CN112813454A - Natural gas reforming and carbon dioxide combined hydrogen production power generation system and method - Google Patents
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Abstract
The invention discloses a natural gas reforming and carbon dioxide combined hydrogen production power generation system and a method. The natural gas reforming and carbon dioxide combined hydrogen production power generation system comprises a natural gas steam reforming hydrogen production system and a carbon dioxide battery system; the natural gas steam reforming hydrogen production system is communicated with the carbon dioxide battery system, and hydrogen and carbon dioxide generated by the natural gas steam reforming hydrogen production system enter a conductive medium in an anode chamber in the carbon dioxide battery system through a communicated pipeline; the anode and the cathode in the carbon dioxide battery system are connected through a lead to supply power to the outside; hydrogen gas is generated in the positive electrode chamber in the carbon dioxide battery system. The carbon dioxide battery system has the function of purifying and purifying hydrogen, and the natural gas is introduced into the aqueous solution conductive medium of the carbon dioxide battery system after steam reforming and carbon monoxide conversion, so that the extraction and separation of the hydrogen can be realized, and purification and separation devices (such as a membrane separation device, a pressure swing adsorption device and the like) in the traditional natural gas steam reforming process system are omitted.
Description
Technical Field
The invention relates to a system and a method for generating power by combining natural gas reforming with carbon dioxide hydrogen production, and belongs to the technical field of natural gas utilization.
Background
The hydrogen is used as a clean and efficient secondary energy source, the heat value of the hydrogen in common fuels is the highest, about 3 times of petroleum, 3.9 times of alcohol and 45 times of coal, and the power generation efficiency and the comprehensive energy efficiency are far higher than those of the traditional fossil energy sources. The hydrogen energy is applied to the traffic field through the fuel cell technology, so that the energy can be saved, the energy efficiency can be improved, the oil and the natural gas can be partially replaced, the external dependence is reduced, and the energy safety level of China is promoted. The hydrogen energy is prepared from a wide range of sources, not only can be prepared by reforming fossil energy such as coal, petroleum and natural gas, thermal cracking of biomass or microbial fermentation, but also can be prepared by using byproduct gases in industries such as coking, chlor-alkali, steel and metallurgy, and can also be prepared by using electrolyzed water. The method is obtained from fossil energy, is beneficial to clean and efficient utilization of primary energy, and improves the quality of a supply side. It is counted that the global hydrogen yield in 2018 is about 6000 million tons, 96% of which is derived from traditional fossil energy, electrolyzed water accounts for 4%, and natural gas hydrogen production accounts for 50%, and the hydrogen production accounts for the vast majority of which is natural gas steam reforming (SMR).
With the increasing demand of people for clean energy of hydrogen, the process for producing hydrogen by steam reforming of natural gas will undoubtedly continue to play an important role in the future hydrogen production, however, the process also faces the problems of high investment, high energy consumption and high carbon emission. The process optimization of the hydrogen production by reforming the hydrocarbons is carried out so as to improve the operation efficiency and reduce the process energy consumption and carbon emission, and the method has important practical significance.
Disclosure of Invention
The invention aims to provide a system and a method for generating power by combining natural gas reforming with carbon dioxide, which are particularly beneficial to preparing hydrogen by reforming natural gas steam and generating hydrogen by using a reaction product carbon dioxide.
The combined system provided by the invention comprises two working sections: the first stage is mainly reforming natural gas steam to prepare hydrogen and carbon dioxide; in the second stage, carbon dioxide is used to generate electric energy and hydrogen under the action of primary battery.
The natural gas steam reforming hydrogen production system mainly has the main functions of carrying out steam reforming on natural gas, and continuously reacting carbon monoxide and steam through carbon monoxide conversion to obtain hydrogen and carbon dioxide; the carbon dioxide battery system utilizes the electrochemical principle to prepare hydrogen and generate electricity from carbon dioxide.
Specifically, the natural gas reforming and carbon dioxide combined hydrogen production power generation system provided by the invention comprises a natural gas steam reforming hydrogen production system and a carbon dioxide battery system;
the natural gas steam reforming hydrogen production system is communicated with the carbon dioxide battery system, and hydrogen and carbon dioxide generated by the natural gas steam reforming hydrogen production system enter a conductive medium in a positive electrode chamber in the carbon dioxide battery system through a communicated pipeline;
the positive electrode and the negative electrode in the carbon dioxide battery system are connected through a lead to supply power to the outside;
hydrogen is generated in the positive electrode chamber in the carbon dioxide battery system.
In the hydrogen production power generation system, in the carbon dioxide battery system, the positive electrode is a composite electrode material composed of noble metal/carbon, and the negative electrode is metallic sodium;
the noble metal can be Pt, Pd, etc., which can catalyze hydrogen ions (H) while being highly conductive+) The electrons are obtained and finally hydrogen is generated.
In the hydrogen production power generation system, in the carbon dioxide battery system, the conductive medium in the anode chamber is purified seawater or water, the conductive medium in the cathode chamber is a non-water-based conductive organic solution,
the non-water-based conductive organic solution can be an alcohol ether sulfonate solution of sodium and the like;
in the above hydrogen production power generation system, the positive electrode chamber and the negative electrode chamber are separated by a conductive partition plate, and the conductive partition plate only allows sodium ions to pass through;
the negative electrode metal sodium loses electrons in the non-water-based conductive organic solution to generate sodium ions (Na)+) Sodium ion (Na)+) The non-water-based conductive organic solution enters the aqueous solution to realize circuit connection; introducing gas into the bottom of the conductive solution at the positive electrode sideSince hydrogen is poorly soluble in water, it is preferentially separated from the cell, while carbon dioxide dissolves in aqueous solution to equilibrium (CO)2+H2O) decomposition to H+And HCO3 -. Electrons from the positive electrode of the cell enter the aqueous solution, the electrons and H+The ions combine in the catalyst to form hydrogen atoms and further hydrogen molecules, which are separated from the cell solution.
In the hydrogen production power generation system, the anode chamber is communicated with a gas-liquid separator I, and a hydrogen product is obtained at a gas outlet of the gas-liquid separator I.
In the hydrogen production and power generation system, the natural gas steam reforming hydrogen production system comprises a natural gas preheater, a natural gas heater and a natural gas conversion hydrogen production device which are connected in sequence;
a water vapor inlet of the natural gas conversion hydrogen production device is connected with a steam generator;
a reformed gas outlet of the natural gas conversion hydrogen production device is connected with a carbon monoxide conversion device;
and a gas outlet of the carbon monoxide conversion device is connected with the carbon dioxide battery system.
In the hydrogen production power generation system, a desulfurization device is arranged between the natural gas preheater and the natural gas heater;
and the inlet of the steam generator is sequentially connected with the desalted water heater and the oxygen removal device.
In the hydrogen production and power generation system, the reformed gas outlet of the natural gas conversion hydrogen production device is sequentially connected with the steam generator, the natural gas heater and the carbon monoxide conversion device;
and a gas outlet of the carbon monoxide conversion device is sequentially connected with the desalted water heater, the natural gas preheater, the cooling heat exchange device, the gas-liquid separation device II and the carbon dioxide battery system.
The method for generating power and preparing hydrogen by combining natural gas reforming with the carbon dioxide hydrogen production power generation system is as follows:
s1, introducing natural gas (with the pressure of 0.5-5.0 MPa and the temperature of 0-25 ℃) into the natural gas steam reforming hydrogen production system in the natural gas reforming and carbon dioxide hydrogen production power generation system, and obtaining hydrogen and carbon dioxide through natural gas steam reforming and carbon monoxide conversion;
s2, introducing the hydrogen and the carbon dioxide obtained in the step S1 into the carbon dioxide battery system, and generating electric energy and producing hydrogen by the carbon dioxide under the action of a primary battery.
Specifically, the natural gas is preheated to 200-250 ℃, desulfurized and heated to 380-480 ℃, and then the natural gas is subjected to steam reforming to obtain reformed gas;
heating the reformed gas to 250-320 ℃, and then carrying out carbon monoxide conversion to obtain the hydrogen and the carbon dioxide;
the pressure of the hydrogen and the carbon dioxide after cooling heat exchange and gas-liquid separation is 0.1MPa to 4.0MPa, and the temperature is 20 ℃ to 30 ℃.
The invention provides a natural gas steam reforming hydrogen production and carbon dioxide hydrogen production combined power generation system and a method for the first time, and the system and the method have the following advantages:
1. compared with the traditional natural gas steam reforming process, the invention provides a set of combined process system, the natural gas steam reforming process system is combined with the carbon dioxide battery system, carbon dioxide is used as a precious raw material to further prepare hydrogen and simultaneously generate electric energy, the problem of carbon emission in hydrogen preparation by natural gas reforming is solved, and the yield of hydrogen is improved;
2. the anode of the carbon dioxide battery system provided by the invention is a composite electrode material consisting of noble metal (Pt, Pd and the like)/carbon, can efficiently conduct electricity and simultaneously catalyze hydrogen ions (H)+) The obtained electrons finally generate hydrogen, and the design of the conductive medium of the battery system is unique, the conductive medium consists of two independent solutions of non-water-based conductive organic solution and aqueous solution (or purified seawater), and the two conductive media consist of one conductive medium which only allows sodium ions (Na)+) Separated by a selectively conductive separator plate;
3. the carbon dioxide battery system has the function of purifying and purifying hydrogen, and the natural gas is introduced into the aqueous solution conductive medium of the carbon dioxide battery system after steam reforming and carbon monoxide conversion, so that the extraction and separation of the hydrogen can be realized, and purification and separation devices (such as a membrane separation device, a pressure swing adsorption device and the like) in the traditional natural gas steam reforming process system are omitted.
Drawings
Fig. 1 is a schematic structural diagram of a natural gas reforming and carbon dioxide combined hydrogen production power generation system.
The respective symbols in the figure are as follows:
the device comprises a natural gas preheater 1, a desulfurization device 2, a natural gas heater 3, a natural gas conversion hydrogen production device 4, a steam generator 5, a carbon monoxide conversion device 6, a desalted water heater 7, a cooling heat exchange device 8, a gas-liquid separation device II 9, a positive electrode 10, a negative electrode 11, a conductive partition plate 12, a gas-liquid separation device I13 and a deoxygenation device 14.
Detailed Description
The present invention will be further described with reference to the accompanying drawings, but the present invention is not limited to the following embodiments.
The invention provides a set of combined system, which combines a natural gas steam reforming process system with a carbon dioxide battery system, further prepares hydrogen by taking carbon dioxide as a precious raw material, and can generate electric energy at the same time, thereby solving the problem of carbon emission in hydrogen preparation by natural gas reforming and improving the yield of hydrogen.
Specifically, the natural gas reforming and carbon dioxide combined hydrogen production power generation system comprises a natural gas steam reforming hydrogen production system and a carbon dioxide battery system, wherein the natural gas steam reforming hydrogen production system is mainly used for carrying out steam reforming on natural gas and continuously reacting carbon monoxide and water vapor through carbon monoxide conversion to obtain hydrogen and carbon dioxide; the carbon dioxide battery system utilizes the electrochemical principle to prepare hydrogen and generate electricity from carbon dioxide.
Fig. 1 is a schematic structural diagram of a natural gas reforming and carbon dioxide combined hydrogen production power generation system provided by the invention, and the hydrogen production power generation system comprises a natural gas steam reforming hydrogen production system and a carbon dioxide battery system.
The structure of the natural gas steam reforming hydrogen production system is as follows: the natural gas preheater 1, the desulphurization device 2, the natural gas heater 3 and the natural gas conversion hydrogen production device 4 are sequentially connected, a steam inlet of the natural gas conversion hydrogen production device 4 is connected with the steam generator 5, a reformed gas outlet of the natural gas conversion hydrogen production device 4 is sequentially connected with the steam generator 5 and the carbon monoxide conversion device 6, and an inlet of the steam generator 5 is sequentially connected with the desalted water heater 7 and the deoxidizing device 14. And a gas outlet of the carbon monoxide conversion device 6 is sequentially connected with a desalted water heater 7, a natural gas preheater 1, a cooling heat exchange device 8, a gas-liquid separation device II 9 and a carbon dioxide battery system.
The structure of the carbon dioxide battery system is as follows: the positive electrode 10 is a composite electrode material composed of noble metal (Pt, Pd, etc)/carbon, the negative electrode 11 is metallic sodium, wherein the positive electrode 10 is immersed in purified seawater or water, the negative electrode 11 is immersed in a non-water-based conductive organic solution, the two conductive media are separated by a conductive separator 12 which only allows sodium ions to pass through, and the positive electrode 10 and the negative electrode 11 are connected through a lead to supply power to the outside. Hydrogen and carbon dioxide generated by the natural gas steam reforming hydrogen production system enter purified seawater or water in a carbon dioxide battery system, and the carbon dioxide generates electric energy and produces the hydrogen under the action of a primary battery. And hydrogen generated by the carbon dioxide battery system and hydrogen introduced from the natural gas steam reforming hydrogen production system are collected after passing through a gas-liquid separation device I13.
The hydrogen production power generation system of the invention has the working process as follows:
firstly, natural gas (the pressure is 0.5 MPa-5.0 MPa, the temperature is 0 ℃ -25 ℃) is heated to 200 ℃ -250 ℃ through a natural gas preheater 1, and then the natural gas is desulfurized by a desulfurizing device 2, the desulfurized natural gas is heated to 380-480 ℃ by a natural gas heater 3 and is mixed with a certain proportion of steam to enter a natural gas conversion hydrogen production device 4 for conversion reaction to obtain reformed gas, the reformed gas sequentially passes through a steam generator 5 and the natural gas heater 3, the temperature of the reformed gas reaches 250-320 ℃, the reformed gas enters a carbon monoxide conversion device 6 for conversion reaction, the reacted gas sequentially passes through a desalted water heater 7, a natural gas preheater 1 and a cooling heat exchange device 8 and then enters a gas-liquid separator II 9 for gas-liquid separation, and the separated gas (the pressure is 0.1-4.0 MPa, and the temperature is 20-30 ℃) is introduced from the bottom of the anode of the carbon dioxide battery system.
In the carbon dioxide battery system, sodium metal as the negative electrode 11 loses electrons in a nonaqueous conductive organic solution to generate sodium ions (Na)+) Sodium ion (Na)+) The circuit is communicated by the conductive partition plate 12 from the non-water-based conductive organic solution into the aqueous solution; in the gas introduced into the bottom of the conductive solution on the side of the positive electrode 12, hydrogen is preferentially separated from the cell because it is poorly soluble in water, while carbon dioxide is dissolved in the aqueous solution to reach the equilibrium of dissolution (CO)2+H2O) decomposition to H+And HCO3 -. Electrons from the cell's positive electrode 12 enter the aqueous solution, the electrons and H+The ions combine in the catalyst to form hydrogen atoms and further hydrogen molecules, which are separated from the cell solution.
In the primary battery system, along with the consumption of the metal sodium of the cathode 11, carbon dioxide is introduced and dissolved continuously to obtain hydrogen; and hydrogen from the carbon dioxide battery system passes through a gas-liquid separator I13 to obtain a hydrogen product.
Claims (10)
1. A natural gas reforming and carbon dioxide combined hydrogen production power generation system comprises a natural gas steam reforming hydrogen production system and a carbon dioxide battery system;
the natural gas steam reforming hydrogen production system is communicated with the carbon dioxide battery system, and hydrogen and carbon dioxide generated by the natural gas steam reforming hydrogen production system enter a conductive medium in a positive electrode chamber in the carbon dioxide battery system through a communicated pipeline;
the positive electrode and the negative electrode in the carbon dioxide battery system are connected through a lead to supply power to the outside;
hydrogen is generated in the positive electrode chamber in the carbon dioxide battery system.
2. The hydrogen-producing power generation system of claim 1, wherein: in the carbon dioxide battery system, the positive electrode is a composite electrode material composed of noble metal/carbon, and the negative electrode is metallic sodium.
3. The hydrogen-producing power generation system according to claim 2, characterized in that: in the carbon dioxide battery system, the conductive medium in the anode chamber is purified seawater or water, and the conductive medium in the cathode chamber is a non-water-based conductive organic solution.
4. A hydrogen-producing power generation system in accordance with claim 2 or 3, characterized in that: the positive electrode chamber is separated from the negative electrode chamber by a conductive partition plate, and the conductive partition plate only allows sodium ions to pass through.
5. The hydrogen-producing power generation system according to any one of claims 1 to 4, characterized in that: the anode chamber is communicated with a gas-liquid separator I, and a hydrogen product is obtained at a gas outlet of the gas-liquid separator I.
6. The hydrogen-producing power generation system according to any one of claims 1 to 5, characterized in that: the natural gas steam reforming hydrogen production system comprises a natural gas preheater, a natural gas heater and a natural gas conversion hydrogen production device which are connected in sequence;
a water vapor inlet of the natural gas conversion hydrogen production device is connected with a steam generator;
a reformed gas outlet of the natural gas conversion hydrogen production device is connected with a carbon monoxide conversion device;
and a gas outlet of the carbon monoxide conversion device is connected with the carbon dioxide battery system.
7. The hydrogen-producing power generation system according to claim 6, wherein: a desulfurization device is arranged between the natural gas preheater and the natural gas heater;
and the inlet of the steam generator is sequentially connected with the desalted water heater and the oxygen removal device.
8. The hydrogen-producing power generation system according to claim 7, wherein: a reformed gas outlet of the natural gas conversion hydrogen production device is sequentially connected with the steam generator, the natural gas heater and the carbon monoxide conversion device;
and a gas outlet of the carbon monoxide conversion device is sequentially connected with the desalted water heater, the natural gas preheater, the cooling heat exchange device, the gas-liquid separation device II and the carbon dioxide battery system.
9. A method for generating power by combining natural gas reforming with carbon dioxide hydrogen production comprises the following steps:
s1, introducing natural gas into the natural gas steam reforming hydrogen production system in the natural gas reforming and carbon dioxide combined hydrogen production power generation system of any one of claims 1 to 8, and obtaining hydrogen and carbon dioxide through natural gas steam reforming and carbon monoxide conversion;
s2, introducing the hydrogen and the carbon dioxide obtained in the step S1 into the carbon dioxide battery system, and generating electric energy and producing hydrogen by the carbon dioxide under the action of a primary battery.
10. The method of claim 9, wherein: preheating the natural gas to 200-250 ℃, heating to 380-480 ℃ after desulfurization, and then carrying out steam reforming on the natural gas to obtain reformed gas;
heating the reformed gas to 250-320 ℃, and then carrying out carbon monoxide conversion to obtain the hydrogen and the carbon dioxide;
the pressure of the hydrogen and the carbon dioxide after cooling heat exchange and gas-liquid separation is 0.1MPa to 4.0MPa, and the temperature is 20 ℃ to 30 ℃.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115806271A (en) * | 2021-09-14 | 2023-03-17 | 斗山恒能有限公司 | Natural gas reforming system and method |
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