CN115108531A - Continuous hydrogen purification system and process for hydrogen-doped natural gas - Google Patents
Continuous hydrogen purification system and process for hydrogen-doped natural gas Download PDFInfo
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- C01B3/001—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes characterised by the uptaking medium; Treatment thereof
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- C01B3/001—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes characterised by the uptaking medium; Treatment thereof
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- C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
- C01B3/508—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by selective and reversible uptake by an appropriate medium, i.e. the uptake being based on physical or chemical sorption phenomena or on reversible chemical reactions
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Abstract
The invention relates to a continuous hydrogen purification system and a purification process of hydrogen-doped natural gas, which comprises the following steps: (1) the hydrogen-doped natural gas enters the first purifying storage tank through the mixed gas inlet pipe to perform hydrogen absorption reaction, when the first valve is opened, the first purifying storage tank enters a hydrogen absorption state, the first natural gas valve is controlled to be opened, when the hydrogen storage alloy in the first purifying storage tank is saturated in adsorption, the second control valve is opened, and the second purifying storage tank enters a hydrogen absorption state; at the moment, the first control valve is closed, the first purification storage tank is in a dehydrogenation state, the initial hydrogen removal can be used for purging according to the required hydrogen purity requirement, the purging is completed, high-purity hydrogen is generated, the valve is opened, and the hydrogen is discharged from a hydrogen outlet; (2) when the hydrogen storage alloy in the purification storage tank II is saturated in adsorption, the control valve I is opened, and the purification storage tank I enters a hydrogen absorption state; at the moment, the second purification storage tank is converted into a hydrogen discharge state; (3) and in the hydrogen discharging state, the first hydrogen valve or the second hydrogen valve is opened to discharge hydrogen through the hydrogen outlet.
Description
Technical Field
The invention relates to the technical field of energy sources, in particular to a continuous hydrogen purification system of hydrogen-doped natural gas and a purification process thereof.
Background
Natural gas and hydrogen belong to the same gas energy carriers, and the physical properties of the natural gas and the hydrogen have certain similarity. Natural gas is widely used in industry and residential areas, and infrastructure such as compression, storage, pipeline transportation and combustion facilities of the natural gas has certain adaptability to hydrogen. Therefore, the corresponding loading ratio can be determined according to the difference of pipeline facilities, and then the loading natural gas is transported by mixing hydrogen with the natural gas to form the loading natural gas and then injecting the loading natural gas into the natural gas pipeline. The existing natural gas pipeline is used for transporting the hydrogen-doped natural gas, so that the transportation cost of the hydrogen can be effectively reduced. But natural gas when loaded with hydrogen will reduce its energy density.
CN213150830U discloses a dual-fuel battery power supply system, which utilizes a pressure swing adsorption apparatus to separate hydrogen-doped natural gas in a fuel gas pipeline into hydrogen and natural gas, however, the pressure swing adsorption apparatus has many defects, and the obtained hydrogen has low purity, low hydrogen recovery rate and high energy consumption, and is a physical method with large floor space of equipment.
Therefore, how to obtain high-purity hydrogen from the hydrogen-doped natural gas and reduce the energy consumption is a problem which needs to be solved urgently.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a continuous hydrogen purification system for hydrogen-loaded natural gas.
The technical scheme adopted by the invention is as follows: the purification system comprises a mixed gas inlet pipe 11 and a purification storage tank, wherein the purification storage tank is divided into a first purification storage tank 15 and a second purification storage tank 14 by a partition, the mixed gas inlet pipe 11 is connected with a gas inlet branch pipe and is respectively connected with the first purification storage tank 15 and the second purification storage tank 14, hydrogen storage alloys are arranged in the first purification storage tank 15 and the second purification storage tank 14, and the hydrogen storage alloys are lanthanum nickel system AB5 LaNi5/MmNi5 and lanthanum nickel system AB5 type LaNi5/MmNi5 derivatives, ferrotitanium system AB type TiFe and ferrotitanium system AB type TiFe derivatives, A2B magnesium group Mg2Ni and A2B magnesium group Mg2Ni derivatives, zirconium system AB2 type and derivatives thereof, BCC type vanadium group solid solution alloys and derivatives thereof and the like;
disc-shaped water paths are arranged in the first purification storage tank 15 and the second purification storage tank 14, the disc-shaped water paths arranged in the first purification storage tank 15 and the second purification storage tank 14 are communicated, the disc-shaped water path in the first purification storage tank 15 is provided with a disc-shaped water intersection I9, and the disc-shaped water path in the second purification storage tank 14 is provided with a disc-shaped water intersection II 10; the flow direction of water in the disc-shaped waterway is controllable;
the first purification storage tank 15 and the second purification storage tank 14 are respectively provided with a hydrogen branch pipe, and the hydrogen branch pipes are communicated with a hydrogen outlet 12;
the first purifying storage tank 15 and the second purifying storage tank 14 are respectively provided with a natural gas branch pipe, and the natural gas branch pipes are communicated with a natural gas outlet 13;
furthermore, a first valve 1 and a second valve 2 are arranged on the air inlet branch pipe, the first valve 1 controls the first purification storage tank 15 to supply air, and the second valve 2 controls the second purification storage tank 14 to supply air;
furthermore, a first hydrogen valve 4 and a second hydrogen valve 5 are arranged on the hydrogen branch pipe, the first hydrogen valve 4 controls the hydrogen discharge of the first purification storage tank 15, and the second hydrogen valve 5 controls the hydrogen discharge of the second purification storage tank 14;
further, a natural gas valve I3 and a natural gas valve II 6 are arranged on the natural gas branch pipe, the natural gas valve I3 controls the natural gas discharge of the purifying storage tank I15, and the natural gas valve II 6 controls the natural gas discharge of the purifying storage tank II 14;
furthermore, a waterway is also arranged in the system, the waterway is provided with a waterway inlet 7 and a waterway outlet 8, and at least one waterway branch pipe connected with the waterway inlet 7 and the waterway outlet 8 is arranged in the first purification storage tank 15 and the second purification storage tank 14;
further, the hydrogen is connected to a buffer tank at an outlet 12;
further, water in the water path is heated by using the waste heat of the tail gas of the hydrogen fuel cell;
a continuous hydrogen purification process of hydrogen-doped natural gas comprises the following steps:
(1) the hydrogen-doped natural gas enters the first purification storage tank 15 or the second purification storage tank 14 through the mixed gas inlet pipe 11 to carry out hydrogen absorption reaction, the first valve 1 and the second valve 2 are opened alternately, when the first valve 1 is opened, the natural gas enters the first purification storage tank 15 to be in a hydrogen absorption state, the first natural gas valve 3 is controlled to be opened, at the moment, the second valve 2 is controlled to be closed, the second purification storage tank 14 is in a dehydrogenation state, pure hydrogen is generated, the valve 5 is opened, and hydrogen is discharged from the hydrogen outlet 12; when the second valve 2 is opened, the second purification storage tank 14 is in a hydrogen absorption state, the second natural gas valve 6 is controlled to be opened, at the moment, the first control valve 1 is closed, the first purification storage tank 15 is in a dehydrogenation state, hydrogen storage is generated, the valve 4 is opened, and hydrogen is discharged from the hydrogen outlet 12;
(2) when the hydrogen storage alloy in the first purification storage tank 15 is saturated in adsorption, closing the first valve 1 and opening the second control valve 2, and entering a second purification storage tank 14 to enter a hydrogen absorption state; at the moment, the first purification storage tank 15 is converted into a hydrogen discharge state, the first control valve 1 is closed, the first purification storage tank is in a dehydrogenation state, the first natural gas valve 3 is opened according to the required hydrogen purity requirement, the initial hydrogen removal gas is used for purging, after purging is finished, the first hydrogen valve 4 is opened, and the hydrogen is discharged from the hydrogen outlet 12;
(3) when the hydrogen storage alloy in the second purification storage tank 14 is saturated in adsorption, closing the second valve 2 and opening the first control valve 1, and enabling the first purification storage tank 15 to enter a hydrogen absorption state; at the moment, the second purification storage tank 14 is converted into a hydrogen discharge state; the second control valve 2 is closed, the second purification storage tank is in a dehydrogenation state, the second natural gas valve 6 is opened according to the required hydrogen purity requirement, the initial hydrogen removal is used for purging, after purging is finished, the second hydrogen valve 5 is opened, and hydrogen is discharged from the hydrogen outlet 12;
further, when the first purification storage tank 15 enters a hydrogen absorption state, and the second purification storage tank 14 is in a hydrogen discharge state, the water flow direction of the disc-shaped water channel is that the disc-shaped water channel first 9 flows to the disc-shaped water channel second 10, the second purification storage tank 14 enters a hydrogen absorption state, and when the first purification storage tank 15 is in a hydrogen discharge state, the water flow direction of the disc-shaped water channel is that the disc-shaped water channel second 10 flows to the disc-shaped water channel first 9;
further, water in the disc-shaped water path is replaced by a liquid-gas phase-change material, and the liquid-gas phase-change material is ammonia, freon, acetone, methanol, Thermomum, or mercury;
compared with the prior art, the invention has the beneficial effects that:
(1) the metal hydride is used as the purification substrate of the hydrogen-doped natural gas, so that the hydrogen in the natural gas can be efficiently, quickly and continuously collected to obtain high-purity hydrogen, and the hydrogen purification device has large volume density, compact structure and small occupied area;
(2) the heat generated in the hydrogen absorption reaction process is transmitted to the hydrogen discharge process, so that the system heat is efficiently utilized, and the energy consumption in the hydrogen discharge process is reduced;
(3) the heat generated by the hydrogen fuel cell and the like is transmitted to the hydrogen discharge process, so that the energy utilization rate of the system is further improved;
(4) the purity of hydrogen can be more than 99.99 percent, and the content of CO impurities which have poisoning effect on the fuel cell is lower than 0.1 ppm;
drawings
FIG. 1 is a schematic diagram of a system for continuous hydrogen purification of hydrogen-loaded natural gas;
Detailed Description
The present invention is further described in detail below with reference to examples so that those skilled in the art can practice the invention with reference to the description.
It will be understood that terms such as "having," "including," and "comprising," when used herein, do not preclude the presence or addition of one or more other elements or groups thereof.
The invention is further illustrated below with reference to fig. 1:
example 1
A continuous hydrogen purification system of hydrogen-doped natural gas comprises a mixed gas inlet pipe 11 and a purification storage tank, wherein the purification storage tank is divided into a first purification storage tank 15 and a second purification storage tank 14 by a partition, the mixed gas inlet pipe 11 is connected with a gas inlet branch pipe and is respectively connected with the first purification storage tank 15 and the second purification storage tank 14, hydrogen storage alloys are arranged in the first purification storage tank 15 and the second purification storage tank 14, and the hydrogen storage alloys are lanthanum-nickel system AB5 LaNi5/MmNi5 and lanthanum-nickel system AB5 LaNi5/MmNi5 derivatives, titanium-iron system AB type TiFe and titanium-iron system AB type TiFe derivatives, A2B magnesium-based Mg2Ni and A2B magnesium-based Mg2Ni derivatives, zirconium system AB2 types and derivatives thereof, BCC type vanadium-based solid solution hydrogen storage alloys and derivatives thereof, and the like;
disc-shaped water paths are arranged in the first purification storage tank 15 and the second purification storage tank 14, the disc-shaped water paths arranged in the first purification storage tank 15 and the second purification storage tank 14 are communicated, the disc-shaped water path in the first purification storage tank 15 is provided with a disc-shaped water intersection I9, and the disc-shaped water path in the second purification storage tank 14 is provided with a disc-shaped water intersection II 10; the flow direction of water in the disc-shaped water path is controllable;
the first purification storage tank 15 and the second purification storage tank 14 are respectively provided with a hydrogen branch pipe, and the hydrogen branch pipes are communicated with a pure hydrogen outlet 12;
the first purifying storage tank 15 and the second purifying storage tank 14 are respectively provided with a natural gas branch pipe, and the natural gas branch pipes are communicated with a natural gas outlet 13;
a first valve 1 and a second valve 2 are arranged on the gas inlet branch pipe, the first valve 1 controls the first purification storage tank 15 to inlet gas, and the second valve 2 controls the second purification storage tank 14 to inlet gas;
a first hydrogen valve 4 and a second hydrogen valve 5 are arranged on the hydrogen branch pipe, the first hydrogen valve 4 controls the hydrogen discharge of the first purification storage tank 15, and the second hydrogen valve 5 controls the hydrogen discharge of the second purification storage tank 14;
a natural gas valve I3 and a natural gas valve II 6 are arranged on the natural gas branch pipe, the natural gas valve I3 controls the natural gas discharge of the purifying storage tank I15, and the natural gas valve II 6 controls the natural gas discharge of the purifying storage tank II 14;
the system is also provided with a water path, the water path is provided with a water path inlet 7 and a water path outlet 8, and at least one water path branch pipe connected with the water path inlet 7 and the water path outlet 8 is arranged in the first purification storage tank 15 and the second purification storage tank 14.
Example 2
A continuous hydrogen purification process of hydrogen-doped natural gas is characterized in that the hydrogen-doped volume proportion of the hydrogen-doped natural gas is 10% -30%, the pressure is the medium pressure (1.1-5 bar) of a municipal pipe network, the pressure of a purification storage tank is the same as the pressure of the municipal pipe network, the pressure of a buffer tank is 1-1.1 bar, the reverse thrust is realized, the flow of the hydrogen-doped natural gas entering the purification storage tank is about 40-120L/min, the volume of the purification storage tank only needs 1L, and the material can be LaNi4.3Al0.7;
the method comprises the following steps:
(1) the hydrogen-doped natural gas enters the first purification storage tank 15 through the mixed gas inlet pipe 11 to perform hydrogen absorption reaction, when the first valve 1 is opened, the first purification storage tank 15 enters a hydrogen absorption state, the first natural gas valve 3 is controlled to be opened, when the hydrogen storage alloy in the first purification storage tank 15 is adsorbed and saturated, the first valve (1) is continuously opened for 3-5min, then the second control valve 2 is opened, and the second purification storage tank 14 enters a hydrogen absorption state; at the moment, the first control valve 1 is closed, the first purification storage tank 15 is in a dehydrogenation state, hydrogen is stored, the valve 4 is opened, and hydrogen is discharged from the hydrogen outlet 12;
(2) when the hydrogen storage alloy in the first purification storage tank 15 is saturated in adsorption, closing the first valve 1 and opening the second control valve 2, and entering a second purification storage tank 14 to enter a hydrogen absorption state; at the moment, the first purification storage tank 15 is converted into a hydrogen discharge state, the first control valve 1 is closed, the first purification storage tank is in a dehydrogenation state, the first natural gas valve 3 is opened according to the required hydrogen purity requirement, the initial hydrogen removal gas is used for purging, after purging is finished, the first hydrogen valve 4 is opened, and the hydrogen is discharged from the hydrogen outlet 12;
(3) when the hydrogen storage alloy in the second purification storage tank 14 is saturated in adsorption, closing the second valve 2 and opening the first control valve 1, and enabling the first purification storage tank 15 to enter a hydrogen absorption state; at the moment, the second purification storage tank 14 is converted into a hydrogen discharge state; the second control valve 2 is closed, the second purification storage tank is in a dehydrogenation state, the second natural gas valve 6 is opened according to the required hydrogen purity requirement, the initial hydrogen removal is used for purging, after purging is finished, the second hydrogen valve 5 is opened, and hydrogen is discharged from the hydrogen outlet 12;
when the first purification storage tank 15 enters a hydrogen absorption state and the second purification storage tank 14 is in a hydrogen discharge state, the water flow direction of the disc-shaped water channel is that the first disc-shaped water channel 9 flows to the second disc-shaped water channel 10, the second purification storage tank 14 enters the hydrogen absorption state, and when the first purification storage tank 15 is in the hydrogen discharge state, the water flow direction of the disc-shaped water channel is that the second disc-shaped water channel 10 flows to the first disc-shaped water channel 9.
Although the embodiments of the invention have been described above, they are not limited to the applications listed in the description and the embodiments, which are fully applicable to the analysis of test data in various fields of research and further modifications will be readily apparent to those skilled in the art, and the invention is therefore not limited to the specific details and embodiments shown and described herein without departing from the general concept defined by the claims and their equivalents.
Claims (10)
1. A continuous hydrogen purification system of hydrogen-doped natural gas is characterized by comprising a mixed gas inlet pipe (11) and a purification storage tank, wherein the purification storage tank is divided into a first purification storage tank (15) and a second purification storage tank (14) by a partition, the mixed gas inlet pipe (11) is connected with a gas inlet branch pipe and is respectively connected with the first purification storage tank (15) and the second purification storage tank (14), hydrogen storage alloys are arranged in the first purification storage tank (15) and the second purification storage tank (14), and the hydrogen storage alloys are lanthanum-nickel AB5 LaNi5/MmNi5 and lanthanum-nickel AB5 LaNi5/MmNi5 derivatives, titanium AB type TiFe and titanium AB type TiFe derivatives, A2B Mg2Ni and A2B Mg2Ni derivatives, zirconium AB2 types and derivatives thereof, BCC type vanadium-based solid solution alloys and derivatives thereof;
disc-shaped water paths are arranged in the first purification storage tank (15) and the second purification storage tank (14), the disc-shaped water paths arranged in the first pure storage tank (15) and the second purification storage tank (14) are communicated, the disc-shaped water path in the first purification storage tank (15) is provided with a disc-shaped water opening I (9), and the disc-shaped water path in the second purification storage tank (14) is provided with a disc-shaped water opening II (10); the flow direction of water in the disc-shaped waterway is controllable;
the first purification storage tank (15) and the second purification storage tank (14) are respectively provided with a hydrogen branch pipe, and the hydrogen branch pipes are communicated with a hydrogen outlet (12);
and the first purifying storage tank (15) and the second purifying storage tank (14) are respectively provided with a natural gas branch pipe, and the natural gas branch pipes are communicated with a natural gas outlet (13).
2. The system for continuously purifying hydrogen-loaded natural gas as claimed in claim 1, wherein a valve I (1) and a valve II (2) are arranged on the gas inlet branch pipe, the valve I (1) controls the gas inlet of the purifying storage tank I (15), and the valve II (2) controls the gas inlet of the purifying storage tank II (14).
3. The continuous hydrogen purification system for natural gas loaded with hydrogen as claimed in claim 1, wherein a first hydrogen valve (4) and a second hydrogen valve (5) are arranged on the hydrogen branch pipe, the first hydrogen valve (4) controls the hydrogen discharge of the first purification storage tank (15), and the second hydrogen valve (5) controls the hydrogen discharge of the second purification storage tank (14).
4. The continuous hydrogen purification system for the hydrogen-loaded natural gas as claimed in claim 1, wherein a natural gas valve I (3) and a natural gas valve II (6) are arranged on the natural gas branch pipe, the natural gas valve I (3) controls the natural gas discharge of the purification storage tank I (15), and the natural gas valve II (6) controls the natural gas discharge of the purification storage tank II (14).
5. The continuous hydrogen purification system for the hydrogen-loaded natural gas as claimed in claim 1, wherein a waterway is further arranged in the system, the waterway is provided with a waterway inlet (7) and a waterway outlet (8), and at least one waterway branch pipe connected with the waterway inlet (7) and the waterway outlet (8) is arranged in the first purification storage tank (15) and the second purification storage tank (14).
6. A continuous hydrogen purification system for natural gas loaded with hydrogen as claimed in claim 1, wherein the hydrogen is connected to a buffer tank at outlet (12).
7. The system for continuously purifying hydrogen-loaded natural gas as claimed in claim 1, wherein the water in the water path is heated by using the waste heat of tail gas of hydrogen fuel cell or the waste heat of hydrogen compression/filling or the waste heat of natural gas compression/filling.
8. The process for purifying a hydrogen-loaded natural gas continuous hydrogen purification system according to any one of claims 1 to 7, comprising the steps of:
(1) the hydrogen-doped natural gas enters the first purification storage tank (15) or the second purification storage tank (14) through the mixed gas inlet pipe 11 to perform hydrogen absorption reaction, the first valve (1) and the second valve (2) are opened alternately, when the first valve (1) is opened, the first purification storage tank (15) enters a hydrogen absorption state, the first natural gas valve (3) is controlled to be opened, at the moment, the second valve (2) is controlled to be closed, the second purification storage tank (14) is in a dehydrogenation state, pure hydrogen is generated, the valve (5) is opened, and the hydrogen is discharged from a hydrogen outlet (12); when the second valve (2) is opened, the second purification storage tank (14) is in a hydrogen absorption state, the second natural gas valve (6) is controlled to be opened, at the moment, the first control valve (1) is closed, the first purification storage tank (15) is in a dehydrogenation state, hydrogen storage is generated, the valve (4) is opened, and hydrogen is discharged from the hydrogen outlet (12);
when the hydrogen storage alloy in the first purification storage tank is saturated in adsorption, opening the second control valve, and enabling the second purification storage tank to enter a hydrogen absorption state;
(2) when the hydrogen storage alloy in the first purification storage tank (15) is saturated in adsorption, closing the first valve (1) and opening the second control valve (2), and entering a second purification storage tank (14) to enter a hydrogen absorption state; at the moment, the first purification storage tank (15) is converted into a hydrogen discharge state, the first control valve (1) is closed, the first purification storage tank is in a dehydrogenation state, the first natural gas valve (3) is opened according to the required hydrogen purity requirement, the initial hydrogen removal is used for purging, after purging is finished, the first hydrogen valve (4) is opened, and hydrogen is discharged from a hydrogen outlet (12);
(3) when the hydrogen storage alloy in the second purification storage tank (14) is saturated in adsorption, closing the second valve (2) and opening the first control valve (1), and enabling the first purification storage tank (15) to enter a hydrogen absorption state; at the moment, the second purification storage tank (14) is converted into a hydrogen discharge state; and (3) closing the control valve II (2), opening the natural gas valve II (6) according to the required hydrogen purity requirement, purging by using the initially removed hydrogen, and opening the hydrogen valve II (5) after purging is finished, so that the hydrogen is discharged from the hydrogen outlet (12).
9. The purification process of claim 8, wherein the first purification tank (15) enters a hydrogen absorption state, the second purification tank (14) enters a hydrogen desorption state, the water flow direction of the disc-shaped water path is that the disc-shaped water path I (9) flows to the disc-shaped water path II (10), the second purification tank (14) enters a hydrogen absorption state, and the water flow direction of the disc-shaped water path is that the disc-shaped water path II (10) flows to the disc-shaped water path I (9) when the first purification tank (15) enters the hydrogen desorption state.
10. The purification process of claim 8, wherein the water in the disk-shaped water circuit is replaced with a liquid-gas phase change material that is ammonia, freon, acetone, methanol, thiuram, or mercury.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210849818.5A CN115108531B (en) | 2022-07-19 | 2022-07-19 | Continuous hydrogen purification system and process for hydrogen-doped natural gas |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210849818.5A CN115108531B (en) | 2022-07-19 | 2022-07-19 | Continuous hydrogen purification system and process for hydrogen-doped natural gas |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115108531A true CN115108531A (en) | 2022-09-27 |
| CN115108531B CN115108531B (en) | 2023-04-11 |
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| CN115108531B (en) | 2023-04-11 |
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