas pipe 1, empty Gas enters via air intake duct 2, by the preheating of preheating chamber, reaches combustion chamber 14 and burns, the flue gas after burning passes through Smoke discharge tube 22 is discharged.
The gas separator 5 is equipped with the one of which of hollow fiber separating film, molecular sieve, acticarbon, utilizes Nitrogen and vapor, the permeability of carbon dioxide, the difference of molecular diameter realize point of row nitrogen and vapor, carbon dioxide From.
The coolant liquid of 6 condenser pipe of condenser is pure deionized water.
The vapor separation of flue gas and reuse method suitable for methane reforming hydrogen manufacturing burner, this method is including the use of upper State device, comprising the following steps:
Methane fuel gas enters via fuel gas pipe 1, and air enters via air intake duct 2, by preheating chamber, reaches combustion Room 14 is burnt to burn, main that following chemical reaction occurs:And release heat offer Hydrogen production from methane vapor reforming, which is carried out, to hydrogen production from methane vapor reforming reaction chamber 13 reacts to obtain hydrogen from product gas escape pipe 15 discharges are collected, and flue gas contains nitrogen, vapor and a small amount of carbon dioxide after burning, are discharged by preheating indoor flue gas Pipeline 22 flows away, while flue gas exchanges heat by preheating chamber, and waste heat is passed to and is wrapped in 16 outer wall of inner tube fuel gas of casing The air in 16 outer tube outer wall air intake duct of methane fuel gas and casing in pipe 1 heats methane fuel gas and air, control Heat transfer boundary condition processed, makes flue-gas temperature be reduced to 100-150 DEG C.Flue gas is after surge tank 4, using gas compressor 21 by gas It conveys into gas separator 5, using nitrogen and water vapour, the permeability of carbon dioxide, the difference of molecular diameter, passes through separator By nitrogen and vapor and a small amount of carbon dioxide separation.Nitrogen is through N after separation2Separating pipe 12 enters N2Collecting tank 11 is collected Get up;Vapor and carbon dioxide pass through 6 water condensing tube of condenser after separation, and vapor is condensed into liquid, with gas titanium dioxide Carbon separation, through H2O separating pipe 8 is collected into liquid water store tank 9, then conveys water inlet pipe 20 through water pump 19 and enter at the top of reaction unit Enter equipped with water inlet pipe 17 and carry out methane-steam reforming hydrogen manufacturing in hydrogen production from methane vapor reforming reaction chamber 13, reaches back Use purpose.Due to the vapor after clean fuel burning in flue gas be it is pure, without any metal impurities, be used for reforming reaction Vapor require the pure water for removing metal ion, therefore, by the vapor in flue gas, to be used for methane reforming anti-after separation It answers, reduces the metal impurities step of removing again of water.Pure vapor heat exchange in Water in Condenser condenser pipe by using Afterwards, the temperature of water rises, and becomes the heat consumption of steam in methane-steam reforming, reducing the heating of process water.Through Carbon dioxide is through CO after condenser separation2Separating pipe 7 enters CO2Collecting tank 10.

Claims (5)

1. a kind of vapor of flue gas suitable for methane reforming hydrogen manufacturing burner separates and reclamation set, which is characterized in that The device includes improved hydrogen production from methane vapor reforming reaction unit, and the reaction unit inner wall is equipped with heat-insulating material, this is anti- It answers and is equipped with raw material tracheae, water inlet pipe at the top of device, reaction unit top is preheating chamber, and preheating chamber center is equipped with casing, in casing Centre is equipped with thermocouple, and casing outer wall of inner tube spiral wound has fuel gas pipe, and casing outer tube outer wall is wound with air intake duct, set Cavity between pipe inner and outer pipes forms smoke discharge tube;Described fuel gas pipe one end, which is stretched out, is connected to gas source at the top of reaction unit, separately The combustion chamber of one end connection preheating chamber lower end;Described air intake duct one end, which is stretched out, is connected to air, the other end at the top of reaction unit It is connected to the combustion chamber of preheating chamber lower end;The smoke discharge tube is sequentially communicated surge tank, gas compressor, gas separator, cold Condenser, liquid water store tank, water pump, most followed by the top of reaction unit water inlet pipe is connected to, and forms a circulation loop;The gas Separator one end is also connected to N2Collecting tank;The condenser is also connected to CO2Collecting tank;The reaction unit lower central is burning Room, hydrogen production from methane vapor reforming reaction chamber are distributed in combustion chamber surrounding, and hydrogen production from methane vapor reforming reaction chamber is respectively with original Expect tracheae, water inlet pipe connection;Hydrogen production from methane vapor reforming reaction chamber is additionally provided with product gas escape pipe;Fuel gas is via fuel gas Pipe enters, and air enters via air intake duct, by the preheating of preheating chamber, reaches combustion chamber and burns, the cigarette after burning Gas is discharged by smoke discharge tube.
2. the vapor separation of flue gas and reuse dress suitable for methane reforming hydrogen manufacturing burner according to claim 1 It sets, which is characterized in that the gas separator is equipped with the one of which of hollow fiber separating film, molecular sieve, acticarbon.
3. the vapor of the flue gas according to claim 1 or claim 2 suitable for methane reforming hydrogen manufacturing burner separates and reuse Device, which is characterized in that the coolant liquid of the condenser condenser pipe is pure deionized water.
4. a kind of vapor of flue gas suitable for methane reforming hydrogen manufacturing burner separates and reuse method, which is characterized in that should Method utilizes claim described device any in claim 1-3, comprising the following steps:
1) methane fuel gas enters via fuel gas pipe, and air enters via air intake duct, by preheating chamber, reaches combustion chamber It burns, and releases heat and be supplied to the progress hydrogen production from methane vapor reforming reaction of hydrogen production from methane vapor reforming reaction chamber Hydrogen is obtained, flue gas flows away by preheating indoor smoke discharge tube road after burning, while flue gas exchanges heat by preheating chamber, Waste heat is passed to the methane fuel gas and air for being wrapped in tube wall inside and outside casing, heat transfer boundary condition is controlled, is reduced to flue-gas temperature 100-150 DEG C, flue gas conveys gas into gas separator after surge tank, using gas compressor, by nitrogen and water Steam and carbon dioxide separation, nitrogen collects after separation;
2) pass through condenser through step 1) vapor obtained after separation and carbon dioxide, vapor is condensed into liquid, with gas Carbon dioxide separation is collected, then is delivered into water inlet pipe at the top of reaction unit and carried out methane-steam reforming hydrogen manufacturing;
3) carbon dioxide after the separation of step 2) condenser is collected.
5. the vapor separation of flue gas and reuse method suitable for methane reforming hydrogen manufacturing burner according to claim 4, It is characterized in that, the temperature of water rises in Water in Condenser condenser pipe after the heat exchange of pure vapor, it is also used for methane vapor Reforming reaction.
CN201811536992.4A 2018-12-14 2018-12-14 Steam separation and recycling device and method for flue gas in methane reforming hydrogen production combustor Active CN109573945B (en)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111692885A (en) * 2020-06-24 2020-09-22 广州汤姆逊电气有限公司 Integrative mutual inductance three-purpose heating function furnace of high temperature pouring
CN112780452A (en) * 2021-01-07 2021-05-11 上海齐耀动力技术有限公司 Reforming combustion system of Stirling engine
CN114772551A (en) * 2022-06-16 2022-07-22 浙江百能科技有限公司 Method and system for efficiently utilizing methane-rich gas
WO2023142929A1 (en) * 2022-01-29 2023-08-03 中国科学院工程热物理研究所 Methane reforming reaction system
CN116768157A (en) * 2023-06-14 2023-09-19 中国科学院工程热物理研究所 Natural gas reforming hydrogen production system and method
CN116768157B (en) * 2023-06-14 2024-06-07 中国科学院工程热物理研究所 Natural gas reforming hydrogen production system and method

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105680072A (en) * 2014-12-03 2016-06-15 中国科学院大连化学物理研究所 Small and medium-size distributed natural gas steam reforming hydrogen production system and method
CN108467014A (en) * 2018-05-16 2018-08-31 张家港氢云新能源研究院有限公司 Reforming reactor in vapor reforming hydrogen production device

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105680072A (en) * 2014-12-03 2016-06-15 中国科学院大连化学物理研究所 Small and medium-size distributed natural gas steam reforming hydrogen production system and method
CN108467014A (en) * 2018-05-16 2018-08-31 张家港氢云新能源研究院有限公司 Reforming reactor in vapor reforming hydrogen production device

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111692885A (en) * 2020-06-24 2020-09-22 广州汤姆逊电气有限公司 Integrative mutual inductance three-purpose heating function furnace of high temperature pouring
CN112780452A (en) * 2021-01-07 2021-05-11 上海齐耀动力技术有限公司 Reforming combustion system of Stirling engine
WO2023142929A1 (en) * 2022-01-29 2023-08-03 中国科学院工程热物理研究所 Methane reforming reaction system
CN114772551A (en) * 2022-06-16 2022-07-22 浙江百能科技有限公司 Method and system for efficiently utilizing methane-rich gas
CN116768157A (en) * 2023-06-14 2023-09-19 中国科学院工程热物理研究所 Natural gas reforming hydrogen production system and method
CN116768157B (en) * 2023-06-14 2024-06-07 中国科学院工程热物理研究所 Natural gas reforming hydrogen production system and method

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