CN112919408A - Hydrogen production system and method, gas supply system, and hydrogen station - Google Patents
Hydrogen production system and method, gas supply system, and hydrogen station Download PDFInfo
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- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
- C01B3/061—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of metal oxides with water
- C01B3/063—Cyclic methods
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- C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
- C01B3/506—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification at low temperatures
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- C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
- C01B3/56—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with solids; Regeneration of used solids
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
- F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
- F17C5/00—Methods or apparatus for filling containers with liquefied, solidified, or compressed gases under pressures
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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
- C01B2203/0811—Methods of heating the process for making hydrogen or synthesis gas by combustion of fuel
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- C01B2203/08—Methods of heating or cooling
- C01B2203/0805—Methods of heating the process for making hydrogen or synthesis gas
- C01B2203/0811—Methods of heating the process for making hydrogen or synthesis gas by combustion of fuel
- C01B2203/0822—Methods of heating the process for making hydrogen or synthesis gas by combustion of fuel the fuel containing hydrogen
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/32—Hydrogen storage
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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Abstract
The invention belongs to the technical field of gas preparation, and particularly relates to a hydrogen production system. The hydrogen production system comprises: a gas production system, a carbon dioxide separation system, and a hydrogen purification system; the gas making system comprises a fuel reactor, a steam reactor and a regeneration reactor, and the fuel reactor, the steam reactor and the regeneration reactor are connected end to form a closed circulation loop; the carbon dioxide separation system is communicated with the fuel reactor and is used for separating carbon dioxide and water; the hydrogen purification system includes: the system comprises a first cooler, a first gas-liquid separation tank, a dryer and a purifier; the steam reactor, the first gas-liquid separation tank, the dryer and the purifier are communicated in sequence; the first cooler is arranged on a pipeline for communicating the steam reactor with the first gas-liquid separation tank. The hydrogen production system provided by the invention can realize hydrogen production and hydrogenation in the hydrogenation station.
Description
Technical Field
The invention belongs to the technical field of gas preparation, and particularly relates to a hydrogen production system, a hydrogen production method, a gas supply system and a hydrogen adding station.
Background
Hydrogen energy is a clean, efficient, safe and sustainable new energy and is considered as the clean energy with the most development potential in the twenty-first century. In recent years, several countries and regions such as the united states, european union, japan, etc. have advanced hydrogen energy and fuel cell development to the national strategic level and have established specific action plans, policies, and development routes. The main reasons for restricting the development of hydrogen energy at the present stage are high hydrogen production cost, weak hydrogen energy infrastructure and the like. Fuel cell vehicles and hydrogen stations are important components in the hydrogen energy industry. A hydrogen refueling station is an important infrastructure for providing a source of hydrogen for a hydrogen energy utilizing device.
The hydrogen production station has two modes of hydrogen production inside the station and hydrogen production outside the station. The hydrogen production in the station usually adopts the processes of electrolyzing water to produce hydrogen and converting natural gas (or liquefied gas) steam into hydrogen. The hydrogen production in the station has the advantages of saving the transportation cost of hydrogen and reducing the volume of a hydrogen storage tank of the hydrogen station; the disadvantages are large occupied area of hydrogen production equipment and limited application. In addition, hydrogen filling of the hydrogen fuel cell vehicle is discontinuous, so that the hydrogen production equipment needs to be started and stopped frequently, and the operation management is complex and difficult. The in-station hydrogen production technology is developed more and more mature in areas such as Japan and Europe.
At present, most domestic hydrogen stations adopt out-of-station hydrogen production, and the out-of-station hydrogen production is limited by transportation distance, road conditions and the like, so that the cost is relatively high. With the development of in-situ hydrogen production technology and the continuous improvement of relevant specifications of domestic hydrogen stations, hydrogen production in the stations is a main source of hydrogen sources of future hydrogen stations.
Therefore, there is a need for an apparatus and method for effecting in-plant hydrogenation.
Disclosure of Invention
The invention aims to provide a hydrogen production system, a hydrogen production method, a gas supply system and a hydrogenation station, which are used for producing hydrogen and hydrogenating in the hydrogenation station.
In order to achieve the above object, a first aspect of the present invention provides a hydrogen production system comprising: a gas production system, a carbon dioxide separation system, and a hydrogen purification system;
the gas making system comprises a fuel reactor, a steam reactor and a regeneration reactor, and the fuel reactor, the steam reactor and the regeneration reactor are connected end to form a closed circulation loop;
the carbon dioxide separation system is communicated with the fuel reactor and is used for separating the carbon dioxide and the water;
the hydrogen purification system comprises a first cooler, a first gas-liquid separation tank, a dryer and a purifier; the steam reactor, the first gas-liquid separation tank, the dryer and the purifier are communicated in sequence; the first cooler is arranged on a pipeline which is communicated with the steam reactor and the first gas-liquid separation tank.
Specifically, the carbon dioxide separation system includes: a second cooler and a second knockout drum; the second gas-liquid separation tank is communicated with the fuel reactor; the second cooler is arranged on a pipeline which communicates the second gas-liquid separation tank with the fuel reactor.
A second aspect of the present invention provides a gas supply system comprising: the hydrogen production system and the hydrogen storage and filling system;
the hydrogen storage and filling system is used for storing the hydrogen prepared by the hydrogen production system and supplying the hydrogen to a hydrogen filling device.
Specifically, the hydrogen storage and filling system comprises: a compressor, a hydrogen storage tank and/or a bundle pipe vehicle, and a pressure detector;
the gas inlet end of the compressor is communicated with the hydrogen purification system, and the gas outlet end of the compressor is communicated with the hydrogen storage tank and/or the tube bundle vehicle;
the pressure detector is arranged on a pipeline for communicating the gas outlet end of the compressor with the hydrogen storage tank.
Preferably, the hydrogen storage and filling system further comprises a hydrogenation machine, and the hydrogenation machine is communicated with the hydrogen storage tank.
Preferably, the gas supply system further comprises: and the control system is used for controlling the rotating speed of the compressor, the hydrogen filling rate of the hydrogenation machine and a valve arranged on a pipeline in the hydrogen storage and filling system.
Preferably, the gas supply system further comprises: a carbon dioxide storage system. The carbon dioxide storage system comprises a carbon dioxide storage tank, and the carbon dioxide storage tank is communicated with a gas phase outlet of the second gas-liquid separation tank.
In a third aspect, the invention provides a hydrogenation station comprising the gas supply system.
In a fourth aspect of the present invention, there is provided a method for producing hydrogen, comprising the steps of:
introducing alkane-containing gas, synthesis gas or naphtha into a combustion reactor, wherein the alkane-containing gas, synthesis gas or naphtha reacts with high-valence metal oxide in the combustion reactor to generate low-valence metal oxide, carbon dioxide and water;
separating the carbon dioxide and water using a carbon dioxide separation system;
feeding the metal oxide with the low valence state into a steam reactor, and reacting with water vapor to generate a product containing hydrogen and a metal oxide with an intermediate valence state;
sending the product containing hydrogen into a hydrogen purification system, and sequentially carrying out cooling, gas-liquid separation, drying treatment and purification impurity removal treatment to obtain a hydrogen product;
and feeding the intermediate-valence metal oxide into a regeneration reactor, reacting with oxygen to generate high-valence metal oxide, and returning the high-valence metal oxide to the combustion reactor for recycling.
In the present invention, the alkane is C1-C4Alkanes, preferably methane. In particular, the alkane-containing gas is selected from pipeline natural gas and compressed natural gas(CNG), Liquefied Natural Gas (LNG), and Liquefied Petroleum Gas (LPG). The synthesis gas is at least one of coal synthesis gas, biomass synthesis gas, petroleum coke synthesis gas and coke synthesis gas. When syngas or naphtha is used as fuel, it is necessary to purify the fuel to reduce the byproduct generation and avoid catalyst poisoning. When at least one of pipeline natural gas (CNG), Compressed Natural Gas (CNG), Liquefied Natural Gas (LNG) and Liquefied Petroleum Gas (LPG) is used for producing hydrogen, the hydrogen is required to be purified to remove non-alkane components such as sulfur, nitrogen and oxygen, and particularly the sulfide is required to be removed to avoid generating unnecessary byproducts and poisoning a catalyst.
In the present invention, the higher valent metal oxide is selected from Fe2O3、Mn2O7、MoO3Or V2O5Preferably Fe2O3；
The metal oxide in a low valence state is selected from FeO, MnO, MoO or VO, and FeO is preferred;
the metal oxide of the intermediate valence is selected from Fe3O4、MnO2、MoO2Or V2O3Preferably Fe3O4。
It will be understood by those skilled in the art that when the higher valent metal oxide is Fe2O3When the metal oxide in the lower valence state is FeO, the metal oxide in the middle valence state is Fe3O4(ii) a When the metal oxide in the higher valence state is Mn2O7When the metal oxide in the lower valence state is MnO, the metal oxide in the intermediate valence state is MnO2(ii) a When the metal oxide in the higher valence state is MoO3When the metal oxide in the lower valence state is MoO, the metal oxide in the intermediate valence state is MoO2(ii) a When the metal oxide in the higher valence state is V2O5When the metal oxide in the lower valence state is VO, the metal oxide in the intermediate valence state is V2O3。
In a preferred embodiment of the present invention, the reaction conditions in the combustion reactor are a reaction temperature of 700 ℃ and 1300 ℃, a reaction pressure of 0.05 to 3.5 MPa; preferably, the reaction temperature is 800-.
The reaction conditions in the steam reactor are 650-1200 ℃ of reaction temperature and 0.05-3.5MPa of reaction pressure; preferably, the reaction temperature is 750-1000 ℃ and the reaction pressure is 0.2-2.5 MPa.
The reaction conditions in the regeneration reactor are that the reaction temperature is 800-1400 ℃ and the reaction pressure is 0.05-3.5 MPa; preferably, the reaction temperature is 1000 ℃ and 1200 ℃, and the reaction pressure is 0.2-2.5 MPa.
Preferably, the drying agent used in the drying process includes: at least one of silica gel, a first molecular sieve, and montmorillonite.
More preferably, the desiccant comprises: the silica gel and the first molecular sieve and/or the montmorillonite. The first molecular sieve is preferably a 3A molecular sieve.
More preferably, in the case where the drying agent is silica gel and the first molecular sieve and/or the montmorillonite, the drying treatment is a drying treatment of the product containing hydrogen gas after cooling and gas-liquid separation by the silica gel and the first molecular sieve and/or the montmorillonite.
Specifically, the purification and impurity removal treatment mode comprises the following steps: at least one of cryogenic, membrane separation, and adsorption separation.
Preferably, the purification and impurity removal treatment mode comprises: membrane separation and adsorption separation.
More preferably, the membrane material used for the membrane separation comprises: at least one of a palladium metal membrane, a palladium metal alloy membrane, a crystalline alloy membrane, an amorphous alloy membrane, polyimide, polysulfone, polyamide, and polyethylene trimethyl silane.
Preferably, the adsorptive separation comprises: at least one of once-through separation, Pressure Swing Adsorption (PSA), and Temperature Swing Adsorption (TSA).
More preferably, the adsorbent material used for the pressure swing adsorption and the temperature swing adsorption is independently selected from at least one of a second molecular sieve, activated alumina, silica gel, and activated carbon.
More preferably, the second molecular sieve used for the pressure swing adsorption and the temperature swing adsorption is independently selected from a 3A molecular sieve and/or a 5A molecular sieve.
More preferably, the operating temperature of the pressure swing adsorption is 40-55 ℃ and the operating pressure is 0.03-2.5 MPa.
More preferably, the operation temperature of the temperature swing adsorption is 50-420 ℃, and the operation pressure is 0.05-2.0 MPa.
Preferably, the hydrogen production method further comprises storing the hydrogen product.
Specifically, the carbon dioxide and water are cooled by a carbon dioxide separation system, and then gas-liquid separation is performed.
More specifically, in the carbon dioxide separation system, the temperature of the cooling is 20 to 55 ℃.
More specifically, in the hydrogen purification system, the temperature of the cooling is 20 to 55 ℃.
The hydrogen production system provided by the invention utilizes metal oxides with different valence states in a combustion reactor, a steam reactor and a regeneration reactor as catalysts, gas containing alkane, synthesis gas or naphtha as fuel, utilizes water vapor to prepare a product containing hydrogen, and a carbon dioxide separation system is used for separating carbon dioxide and water generated in the process of reducing the metal oxide with high valence state into the metal oxide with low valence state, and a first cooler, a first gas-liquid separation tank, a dryer and a purifier in a hydrogen purification system are used for sequentially removing impurities from the product containing hydrogen, so that the content of hydrogen in the product is more than 99.9999%, hydrogen production and hydrogenation in a hydrogenation station are realized, and direct energy supply can be realized. Not only so, the metal oxide can be recycled.
The hydrogen provided by the gas supply system provided by the invention can be directly used for supplying energy and can also be used for supplying carbon dioxide.
The hydrogen station provided by the invention can realize hydrogen production and hydrogenation in the station and directly supply energy.
The hydrogen production scale of the hydrogenation station provided by the invention can be adjusted according to the actual hydrogen consumption, the gas production system is in a hot standby state, and one-key start-stop can be realized. The gas supply system is flexible to operate, all valves are automatically controlled, and manual operation is not needed.
The hydrogen station provided by the invention omits complex procedures such as hydrogen filling, transportation, gas unloading and the like, and avoids the long transportation time and line of hydrogen production from the station, and potential safety hazards caused by improper operation, equipment aging and the like in the loading and unloading process.
The hydrogen station provided by the invention can realize hydrogen production and hydrogenation in the station, avoid potential risks of hydrogen in the transportation process, save the transportation cost of hydrogen and reduce the volume of a hydrogen storage tank in the hydrogen station.
The hydrogen station provided by the invention can provide hydrogen with various filling pressure grades according to different hydrogen pressure grade requirements of users, thereby fully meeting the market requirements.
The hydrogen production method provided by the invention utilizes metal oxides with different valence states in a combustion reactor, a steam reactor and a regeneration reactor as catalysts, uses alkane-containing gas, synthesis gas or naphtha as fuel, utilizes water vapor to prepare a product containing hydrogen, uses a carbon dioxide separation system to separate carbon dioxide and water generated in the process of reducing high-valence metal oxides into low-valence metal oxides, and uses a hydrogen purification system to carry out cooling, gas-liquid separation, drying treatment and purification impurity removal treatment on the product containing hydrogen to obtain the hydrogen product with the hydrogen content of 99.9999%, so that hydrogen production and hydrogenation in a hydrogenation station can be realized, and direct energy supply can be realized. Moreover, the metal oxide can be recycled.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
The above and other objects, features and advantages of the present invention will become more apparent by describing in more detail exemplary embodiments thereof with reference to the attached drawings, in which like reference numerals generally represent like parts throughout.
Fig. 1 shows a schematic diagram of a hydrogen production system provided by the present invention.
Fig. 2 shows a schematic view of a gas supply system provided by the present invention.
Reference numerals:
101. a fuel reactor; 102. a steam reactor; 103. a regeneration reactor;
2. a carbon dioxide separation system;
201 a second cooler; 202. a second knock-out pot;
3. a hydrogen purification system;
301. a first cooler; 302. a first gas-liquid separation tank; 303. a dryer; 304. a purifier;
10. a hydrogen production system;
20. hydrogen storage and filling system:
2001. a compressor; 2002. a hydrogen storage tank; 2003. a tube bundling vehicle; 2004. a pressure detector; 2005. A hydrogenation machine; 2006. a hydrogen fuel cell vehicle;
30. a control system;
40. a fuel gas purification system;
f1, a first control valve;
f2, second control valve;
f3, pressure reducing valve;
f4, third control valve.
Detailed Description
Preferred embodiments of the present invention will be described in more detail below. While the following describes preferred embodiments of the invention, it should be understood that the invention may be embodied in various forms and should not be construed as limited to the embodiments set forth herein.
The invention provides a hydrogen production method. Referring to fig. 1, fig. 1 shows a schematic diagram of a hydrogen production system provided by the present invention. As shown in fig. 1, the hydrogen production method comprises the following steps:
the alkane-containing gas, syngas or naphtha is introduced into the combustion reactor 101, and the alkane-containing gas, syngas or naphtha reacts with the higher-valent metal oxide in the combustion reactor 101 to produce lower-valent metal oxide, carbon dioxide and water.
The carbon dioxide and water are separated using a carbon dioxide separation system 2.
The reduced metal oxide is fed to steam reactor 102 and reacts with steam to produce a product containing hydrogen and an intermediate metal oxide.
And (3) sending the product containing the hydrogen into a hydrogen purification system 3, and sequentially carrying out cooling, gas-liquid separation, drying treatment and purification impurity removal treatment to obtain a hydrogen product.
And feeding the intermediate-valence metal oxide into a regeneration reactor 103, reacting with oxygen to generate high-valence metal oxide, and returning the high-valence metal oxide to the combustion reactor 101 for recycling.
The hydrogen production method provided by the invention utilizes metal oxides with different valence states in a combustion reactor 101, a steam reactor 102 and a regeneration reactor 103 as catalysts, uses alkane-containing gas, synthesis gas or naphtha as fuel, utilizes water vapor to prepare a product containing hydrogen, uses a carbon dioxide separation system to separate carbon dioxide and water generated in the process of reducing high-valence-state metal oxides into low-valence-state metal oxides, and uses a hydrogen purification system to carry out cooling, gas-liquid separation, drying treatment and purification impurity removal treatment on the product containing hydrogen to obtain the hydrogen with the hydrogen content of 99.9999 percent, realizes hydrogen production and hydrogenation in a hydrogenation station, and can directly supply energy. Moreover, the metal oxide can be recycled.
In the production of hydrogen using alkane-containing gas, synthesis gas or naphtha, it is preferable to purify alkane-containing gas, synthesis gas or naphtha as a fuel to remove impurities such as sulfides, to reduce the difficulty and cost of purifying hydrogen-containing products, and to prevent catalyst poisoning.
The alkane used in the present invention is preferably C1-C4Alkanes, more preferably methane, and alkane-containing gases in the petroleum industry, and especially methane-containing gases, are almost all suitable for use in the present invention. For example, the said alkaneIs selected from at least one of pipeline natural gas (LNG), Compressed Natural Gas (CNG), Liquefied Natural Gas (LNG) and Liquefied Petroleum Gas (LPG). The synthesis gas is at least one of coal synthesis gas, biomass synthesis gas, petroleum coke synthesis gas and coke synthesis gas.
In the present invention, the higher valent metal oxide is selected from Fe2O3、Mn2O7、MoO3Or V2O5Preferably Fe2O3；
The metal oxide in a low valence state is selected from FeO, MnO, MoO or VO, and FeO is preferred;
the metal oxide of the intermediate valence is selected from Fe3O4、MnO2、MoO2Or V2O3Preferably Fe3O4。
It will be understood by those skilled in the art that when the higher valent metal oxide is Fe2O3When the metal oxide in the lower valence state is FeO, the metal oxide in the middle valence state is Fe3O4(ii) a When the metal oxide in the higher valence state is Mn2O7When the metal oxide in the lower valence state is MnO, the metal oxide in the intermediate valence state is MnO2(ii) a When the metal oxide in the higher valence state is MoO3When the metal oxide in the lower valence state is MoO, the metal oxide in the intermediate valence state is MoO2(ii) a When the metal oxide in the higher valence state is V2O5When the metal oxide in the lower valence state is VO, the metal oxide in the intermediate valence state is V2O3。
Below with CH4The catalytic reaction with iron oxide is an example to illustrate the chemical reaction that occurs during the production of hydrogen.
The first step is as follows: 4Fe2O3+CH4＝8FeO+CO2+2H2O△H1123K＝305.754kJ
The second step is that: 8FeO +8/3H2O＝8/3Fe3O4+H2△H1173K＝-122.973kJ
The third step: 8/3Fe3O4+2/3O2＝4Fe2O3△H1173K＝-321.136kJ
The general reaction formula is as follows: 3CH4+2H2O+2O2＝3CO2+8H2△H1173K＝-139.126kJ
In the present invention, the drying treatment is mainly used for removing moisture from the product containing hydrogen, and materials having hygroscopic properties without heat release are basically suitable for the present invention. The skilled person can select the drying agent to be used in the drying process according to the actual situation. Specifically, the drying agent used in the drying process includes: at least one of silica gel, a first molecular sieve, and montmorillonite. Preferably, the desiccant comprises: the silica gel and the first molecular sieve and/or the montmorillonite. More preferably, the first molecular sieve is a 3A molecular sieve.
More preferably, in the case where the drying agent is silica gel and the first molecular sieve and/or the montmorillonite, the drying treatment is a drying treatment of the product containing hydrogen gas after cooling and gas-liquid separation by the silica gel and the first molecular sieve and/or the montmorillonite.
In the present invention, the impurities in the hydrogen-containing product contain not only moisture but also CO and CO2、O2、Ar、N2One skilled in the art can purify the hydrogen-containing product by purging the gas to remove impurities. Specifically, the purification and impurity removal treatment mode comprises the following steps: at least one of cryogenic cooling, membrane separation and adsorption separation. Because cryogenic cooling requires lower temperature and higher energy consumption, the purification and impurity removal treatment preferably comprises the following steps: membrane separation and adsorption separation. And sequentially carrying out purification and impurity removal treatment on the product containing the hydrogen by membrane separation and adsorption separation.
One skilled in the art can select the membrane material used for membrane separation based on the impurities contained in the hydrogen-containing product. Preferably, the membrane material used for the membrane separation comprises: at least one of a palladium metal membrane, a palladium metal alloy membrane, a crystalline alloy membrane, an amorphous alloy membrane, polyimide, polysulfone, polyamide, and polyvinyltrimethylsilane.
The skilled person can select the mode of adsorptive separation and the adsorbent material used for adsorptive separation according to the impurities contained in the product containing hydrogen. Preferably, the adsorptive separation comprises: at least one of once-through separation, Pressure Swing Adsorption (PSA), and Temperature Swing Adsorption (TSA). More preferably, the adsorption material used for the pressure swing adsorption and the temperature swing adsorption is independently selected from at least one of a second molecular sieve, activated alumina, silica gel and activated carbon. More preferably, the second molecular sieve used for the pressure swing adsorption and the temperature swing adsorption is independently selected from a 3A molecular sieve and/or a 5A molecular sieve. Preferably, the operating temperature of the pressure swing adsorption is 40-55 ℃, and the operating pressure is 0.03-2.5MPa, further 0.1-2.35 MPa. Preferably, the operating temperature of the temperature swing adsorption is 50-420 ℃, further 60-400 ℃, and the operating pressure is 0.05-2.0MPa, further 0.15-1.7 MPa.
Specifically, the hydrogen production method further comprises storing the hydrogen product.
The invention also provides a hydrogen production system. With continued reference to FIG. 1, the hydrogen production system includes: a gas production system, a carbon dioxide separation system 2, and a hydrogen purification system 3; the gas making system comprises a fuel reactor 101, a steam reactor 102 and a regeneration reactor 103, and the fuel reactor 101, the steam reactor 102 and the regeneration reactor 103 are connected end to form a closed circulation loop; the carbon dioxide separation system 2 is in communication with the fuel reactor 101 for separating the carbon dioxide and water; the hydrogen purification system 3 includes: a first cooler 301, a first gas-liquid separation tank 302, a dryer 303, and a purifier 304; the steam reactor 102, the first gas-liquid separation tank 302, the dryer 303 and the purifier 304 are communicated in sequence; the first cooler 301 is disposed on a pipe connecting the vapor reactor 102 and the first gas-liquid separation tank 302.
The hydrogen production system provided by the invention utilizes metal oxides with different valence states in a combustion reactor, a steam reactor and a regeneration reactor as catalysts, gas containing alkane, synthesis gas or naphtha is used as fuel, a product containing hydrogen is prepared by utilizing water vapor, carbon dioxide and water are generated in the process of separating high-valence metal oxide into low-valence metal oxide through a carbon dioxide separation system 2, the water vapor and the low-valence metal oxide react in the steam reactor 102 to generate a product containing hydrogen, cooling, gas-liquid separation, drying treatment and purification impurity removal treatment are sequentially carried out through a first cooler 301, a first gas-liquid separation tank 302, a dryer 303 and a purifier 304 in a hydrogen purification system 3, so that the hydrogen content in the hydrogen product is more than 99.9999 percent, hydrogen production and hydrogenation in a hydrogenation station are realized, can supply energy directly.
In the present invention, two or more dryers and purifiers may be connected in series to sufficiently remove impurities from the product containing hydrogen.
The present invention is not particularly limited with respect to the forms of the fuel reactor 101, the steam reactor 102 and the regeneration reactor 103, and may take the form of reactors commonly used in the art, for example, the fuel reactor 101, the steam reactor 102 and the regeneration reactor 103 may be independently selected from at least one of a fluidized bed reactor, a moving bed reactor and an ebullated bed reactor. Preferably, the fuel reactor 101 and the steam reactor 102 may be radial moving bed reactors, and the regeneration reactor 103 may be a fluidized bed reactor.
In the present invention, the carbon dioxide separation system is mainly used to separate moisture and carbon dioxide generated in the process of reducing a metal oxide having a high valence to a metal oxide having a low valence. The person skilled in the art can select the composition of the carbon dioxide separation system according to actual needs. Referring to fig. 2, the carbon dioxide separation system 2 includes: a second cooler 201 and a second knock-out pot 202; the second knock-out pot 202 is in communication with the fuel reactor 101; the second cooler 201 is provided in a pipe that communicates the second knock-out pot 202 with the fuel reactor 101.
The invention also provides a gas supply system. Referring to fig. 2, the gas supply system includes: the hydrogen production system 10 and the hydrogen storage and charging system 20 described above; the hydrogen storage and filling system 20 is used to store the hydrogen gas produced by the hydrogen production system 10 and to supply the hydrogen gas to a hydrogen filling apparatus. The gas supply system is capable of providing available hydrogen gas to the filling device.
Specifically, the gas supply system further includes: a carbon dioxide storage system. The carbon dioxide storage system comprises a carbon dioxide storage tank, and the carbon dioxide storage tank is communicated with a gas phase outlet of the second gas-liquid separation tank.
Specifically, with continued reference to fig. 2, the hydrogen storage and filling system 20 includes: a compressor 2001, a hydrogen storage tank 2002 and/or a bundle pipe vehicle 2003, and a pressure detector 2004; an air inlet end of the compressor 2001 is communicated with the hydrogen purification system 3, and an air outlet end of the compressor 2001 is communicated with the hydrogen storage tank 2002 and/or the tube bundle vehicle 2003; the pressure detector 2004 is provided on a line connecting the gas outlet end of the compressor 2001 and the hydrogen storage tank 2002.
The invention does not specifically limit the form of the compressor, and only needs to meet the requirements of hydrogen pressurization, no pollution to hydrogen, realization of frequent start and stop and the like. In particular, the compressor may be a diaphragm compressor, a piston compressor, a ram compressor or an ion compressor. The hydrogen storage tank of the present invention is not particularly limited. The selection can be made by those skilled in the art according to the amount of hydrogen required and the hydrogen filling characteristics. For example, the volume of the hydrogen storage tank required for filling 100kg/h of hydrogen gas is 5m3And (4) storage tank. The invention does not specifically require the form of the hydrogen storage tank, as long as the indexes such as hydrogen storage pressure, fatigue strength and the like are met. Specifically, the hydrogen storage tank may be at least one of a type i bottle, a type ii bottle, a type iii bottle, and a type iv bottle.
With continued reference to fig. 2, the hydrogen storage and filling system 20 further includes a hydrogenation unit 2005, the hydrogenation unit 2005 being in communication with the hydrogen storage tank 2002. The hydrogen engine 2005 can charge the hydrogen in the hydrogen storage tank 2002 to the hydrogen fuel cell vehicle 2006 to directly supply power to the vehicle.
Referring to fig. 2, a first control valve F1 is disposed on a pipeline connecting the outlet end of the compressor 2001 and the hydrogen storage tank 2002, and a third control valve F4 is disposed on a connecting pipeline connecting the hydrogen storage tank 2002 and the hydrogenation unit 2005. A second control valve F2 is provided on a pipeline connecting the outlet end of the compressor 2001 and the tube bundle vehicle 2003, and a pressure reducing valve F3 is provided on the pipeline for reducing the pressure of the hydrogen gas to realize the filling of the hydrogen gas into a filling device, such as the fuel cell vehicle 2006.
The gas supply system can set different hydrogen pressure grades and consumption according to the actual requirements of users, provides hydrogen with various filling pressure grades, and fully meets the market requirements. And the pressure of a purified hydrogen product generated by the hydrogen production system is increased to 45MPa by a compressor and the hydrogen product is stored in a hydrogen storage tank. The gas supply system can be used for filling hydrogen into the fuel cell vehicle through the hydrogenation machine, the pressure of the hydrogen during filling is 35MPa, and the hydrogen can also be directly filled into the bundle tube vehicle through decompression or a compressor with the outlet pressure of 20 MPa.
With continued reference to fig. 2, the gas supply system further comprises: a control system 30, wherein the control system 30 is used for controlling the rotation speed of the compressor 2001, the hydrogen filling rate of the hydrogenation machine 2005 and valves arranged on pipelines in the hydrogen storage and filling system 20. When an emergency occurs, such as hydrogen leakage, earthquake and other working conditions, the control system 30 automatically cuts off the first control valve F1 and the second control valve F2, so that the safety of the gas supply system is ensured.
The invention also provides a hydrogen filling station. The hydrogenation station comprises the gas supply system. The hydrogen station provided by the invention can realize hydrogen production and hydrogenation in the station, simultaneously avoid potential risks of hydrogen in the transportation process, save the transportation cost of hydrogen and reduce the volume of a hydrogen storage tank in the hydrogen station.
Example 1
The present embodiment provides a method for producing hydrogen. Referring to fig. 1 and 2, the method includes the steps of:
alkane is passed into combustion reactor 101 and reacts with the higher valent metal oxide in combustion reactor 101 to produce lower valent metal oxide, carbon dioxide and water.
The second cooler 201 and the second gas-liquid separation tank 202 are used for cooling the carbon dioxide and the water in sequence and performing gas-liquid separation to obtain a carbon dioxide product.
The reduced metal oxide is fed to steam reactor 102 and reacts with steam to produce a product containing hydrogen and an intermediate metal oxide.
And (3) sending the product containing the hydrogen into a hydrogen purification system 3, and sequentially cooling by a first cooler 301, carrying out gas-liquid separation by a first gas-liquid separation tank 302, carrying out drying treatment by a dryer 303, and carrying out purification and impurity removal treatment by a purifier 304 to obtain a hydrogen product. The drying agent in the dryer 303 is the silica gel, the 3A molecular sieve and the montmorillonite.
Purifying and impurity removing, wherein pressure swing adsorption and temperature swing adsorption are carried out, adsorbents used respectively are a 3A molecular sieve and a 5A molecular sieve, the operating temperature of the pressure swing adsorption is 50 ℃, and the operating pressure is 2.3 MPa; the operation temperature of the temperature swing adsorption is 380 ℃, and the operation pressure is 1.8 MPa.
The purity of the hydrogen in the hydrogen product is 99.9999 percent through detection.
Example 2
Example 2 is the addition of the oxidation of the metal oxide in the intermediate valence state to the metal oxide in the higher valence state to example 1. The intermediate valence metal oxide is sent into a regeneration reactor 103 to react with oxygen, the reaction temperature is 800-.
Example 3
This example provides a method for producing hydrogen using hydrogen. Referring to fig. 1 and 2, the method includes the steps of:
passing methane into a combustion reactor 101, said methane and Fe in said combustion reactor 1012O3Reacting at 1000 deg.C and 2MPa to obtain FeO, carbon dioxide and water.
The second cooler 201 and the second gas-liquid separation tank 202 are used for cooling the carbon dioxide and the water in sequence and performing gas-liquid separation to obtain a carbon dioxide product.
FeO is fed into a steam reactor 102 to react with water vapor at 900 ℃ and 2.1MPa to generate a product containing hydrogen and Fe3O4。
And (3) sending the product containing the hydrogen into a hydrogen purification system 3, and sequentially cooling by a first cooler 301, carrying out gas-liquid separation by a first gas-liquid separation tank 302, carrying out drying treatment by a dryer 303, and carrying out purification and impurity removal treatment by a purifier 304 to obtain a hydrogen product. The drying agent in the dryer 303 is the silica gel, the 3A molecular sieve and the montmorillonite.
Purifying and impurity removing, wherein pressure swing adsorption and temperature swing adsorption are carried out, adsorbents used respectively are a 3A molecular sieve and a 5A molecular sieve, the operating temperature of the pressure swing adsorption is 50 ℃, and the operating pressure is 2.0 MPa; the operation temperature of the temperature swing adsorption is 380 ℃, and the operation pressure is 1.8 MPa.
Mixing Fe3O4Feeding into a regeneration reactor 103, reacting with oxygen at 1200 deg.C under 2MPa to obtain Fe2O3And returned to the combustion reactor 101 for reuse.
The purity of the hydrogen in the hydrogen product is 99.9999 percent through detection.
Example 4
This example provides a method for producing hydrogen using hydrogen. Referring to fig. 1 and 2, the method includes the steps of:
passing methane into a combustion reactor 101, said methane and Mn in said combustion reactor 1012O7And reacting at 1000 ℃ and 3.5MPa to generate MnO, carbon dioxide and water.
The second cooler 201 and the second gas-liquid separation tank 202 are used for cooling the carbon dioxide and the water in sequence and performing gas-liquid separation to obtain a carbon dioxide product.
MnO is fed into a steam reactor 102 to react with water vapor at 900 ℃ and under 3.5MPa to generate a product containing hydrogen and MoO2。
And (3) sending the product containing the hydrogen into a hydrogen purification system 3, and sequentially cooling by a first cooler 301, carrying out gas-liquid separation by a first gas-liquid separation tank 302, carrying out drying treatment by a dryer 303, and carrying out purification and impurity removal treatment by a purifier 304 to obtain a hydrogen product. The drying agent in the dryer 303 is the silica gel, the 3A molecular sieve and the montmorillonite.
Purifying and impurity removing, wherein pressure swing adsorption and temperature swing adsorption are carried out, adsorbents used respectively are a 3A molecular sieve and a 5A molecular sieve, the operating temperature of the pressure swing adsorption is 50 ℃, and the operating pressure is 3.3 MPa; the operation temperature of the temperature swing adsorption is 380 ℃, and the operation pressure is 3 MPa.
Adding MoO2Feeding into a regeneration reactor 103, reacting with oxygen at 800 deg.C under 3.4MPa to obtain Mn2O7And returned to the combustion reactor 101 for reuse.
The purity of the hydrogen in the hydrogen product is 99.9999 percent through detection.
Example 5
This example provides a method for producing hydrogen using hydrogen. Referring to fig. 1 and 2, the method includes the steps of:
introducing petroleum coke-made synthesis gas into a combustion reactor 101, wherein the synthesis gas and Fe in the combustion reactor 1012O3Reacting at 700 deg.C and 0.25MPa to obtain FeO, carbon dioxide and water.
The second cooler 201 and the second gas-liquid separation tank 202 are used for cooling the carbon dioxide and the water in sequence and performing gas-liquid separation to obtain a carbon dioxide product.
FeO is fed into a steam reactor 102 to react with water vapor at the temperature of 650 ℃ and the pressure of 0.25MPa to generate a product containing hydrogen and Fe3O4。
And (3) sending the product containing the hydrogen into a hydrogen purification system 3, and sequentially cooling by a first cooler 301, carrying out gas-liquid separation by a first gas-liquid separation tank 302, carrying out drying treatment by a dryer 303, and carrying out purification and impurity removal treatment by a purifier 304 to obtain a hydrogen product. The drying agent in the dryer 303 is the silica gel, the 3A molecular sieve and the montmorillonite.
Purifying and impurity removing, wherein pressure swing adsorption and temperature swing adsorption are carried out, adsorbents used respectively are a 3A molecular sieve and a 5A molecular sieve, the operating temperature of the pressure swing adsorption is 40 ℃, and the operating pressure is 0.23 MPa; the operation temperature of the temperature swing adsorption is 400 ℃, and the operation pressure is 0.2 MPa.
The purity of the hydrogen in the hydrogen product is 99.9999 percent through detection.
Example 6
This example provides a method for producing hydrogen using hydrogen. Referring to fig. 1 and 2, the method includes the steps of:
and purifying the liquefied natural gas to remove impurities and removing non-alkane components in the liquefied natural gas.
Introducing the purified and impurity-removed liquefied natural gas into a combustion reactor 101, wherein the liquefied natural gas and Fe in the combustion reactor 1012O3Reacting at 1000 deg.C and 2MPa to obtain FeO, carbon dioxide and water.
The second cooler 201 and the second gas-liquid separation tank 202 are used for cooling the carbon dioxide and the water in sequence and performing gas-liquid separation to obtain a carbon dioxide product.
FeO is fed into a steam reactor 102 to react with water vapor at 900 ℃ and 2MPa to generate a product containing hydrogen and Fe3O4。
And (3) sending the product containing the hydrogen into a hydrogen purification system 3, and sequentially cooling by a first cooler 301, carrying out gas-liquid separation by a first gas-liquid separation tank 302, carrying out drying treatment by a dryer 303, and carrying out purification and impurity removal treatment by a purifier 304 to obtain a hydrogen product. The drying agent in the dryer 303 is the silica gel, the 3A molecular sieve and the montmorillonite.
Purifying and impurity removing, wherein pressure swing adsorption and temperature swing adsorption are carried out, adsorbents used respectively are a 3A molecular sieve and a 5A molecular sieve, the operating temperature of the pressure swing adsorption is 55 ℃, and the operating pressure is 1.93 MPa; the operation temperature of the temperature swing adsorption is 420 ℃, and the operation pressure is 1.75 MPa.
The purity of the hydrogen in the hydrogen product is 99.9999 percent through detection.
Example 7
This example provides a method for producing hydrogen using hydrogen. Referring to fig. 1 and 2, the method includes the steps of:
and purifying the liquefied petroleum gas to remove impurities and remove non-alkane components in the liquefied petroleum gas.
Introducing the purified liquefied petroleum gas into a combustion reactor 101, wherein the liquefied petroleum gas and V in the combustion reactor 1012O5Reacting at 900 deg.c and 1.5MPa to produce VO, carbon dioxide and water.
The second cooler 201 and the second gas-liquid separation tank 202 are used for cooling the carbon dioxide and the water in sequence and performing gas-liquid separation to obtain a carbon dioxide product.
VO is sent into a steam reactor 102 to react with water vapor at the temperature of 1100 ℃ and the reaction pressure of 1.5MPa to generate a product containing hydrogen and V2O3。
And (3) sending the product containing the hydrogen into a hydrogen purification system 3, and sequentially cooling by a first cooler 301, carrying out gas-liquid separation by a first gas-liquid separation tank 302, carrying out drying treatment by a dryer 303, and carrying out purification and impurity removal treatment by a purifier 304 to obtain a hydrogen product. The drying agent in the dryer 303 is the silica gel, the 3A molecular sieve and the montmorillonite.
Purifying and impurity removing, wherein pressure swing adsorption and temperature swing adsorption are carried out, adsorbents used respectively are a 3A molecular sieve and a 5A molecular sieve, the operating temperature of the pressure swing adsorption is 55 ℃, and the operating pressure is 1.33 MPa; the operation temperature of the temperature swing adsorption is 420 ℃, and the operation pressure is 1.25 MPa.
The purity of the hydrogen in the hydrogen product is 99.9999 percent through detection.
Example 8
This example provides a method for producing hydrogen using hydrogen. Referring to fig. 1 and 2, the method includes the steps of:
purifying the naphtha to remove impurities and remove components such as sulfur, nitrogen and the like.
Introducing the naphtha after purification and impurity removal into a combustion reactor 101, wherein the naphtha and Fe in the combustion reactor 1012O3Reacting at 950 ℃ and 1.3MPa to generate FeO, carbon dioxide and water.
The second cooler 201 and the second gas-liquid separation tank 202 are used for cooling the carbon dioxide and the water in sequence and performing gas-liquid separation to obtain a carbon dioxide product.
FeO is fed into a steam reactor 102 to react with water vapor at 900 ℃ and 1.2MPa to generate a product containing hydrogen and Fe3O4。
And (3) sending the product containing the hydrogen into a hydrogen purification system 3, and sequentially cooling by a first cooler 301, carrying out gas-liquid separation by a first gas-liquid separation tank 302, carrying out drying treatment by a dryer 303, and carrying out purification and impurity removal treatment by a purifier 304 to obtain a hydrogen product. The drying agent in the dryer 303 is the silica gel, the 3A molecular sieve and the montmorillonite.
Purifying and impurity removing, wherein pressure swing adsorption and temperature swing adsorption are carried out, adsorbents used respectively are a 3A molecular sieve and a 5A molecular sieve, the operating temperature of the pressure swing adsorption is 55 ℃, and the operating pressure is 1.0 MPa; the operation temperature of the temperature swing adsorption is 420 ℃, and the operation pressure is 0.75 MPa.
The purity of the hydrogen in the hydrogen product is 99.9999 percent through detection.
Example 9
The present embodiment provides a hydrogen production system. Referring to fig. 2, the hydrogen production system includes: a gas production system, a carbon dioxide separation system 2, and a hydrogen purification system 3; the gas making system comprises a fuel reactor 101, a steam reactor 102 and a regeneration reactor 103, and the fuel reactor 101, the steam reactor 102 and the regeneration reactor 103 are connected end to form a closed circulation loop; the carbon dioxide separation system 2 includes: a second cooler 201 and a second knock-out pot 202; the second knock-out pot 202 is in communication with the fuel reactor 101; the second cooler 201 is provided on a pipe connecting the second knock-out pot 202 and the fuel reactor 101; the hydrogen purification system 3 includes a first cooler 301, a first gas-liquid separation tank 302, a dryer 303, and a purifier 304; the steam reactor 102, the first gas-liquid separation tank 302, the dryer 303 and the purifier 304 are communicated in sequence; the first cooler 301 is disposed on a pipeline connecting the steam reactor 102 and the first gas-liquid separation tank 302.
Example 10
The present embodiment provides a gas supply system. Referring to fig. 2, the gas supply system includes: the hydrogen production system 10, the hydrogen storage and charging system 20, and the control system 30 provided in example 2; the hydrogen storage and filling system 20 is used for storing the hydrogen gas produced by the hydrogen production system 10 and supplying the hydrogen gas to a hydrogen filling apparatus. The hydrogen storage and filling system 20 includes: a compressor 2001, a hydrogen storage tank 2002, a bundle pipe vehicle 2003, a pressure detector 2004, and a hydrogenation machine 2005; an inlet end of the compressor 2001 is communicated with the hydrogen purification system 3, and an outlet end of the compressor 2001 is communicated with the hydrogen storage tank 2002 and the tube bundle vehicle 2003; the pressure detector 2004 is provided on a line that communicates the gas outlet end of the compressor 2001 with the hydrogen storage tank 2002; the hydrogenation machine 2005 is communicated with the hydrogen storage tank 2002, and the hydrogenation machine 2005 charges hydrogen in the hydrogen storage tank 2002 into the hydrogen fuel cell vehicle 2006; a first control valve F1 is arranged on a pipeline for communicating the gas outlet end of the compressor 2001 with the hydrogen storage tank 2002, and a third control valve F4 is arranged on a communication pipeline between the hydrogen storage tank 2002 and the hydrogenation unit 2005; a pipeline for communicating the gas outlet end of the compressor 2001 with the tube bundle vehicle 2003 is provided with a second control valve F2, and the pipeline is also provided with a pressure reducing valve F3 for reducing the pressure of hydrogen to realize the filling of the hydrogen into the fuel cell vehicle 2006; the control system 30 is used to control the rotation speed of the compressor 2001, the hydrogen filling rate of the hydrogen adding machine 2005, and valves provided on the lines in the hydrogen storage and filling system 20, such as a first control valve F1, a second control valve F2, a pressure reducing valve F3, and a third control valve F4.
Example 11
The present example provides a hydrogen refueling station. The hydrogenation station included the gas supply system of example 3. The hydrogen storage and filling system 20 provides hydrogen at two pressure levels of 35MPa and 20 MPa.
Having described embodiments of the present invention, the foregoing description is intended to be exemplary, not exhaustive, and not limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the described embodiments.
Claims (10)
1. A hydrogen production system, comprising:
a gas production system, a carbon dioxide separation system (2), and a hydrogen purification system (3);
the gas making system comprises a fuel reactor (101), a steam reactor (102) and a regeneration reactor (103), and the fuel reactor (101), the steam reactor (102) and the regeneration reactor (103) are connected end to form a closed circulation loop;
the carbon dioxide separation system (2) is in communication with the fuel reactor (101) for separating carbon dioxide and water;
the hydrogen purification system (3) includes: a first cooler (301), a first gas-liquid separation tank (302), a dryer (303) and a purifier (304); the steam reactor (102), the first gas-liquid separation tank (302), the dryer (303) and the purifier (304) are communicated in sequence; the first cooler (301) is arranged on a pipeline which communicates the steam reactor (102) with the first gas-liquid separation tank (302).
2. The hydrogen production system as claimed in claim 1, wherein the carbon dioxide separation system (2) comprises: a second cooler (201) and a second knock-out pot (202); the second gas-liquid separation tank (202) is communicated with the fuel reactor (101); the second cooler (201) is provided on a pipe that communicates the second gas-liquid separation tank (202) with the fuel reactor (101).
3. A gas supply system, comprising: a hydrogen production system (10) and a hydrogen storage and charging system (20) as claimed in claim 1 or 2;
the hydrogen storage and filling system (20) is used for storing the hydrogen prepared by the hydrogen production system (10) and supplying the hydrogen to a hydrogen filling device;
preferably, the hydrogen gas storage and filling system (20) comprises: a compressor (2001), a hydrogen storage tank (2002) and/or a bundle pipe vehicle (2003), and a pressure detector (2004);
the air inlet end of the compressor (2001) is communicated with the hydrogen purification system (3), and the air outlet end of the compressor (2001) is communicated with the hydrogen storage tank (2002) and/or the tube bundle vehicle (2003);
the pressure detector (2004) is arranged on a pipeline which communicates the gas outlet end of the compressor (2001) with the hydrogen storage tank (2002);
preferably, the hydrogen gas storage and filling system (20) further comprises a hydrogenation machine (2005), the hydrogenation machine (2005) being in communication with the hydrogen storage tank (2002);
preferably, the gas supply system further comprises: a control system (30), said control system (30) for controlling the rotational speed of said compressor (2001), the hydrogen filling rate of the hydrotreater (2005), and valves provided on the lines in said hydrogen storage and filling system (20).
4. A hydrogen station, characterized in that it comprises a gas supply system according to claim 3.
5. A method for producing hydrogen in the hydrogen production system of claim 1 or 2, comprising the steps of:
introducing alkane-containing gas, synthesis gas or naphtha into a combustion reactor (101), wherein the alkane-containing gas, synthesis gas or naphtha reacts with high-valence metal oxide in the combustion reactor (101) to generate low-valence metal oxide, carbon dioxide and water;
separating the carbon dioxide and water with a carbon dioxide separation system (2);
feeding the reduced metal oxide to a steam reactor (102) for reaction with steam to produce a hydrogen-containing product and an intermediate metal oxide;
sending the product containing the hydrogen into a hydrogen purification system (3), and sequentially carrying out cooling, gas-liquid separation, drying treatment and purification impurity removal treatment to obtain a hydrogen product;
and (3) sending the metal oxide with the intermediate valence state into a regeneration reactor (103), reacting with oxygen to generate metal oxide with a high valence state, and returning the metal oxide to the combustion reactor (101) for recycling.
6. The method of producing hydrogen of claim 5 wherein the alkane is C1-C4An alkane;
preferably, the alkane is derived from at least one of pipeline natural gas, compressed natural gas, liquefied natural gas and liquefied petroleum gas.
7. Process for producing hydrogen as claimed in claim 5 or 6, characterized in that the metal oxide in the higher valence state is selected from Fe2O3、Mn2O7、MoO3Or V2O5Preferably Fe2O3；
The metal oxide in a low valence state is selected from FeO, MnO, MoO or VO, and FeO is preferred;
the metal oxide of the intermediate valence is selected from Fe3O4、MnO2、MoO2Or V2O3Preferably Fe3O4。
8. The method for producing hydrogen according to claim 5 or 6, wherein the reaction conditions in the combustion reactor (101) are a reaction temperature of 700 ℃ and 1300 ℃, a reaction pressure of 0.05 to 3.5 MPa;
the reaction conditions in the steam reactor (102) are 650-1200 ℃ of reaction temperature and 0.05-3.5MPa of reaction pressure;
the reaction conditions in the regeneration reactor (103) are that the reaction temperature is 800-1400 ℃ and the reaction pressure is 0.05-3.5 MPa.
9. The method for producing hydrogen as claimed in claim 5 or 6, wherein the drying agent used in the drying process comprises: at least one of silica gel, a first molecular sieve and montmorillonite;
preferably, the desiccant comprises: the silica gel and the first molecular sieve and/or the montmorillonite;
more preferably, the first molecular sieve is a 3A molecular sieve;
more preferably, the drying treatment is that the product containing hydrogen is cooled and subjected to gas-liquid separation, and then sequentially subjected to the silica gel and the first molecular sieve and/or the montmorillonite drying treatment.
10. The hydrogen production method according to claim 5 or 6, characterized in that the purification and impurity removal treatment mode comprises: at least one of cryogenic, membrane separation and adsorption separation;
preferably, the purification and impurity removal treatment mode comprises: membrane separation and adsorption separation;
preferably, the membrane material used for the membrane separation comprises: at least one of a palladium metal membrane, a palladium metal alloy membrane, a crystalline alloy membrane, an amorphous alloy membrane, polyimide, polysulfone, polyamide, and polyvinyltrimethylsilane;
the adsorptive separation comprises: at least one of once-through separation, pressure swing adsorption and temperature swing adsorption;
more preferably, the adsorption material used for the pressure swing adsorption and the temperature swing adsorption is independently selected from at least one of a second molecular sieve, activated alumina, silica gel and activated carbon;
more preferably, the second molecular sieve used for the pressure swing adsorption and the temperature swing adsorption is independently selected from a 3A molecular sieve and/or a 5A molecular sieve;
more preferably, the operating temperature of the pressure swing adsorption is 40-55 ℃, and the operating pressure is 0.03-2.5 MPa;
the operation temperature of the temperature swing adsorption is 50-420 ℃, and the operation pressure is 0.05-2.0 MPa.
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| CN114162781A (en) * | 2021-12-27 | 2022-03-11 | 李东峰 | Method and system for producing hydrogen from liquid steel slag |
| CN114186464A (en) * | 2021-12-14 | 2022-03-15 | 西安交通大学 | Hydrogenation station earthquake accident assessment method and system |
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| CN103525466A (en) * | 2013-10-22 | 2014-01-22 | 东南大学 | Method and device for indirectly liquefying coal and separating carbon dioxide |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103525466A (en) * | 2013-10-22 | 2014-01-22 | 东南大学 | Method and device for indirectly liquefying coal and separating carbon dioxide |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114186464A (en) * | 2021-12-14 | 2022-03-15 | 西安交通大学 | Hydrogenation station earthquake accident assessment method and system |
| CN114186464B (en) * | 2021-12-14 | 2024-01-16 | 西安交通大学 | Method and system for evaluating earthquake accidents of hydrogen station |
| CN114162781A (en) * | 2021-12-27 | 2022-03-11 | 李东峰 | Method and system for producing hydrogen from liquid steel slag |
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