CN211998799U - Methanol steam reforming and hydrogen separation integrated low-pressure hydrogen production system - Google Patents
Methanol steam reforming and hydrogen separation integrated low-pressure hydrogen production system Download PDFInfo
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- CN211998799U CN211998799U CN201921826132.4U CN201921826132U CN211998799U CN 211998799 U CN211998799 U CN 211998799U CN 201921826132 U CN201921826132 U CN 201921826132U CN 211998799 U CN211998799 U CN 211998799U
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Abstract
The utility model relates to a methanol steam reforming and hydrogen separation integrated low-pressure hydrogen production system, which comprises a reforming and separating device, a three-phase heat exchange device, an air compressor, a steam trap, a refrigerator, a carbon dioxide separating device and a water gas reforming device; the pressure controlled by the air compressor is 5-30 MPa, and the temperature controlled by the refrigerator is-35-30.8 ℃. The gas in the system is circularly purified, the theoretical yield can reach 100 percent, and the yield of the hydrogen is more than or equal to 95 percent.
Description
Technical Field
The utility model relates to a methanol steam reforming and hydrogen separation integrated low-pressure hydrogen production system and a method thereof.
Background
The hydrogen energy is the most ideal energy in the 21 st century, is used as automobile fuel, is easy to start at low temperature, has small corrosion effect on an engine, and can prolong the service life of the engine. Because the hydrogen and the air can be uniformly mixed, a carburetor used on a common automobile can be completely omitted, and the structure of the existing automobile can be simplified. It is more interesting to add only 4% hydrogen to the gasoline. When it is used as fuel of automobile engine, it can save oil by 40%, and has no need of making great improvement on gasoline engine. A hydrogen fuel cell serves as a power generation system.
No pollution, and no pollution to environment caused by fuel cell. It is through electrochemical reaction, rather than combustion (gasoline, diesel) or energy storage (battery) -the most typical traditional backup power scheme. Combustion releases pollutants like COx, NOx, SOx gases and dust. As described above, the fuel cell generates only water and heat. If the hydrogen is generated by renewable energy sources (photovoltaic panels, wind power generation, etc.), the whole cycle is a complete process without generating harmful emissions.
No noise, quiet fuel cell operation, about only 55dB noise, which corresponds to the level of normal human conversation. This makes the fuel cell suitable for a wide range of applications, including indoor installations, or where there is a limit to noise outdoors.
The efficiency is high, the generating efficiency of the fuel cell can reach more than 50%, which is determined by the conversion property of the fuel cell, chemical energy is directly converted into electric energy without intermediate conversion of heat energy and mechanical energy (a generator), and the efficiency is reduced once more because of once more energy conversion.
At present, the main source of hydrogen of a hydrogen energy source hydrogenation station is that an energy storage tank is transported back from outside, and the whole hydrogenation station needs to store a large amount of hydrogen; research finds that hydrogen in the hydrogen energy industry comprises four links, namely hydrogen preparation, hydrogen storage, hydrogen transportation and hydrogen addition (adding hydrogen into a hydrogen energy vehicle), wherein the two links of hydrogen preparation and hydrogen addition are safe at present, accidents easily occur in the hydrogen storage link, and the cost of the hydrogen transportation link is high and is related to the characteristics of hydrogen; the problems of explosion of the hydrogenation station and the reason of high hydrogenation cost frequently occur in the current news.
Therefore, in order to reduce the problem of large amount of hydrogen storage in the existing hydrogen refueling station and shorten or reduce the high cost of the hydrogen transportation link, a hydrogen refueling station system needs to be redesigned.
SUMMERY OF THE UTILITY MODEL
The to-be-solved technical problem of the utility model is: the defects of the prior art are overcome, the methanol steam reforming and hydrogen separation integrated low-pressure hydrogen production system is provided, and the problem that the hydrogen production system is numerous and complicated due to a split structure between a reformer and a hydrogen separation device in the conventional hydrogen production system is solved;
meanwhile, a low-pressure hydrogen production method is provided, and the problems that the existing hydrogen production process is complex and the circular hydrogen production cannot be realized are solved.
The utility model provides a technical scheme that its technical problem adopted is:
a methanol steam reforming and hydrogen separation integrated low-pressure hydrogen production system comprises a reforming and separating device, a three-phase heat exchange device, an air compressor, a steam trap, a refrigerator, a carbon dioxide separating device and a water gas reforming device;
the reforming separation device is connected with a methanol steam inlet pipe, a hydrogen outlet pipe and a carbon dioxide mixed residual gas outlet pipe, the carbon dioxide mixed residual gas outlet pipe is sequentially connected with a three-phase heat exchange device, an air compressor, a steam trap, a refrigerator, a carbon dioxide separation device and a water gas reforming device, the outlet of the water gas reforming device is connected with a reforming mixed gas outlet pipe, and the reforming mixed gas outlet pipe is connected with the inlet of the reforming separation device;
the methanol steam inlet pipe and the hydrogen outlet pipe are both connected with the three-phase heat exchange device;
the methanol steam inlet pipe is connected with a liquid pump, and the pump pressure of the liquid pump is 2-5 MPa;
the pressure controlled by the air compressor is 5-30 MPa, and the temperature controlled by the refrigerator is-35-30.8 ℃.
Further, the reforming separation device comprises a reaction cavity, a heating cavity is arranged outside the reaction cavity and is suitable for providing reaction temperature for the reaction cavity; the reaction cavity comprises a methanol steam inlet and a carbon dioxide mixed residual gas outlet;
catalyst filler is filled in the reaction cavity, methanol steam is input into the reaction cavity from a methanol steam inlet to perform catalytic reaction, and mixed gas of hydrogen, carbon dioxide and carbon monoxide is generated;
a hydrogen absorption pipe is inserted into the catalyst filler of the reaction cavity, and the hydrogen absorption pipe is suitable for separating the generated mixed gas of hydrogen, carbon dioxide and carbon monoxide into pure hydrogen and carbon dioxide mixed residual gas; pure hydrogen is output and collected from the outlet of the hydrogen absorption pipe, and carbon dioxide mixed residual gas is output from the outlet of the carbon dioxide mixed residual gas.
Further, the hydrogen absorption pipe is a niobium pipe, the catalyst filler comprises an inner layer catalytic filler and an outer layer catalytic filler, the niobium pipe is inserted into the inner layer catalytic filler, and the inner layer catalytic filler is wrapped by the outer layer catalytic filler;
the inner layer catalytic filler is a copper-based filler, and the outer layer catalytic filler is a zirconium-based filler;
the temperature of the methanol vapor for catalytic reaction is 200-500 ℃, and the temperature of the niobium tube for hydrogen separation is 200-500 ℃.
Further, the hydrogen absorption pipe is a palladium membrane pipe or a palladium alloy membrane pipe, the catalyst filler comprises an inner layer catalytic filler and an outer layer catalytic filler, the palladium membrane pipe or the palladium alloy membrane pipe is inserted into the inner layer catalytic filler, and the inner layer catalytic filler is wrapped by the outer layer catalytic filler;
the inner layer catalytic filler is a copper-based filler, and the outer layer catalytic filler is a zirconium-based filler;
the temperature of the methanol steam for catalytic reaction is 200-500 ℃, and the temperature of the palladium membrane tube or the palladium alloy membrane tube for hydrogen separation is 250-550 ℃.
Further, the hydrogen outlet pipe is connected with a hydrogen storage tank, a compressor is arranged on the hydrogen outlet pipe and is suitable for pressing pure hydrogen into the hydrogen storage tank, and the hydrogen storage tank is connected with a hydrogenation machine.
In another aspect, a method for producing hydrogen from methanol water at low pressure comprises the following steps:
s1, feeding methanol water into a methanol steam pipe inlet pipe by a liquid pump, wherein the pump pressure is 2-5 MPa, heating and vaporizing the methanol water to form methanol steam, feeding the methanol steam into a reaction cavity of a reforming and separating device, and decomposing the methanol steam into a mixed gas of hydrogen, carbon dioxide and carbon monoxide;
the gas phase component of the mixed gas of hydrogen, carbon dioxide and carbon monoxide is 65-75% of hydrogen, 20-26% of carbon dioxide and 0.3-3% of carbon monoxide;
s2, separating the mixed gas of hydrogen, carbon dioxide and carbon monoxide by a hydrogen absorption pipe, and outputting the separated pure hydrogen from the hydrogen absorption pipe to be collected; the residual carbon dioxide mixed residual gas is output from the reaction cavity, the pressure of the carbon dioxide mixed residual gas is controlled by an air compressor, the temperature of the carbon dioxide mixed residual gas is controlled by a refrigerator, and then the carbon dioxide mixed residual gas is sent into a carbon dioxide separation device for carbon dioxide liquefaction and separation;
the gas phase components of the carbon dioxide mixed residual gas comprise 25-45% of hydrogen, 55-75% of carbon dioxide, 0-3% of water and 0.3-3% of carbon monoxide;
the pressure controlled by the air compressor is 5-30 MPa, and the temperature controlled by the refrigerator is-35-30.8 ℃;
s3, preparing the carbon dioxide mixed residual gas into liquid carbon dioxide and hydrogen mixed residual gas in a carbon dioxide separator, and outputting and collecting the liquid carbon dioxide;
the components of the hydrogen mixed residual gas comprise 65-75% of hydrogen, 20-26% of carbon dioxide and 3-9% of carbon monoxide;
s4, feeding the hydrogen mixed residual gas into a water gas reforming device for reforming, preparing a reformed mixed gas by water distribution, and distributing water according to the content of carbon monoxide, wherein the water distribution ratio (carbon monoxide: water) is 1: 1-20;
the water gas reforming reaction device reforms the fed hydrogen mixed residual gas into a reformed mixed gas by water distribution, and the gas phase components of the reformed mixed gas comprise 62-77% of hydrogen, 22-27% of carbon dioxide and 0.5-1.5% of carbon monoxide;
so that the proportion of hydrogen, carbon dioxide and carbon monoxide in the reforming mixed gas is close to the proportion of hydrogen, carbon dioxide and carbon monoxide in the mixed gas of hydrogen, carbon dioxide and carbon monoxide;
and S5, mixing the reformed mixed gas with the mixed gas of hydrogen, carbon dioxide and carbon monoxide, and feeding the reformed mixed gas together with the mixed gas of hydrogen, carbon dioxide and carbon monoxide into the reaction cavity again for hydrogen separation.
Further, the pure hydrogen of output and carbon dioxide mixed residual gas are all exported after three-phase heat transfer device heat transfer cooling, methanol-water is vaporized into methanol-water vapour through three-phase heat transfer device heat transfer.
Further, the methanol water is replaced by natural gas.
The utility model has the advantages that:
the utility model discloses a hydrogen manufacturing system makes up into an equipment with reformer and hydrogen separator among the traditional hydrogen manufacturing system, makes the reforming reaction of methanol-steam and the mist separation reaction of hydrogen, carbon dioxide and carbon monoxide all go on in a reaction chamber, promotes hydrogen manufacturing system's hydrogen manufacturing efficiency, also makes whole hydrogen manufacturing system structure obtain optimizing retrench to rely on this hydrogen manufacturing system to make miniature hydrogen manufacturing equipment.
The utility model discloses among the hydrogen manufacturing system, provide the reforming reaction environment of low pressure through the liquid pump, make whole hydrogen manufacturing system can be more safe and stable's operation. And providing the working pressure and temperature of the output carbon dioxide mixed residual gas in a carbon dioxide liquefying device through an air compressor and a refrigerating machine, separating the carbon dioxide mixed residual gas into hydrogen mixed residual gas with a preset molar ratio, and then preparing the hydrogen mixed residual gas into reformed mixed gas through a water gas reforming device.
Secondly, the carbon dioxide mixed residual gas generated in the hydrogen production system is recycled, the pressure and the temperature of the liquid carbon dioxide separated from the carbon dioxide mixed residual gas are controlled by an air compressor and a refrigerator, the carbon dioxide mixed residual gas is separated into hydrogen mixed residual gas and liquid carbon dioxide by a carbon dioxide liquefying device, the liquid carbon dioxide can be stored, and the carbon dioxide liquefying device controls the gas-phase components in the hydrogen mixed residual gas by controlling the pressure and the temperature during separation, so that the molar ratio of the carbon dioxide in the hydrogen mixed residual gas is lower than 26%, and the hydrogen mixed residual gas is prepared for the subsequent reformed mixed gas; and finally, reforming the hydrogen mixed residual gas through water gas water distribution, wherein carbon monoxide in the hydrogen mixed residual gas is reduced to 0.5-1.5% from 3-9%, and the gas phase component of the reformed mixed gas is as follows: 62-77% of hydrogen, 22-27% of carbon dioxide and 0.5-1.5% of carbon monoxide; the gas phase component of the reformed mixed gas is close to the mixed gas component of the hydrogen, the carbon dioxide and the carbon monoxide prepared by the reformer, the reformed mixed gas and the mixed gas can be mixed and then enter the membrane separation and purification device for hydrogen purification and separation to prepare hydrogen, the gas in the system is circularly purified, the theoretical yield can reach 100 percent, and the hydrogen yield is more than or equal to 95 percent.
Meanwhile, the hydrogen station system for preparing hydrogen by using methanol directly consumes customers, saves freight compared with factory hydrogen in selling price, recovers the hydrogen in the carbon dioxide residual gas, can realize the yield of 100 percent theoretically, is actually more than 90 to 99 percent, and simultaneously recovers CO2Theoretical yield of 100% and actual yield90-99 percent. The process is combined with a hydrogenation station, so that high yield of hydrogen can be realized, and more CO can be recovered2And economic benefit is obtained, safety (high-pressure hydrogen storage is reduced), economy (methanol transportation cost is much lower than that of hydrogen) and CO recovery are really realized2Zero emission is realized, and ecological benefits are obtained.
On the one hand, hydrogen production is harmless and zero-state emission; on the other hand, the carbon dioxide emission reduction is made into methanol, greenhouse gas is changed into useful methanol liquid fuel, the methanol liquid fuel is taken as a hydrogenation station, the solar fuel has rich sources, light, wind, water and nuclear energy are all available, the carbon dioxide hydrogenation is used for preparing the methanol, and the methanol can be transported, stored and transported. The problems of manufacture, storage, transportation, installation and the like are solved in the whole view,
firstly, the liquid sunlight hydrogen station solves the safety problem of the high-pressure hydrogen station; secondly, the problems of storage, transportation and safety of hydrogen are solved; thirdly, hydrogen can be used as renewable energy to realize the aim of cleaning the whole process; fourthly, the liquid sunlight hydrogenation station can recover carbon dioxide, so that carbon dioxide emission reduction is realized, no further carbon dioxide is generated, and the carbon dioxide is always circulated therein; fifthly, the liquid sunlight hydrogenation station technology can be expanded to other chemical synthesis fields and can also be used for chemical hydrogenation; sixth, the system can be shared with a gas station and a methanol adding station. The system is particularly suitable for community distributed thermoelectric combined energy supply and the existing gas stations.
Drawings
The present invention will be further explained with reference to the accompanying drawings.
FIG. 1 is a diagram of a methanol steam reforming and hydrogen separation integrated low-pressure hydrogen production system of the present invention;
FIG. 2 is a schematic diagram of a reforming separation apparatus;
the device comprises a liquid pump 1, a three-phase heat exchange device 2, a reforming separation device 3, an inner-layer catalytic filler 31A, an outer-layer catalytic filler 31B, a hydrogen absorption pipe 32, a heating cavity 33, a carbon dioxide separation device 4, a water gas reforming device 5, a refrigerator 6, a refrigerator 7, an air compressor 8 and a steam trap.
Detailed Description
The invention will now be further described with reference to specific embodiments. The drawings are simplified schematic diagrams only illustrating the basic structure of the present invention in a schematic manner, and thus show only the components related to the present invention.
Example one
As shown in fig. 1 and fig. 2, a methanol steam reforming and hydrogen separation integrated low-pressure hydrogen production system comprises a reforming and separating device 3, a three-phase heat exchange device 2, an air compressor 7, a steam trap 8, a refrigerator 6, a carbon dioxide separating device 4 and a water gas reforming device 5.
The reforming separation device 3 is connected with a methanol steam inlet pipe, a hydrogen outlet pipe and a carbon dioxide mixed residual gas outlet pipe, the carbon dioxide mixed residual gas outlet pipe is sequentially connected with the three-phase heat exchange device 2, the air compressor 7, the steam trap 8, the refrigerator 6, the carbon dioxide separation device 4 and the water gas reforming device 5, the outlet of the water gas reforming device 5 is connected with a reforming mixed gas outlet pipe, and the reforming mixed gas outlet pipe is connected with the inlet of the reforming separation device 3; the methanol steam inlet pipe and the hydrogen outlet pipe are both connected with the three-phase heat exchange device 2; the methanol steam inlet pipe is connected with a liquid pump 1, and the pump pressure of the liquid pump 1 is 2-5 MPa; the pressure controlled by the air compressor 7 is 5-30 MPa, and the temperature controlled by the refrigerator 6 is-35-30.8 ℃.
Specifically, as shown in fig. 2, the reforming separation device 3 includes a reaction chamber, and the reaction chamber includes a methanol steam inlet and a carbon dioxide mixed residual gas outlet;
catalyst filler is filled in the reaction cavity, methanol steam is input into the reaction cavity from a methanol steam inlet to perform catalytic reaction, and mixed gas of hydrogen, carbon dioxide and carbon monoxide is generated;
a hydrogen absorption pipe 32 is inserted into the catalyst packing of the reaction cavity, and the hydrogen absorption pipe 32 is suitable for separating the generated mixed gas of hydrogen, carbon dioxide and carbon monoxide into mixed residual gas of pure hydrogen and carbon dioxide; pure hydrogen is output and collected from the outlet of the hydrogen absorption pipe 32, and carbon dioxide mixed residual gas is output from the outlet of the carbon dioxide mixed residual gas.
Specifically, the hydrogen absorption pipe 32 is a niobium pipe, the catalyst filler includes an inner catalytic filler 31A and an outer catalytic filler 31B, the niobium pipe is inserted into the inner catalytic filler 31A, and the outer catalytic filler 31B wraps the inner catalytic filler 31A; the inner layer catalytic filler is a copper-based filler, and the outer layer catalytic filler is a zirconium-based filler; the temperature of the methanol vapor for catalytic reaction is 200-500 ℃, and the temperature of the niobium tube for hydrogen separation is 200-500 ℃.
Or, the hydrogen absorption tube 32 is a palladium membrane tube or a palladium alloy membrane tube, the catalyst filler includes an inner layer catalytic filler 31A and an outer layer catalytic filler 31B, the niobium tube is inserted into the inner layer catalytic filler 31A, and the outer layer catalytic filler 31B wraps the inner layer catalytic filler 31A; the inner layer catalytic filler is a copper-based filler, and the outer layer catalytic filler is a zirconium-based filler; the temperature of the methanol steam for catalytic reaction is 200-500 ℃, and the temperature of the palladium membrane tube or the palladium alloy membrane tube for hydrogen separation is 250-550 ℃.
The function of the niobium tube, the palladium membrane tube or the palladium alloy membrane tube is the same, the mixed gas of hydrogen, carbon dioxide and carbon monoxide generated in the reaction cavity is subjected to hydrogen absorption and separation, pure hydrogen is output and collected, and the residual mixed gas of carbon dioxide is output for recovery operation.
Specifically, a heating cavity 33 for providing working heat to the reaction cavity is arranged outside the reaction cavity, and the heat of the heating cavity 33 is provided by the heat generated by the combustion of the carbon dioxide mixed residual gas. Therefore, the use of other equipment for supplying heat by using the reaction cavity can be reduced, and the cost is reduced.
The hydrogen outlet pipe is connected with a hydrogen storage tank, a compressor is arranged on the hydrogen outlet pipe and is suitable for pressing pure hydrogen into the hydrogen storage tank, and the hydrogen storage tank is connected with a hydrogenation machine. The hydrogen production system realizes on-site hydrogen production, the prepared hydrogen is directly stored in the hydrogen storage tank, and the prepared pure hydrogen is directly added into the hydrogen vehicle through the hydrogenation machine.
During operation, methanol water is vaporized into methanol steam through the three-phase heat exchange device 2, the methanol steam enters the reaction cavity, the heating cavity 33 is heated to control the temperature in the reaction cavity, and the methanol steam is subjected to catalytic reaction at the approximate temperature and under the action of the catalyst filler, so that the multi-component and multi-reaction gas-solid catalytic reaction system is formed;
the reaction equation is:
CH3OH→CO+2H2(ii) a (reversible reaction)
H2O+CO→CO2+H2(ii) a (reversible reaction)
CH3OH+H2O→CO2+3H2(ii) a (reversible reaction)
2CH3OH→CH3OCH3+H2O; (side reaction)
CO+3H2→CH4+H2O; (side reaction)
The reforming reaction generates a mixed gas of hydrogen, carbon dioxide and carbon monoxide. The mixed gas of hydrogen, carbon dioxide and carbon monoxide moves upwards to pass through a hydrogen absorption pipe 32, the hydrogen absorption pipe 32 separates the hydrogen in the mixed gas, pure hydrogen is collected into a hydrogen storage tank after being output through the hydrogen absorption pipe 32, the residual carbon dioxide mixed residual gas is output from a carbon dioxide mixed residual gas outlet pipe of a reaction cavity, the carbon dioxide mixed residual gas is cooled through a three-phase heat exchange device 2, the pressure and the temperature of the mixed gas entering a carbon dioxide separation device 4 are controlled through an air compressor 7 and a refrigerator 6, then the carbon dioxide mixed residual gas and the carbon dioxide separation device 4 are liquefied and separated, the separated liquid carbon dioxide is collected, the separated hydrogen mixed residual gas is sent into a water gas reforming device 5, the hydrogen mixed residual gas is changed into reformed mixed gas after water gas reforming, the proportion of the gas phase component of the reformed mixed gas and the mixed gas component of hydrogen, carbon dioxide and carbon monoxide generated by reforming reaction is, therefore, the reformed mixed gas is sent into the reaction cavity to circularly absorb hydrogen, so that the hydrogen yield of the whole low-pressure hydrogen production system is improved, the conveying pressure of the reformed mixed gas is provided by the upstream air compressor 7, and if the conveying pressure of the reformed mixed gas is not enough, an air pump can be arranged on the reformed mixed gas outlet pipe to provide the conveying air pressure.
In the low-pressure hydrogen production system, the pressure provided by the liquid pump 1 is 2-5 MPa, the whole hydrogen production system operates in a low-pressure state, and the hydrogen production operation is safer; the reformer and the hydrogen separation device are combined into one device, so that the structure of the whole hydrogen production system is optimized and simplified, and the hydrogen production system can be made into a small hydrogen production device.
Example two
A methanol water low pressure hydrogen production system adopts above-mentioned low pressure hydrogen production system, includes the following steps:
s1, feeding methanol water into a methanol steam pipe inlet pipe by a liquid pump 1, wherein the pump pressure is 2-5 MPa, heating and vaporizing the methanol water through a three-phase heat exchange device 2 to form methanol steam, feeding the methanol steam into a reaction cavity of a reforming and separating device 3, and decomposing the methanol steam into a mixed gas of hydrogen, carbon dioxide and carbon monoxide;
the gas phase component of the mixed gas of hydrogen, carbon dioxide and carbon monoxide is 65-75% of hydrogen, 20-26% of carbon dioxide and 0.3-3% of carbon monoxide;
s2, separating the mixed gas of hydrogen, carbon dioxide and carbon monoxide by the hydrogen absorption pipe 32, and outputting the separated pure hydrogen from the hydrogen absorption pipe 32 to be collected; outputting the residual carbon dioxide mixed residual gas from the reaction cavity, wherein the gas phase components of the carbon dioxide mixed residual gas comprise 25-45% of hydrogen, 55-75% of carbon dioxide, 0-3% of water and 0.3-3% of carbon monoxide;
controlling the pressure of the carbon dioxide mixed residual gas by an air compressor 7, controlling the temperature of the carbon dioxide mixed residual gas by a refrigerator 6, wherein the pressure controlled by the air compressor 7 is 5-30 MPa, and the temperature controlled by the refrigerator 6 is-35-30.8 ℃; then sending the carbon dioxide mixed residual gas into a carbon dioxide separation device 4 for carbon dioxide liquefaction and separation;
s3, preparing the carbon dioxide mixed residual gas into liquid carbon dioxide and hydrogen mixed residual gas in a carbon dioxide separator, and outputting and collecting the liquid carbon dioxide; the components of the hydrogen mixed residual gas comprise 65-75% of hydrogen, 20-26% of carbon dioxide and 3-9% of carbon monoxide;
the molar ratio of carbon dioxide in the gaseous phase components of the hydrogen mixed residual gas is controlled to be 20-26%, and the selection of the pressure and the temperature of the carbon dioxide liquefying device during working is shown in the following table:
| scheme(s) | Pressure (Mpa) | Temperature (. degree.C.) |
| Scheme 1 | 5 | -35 |
| |
7 | -25 |
| |
10 | -10 |
| Scheme 4 | 15 | 0 |
| |
20 | 20 |
| |
25 | 25 |
| |
30 | 30.8 |
S4, feeding the hydrogen mixed residual gas into a water gas reforming device 5 for reforming, preparing a reformed mixed gas by water distribution, and distributing water according to the content of carbon monoxide, wherein the water distribution ratio (carbon monoxide: water) is 1: 1-20;
the water gas reforming reaction device reforms the fed hydrogen mixed residual gas into a reformed mixed gas by water distribution, and the gas phase components of the reformed mixed gas comprise 62-77% of hydrogen, 22-27% of carbon dioxide and 0.5-1.5% of carbon monoxide;
so that the proportion of hydrogen, carbon dioxide and carbon monoxide in the reforming mixed gas is close to the proportion of hydrogen, carbon dioxide and carbon monoxide in the mixed gas of hydrogen, carbon dioxide and carbon monoxide;
and S5, feeding the reformed mixed gas into the reaction cavity to be mixed with the mixed gas of hydrogen, carbon dioxide and carbon monoxide, and feeding the reformed mixed gas together with the mixed gas of hydrogen, carbon dioxide and carbon monoxide into the reaction cavity again to separate hydrogen.
Specifically, the mixed residual gas of pure hydrogen and carbon dioxide of output all exports after 2 heat transfer cooling of three-phase heat transfer device, the methanol-water vaporizes into methanol-water vapour through 2 heat transfer of three-phase heat transfer device.
In this embodiment, the methanol-water may be replaced by natural gas, and hydrogen is produced from natural gas to obtain a mixed gas of hydrogen, carbon dioxide and carbon monoxide.
The utility model discloses a low pressure hydrogen manufacturing method relies on methanol-water low pressure hydrogen manufacturing system in embodiment one, regards methanol-water as the hydrogen manufacturing raw materials, and methanol-water vapor after the methanol-water vaporization reacts the mist that generates hydrogen, carbon dioxide and carbon monoxide in the reaction intracavity, then the mist of hydrogen, carbon dioxide and carbon monoxide directly reacts hydrogen absorption with hydrogen absorption pipe 32 in the reaction intracavity, and pure hydrogen can direct output gather, and hydrogen manufacturing efficiency improves greatly. Then, conveying the generated carbon dioxide mixed residual gas, passing through an air compressor 7 and a refrigerator 6, controlling the pressure and the temperature of the carbon dioxide mixed residual gas in a carbon dioxide separation device 4 to liquefy and separate the carbon dioxide in the carbon dioxide mixed residual gas, controlling the components of the separated hydrogen mixed residual gas to ensure that the molar ratio of the carbon dioxide in the hydrogen mixed residual gas is lower than 26 percent, and preparing the hydrogen mixed residual gas for the subsequent reforming mixed gas; and finally, reforming the hydrogen mixed residual gas through water gas water distribution, reducing carbon monoxide in the hydrogen mixed residual gas from 3-9% originally to 0.5-1.5%, and reforming the gas phase components of the mixed gas: 62-77% of hydrogen, 22-27% of carbon dioxide and 0.5-1.5% of carbon monoxide; the gas phase component of the reformed mixed gas is close to the mixed gas component of the hydrogen, the carbon dioxide and the carbon monoxide prepared by the reformer, the reformed mixed gas and the mixed gas can be mixed and then enter the membrane separation and purification device for hydrogen purification and separation to prepare hydrogen, the gas in the system is circularly purified, the theoretical yield can reach 100 percent, and the hydrogen yield is more than or equal to 95 percent.
In light of the foregoing, it will be apparent to those skilled in the art from this disclosure that various changes and modifications can be made without departing from the spirit and scope of the invention. The technical scope of the present invention is not limited to the content of the specification, and must be determined according to the scope of the claims.
Claims (5)
1. A methanol steam reforming and hydrogen separation integrated low-pressure hydrogen production system is characterized by comprising a reforming and separating device, a three-phase heat exchange device, an air compressor, a steam trap, a refrigerator, a carbon dioxide separating device and a water gas reforming device;
the reforming separation device is connected with a methanol steam inlet pipe, a hydrogen outlet pipe and a carbon dioxide mixed residual gas outlet pipe, the carbon dioxide mixed residual gas outlet pipe is sequentially connected with a three-phase heat exchange device, an air compressor, a steam trap, a refrigerator, a carbon dioxide separation device and a water gas reforming device, the outlet of the water gas reforming device is connected with a reforming mixed gas outlet pipe, and the reforming mixed gas outlet pipe is connected with the inlet of the reforming separation device;
the methanol steam inlet pipe and the hydrogen outlet pipe are both connected with the three-phase heat exchange device;
the methanol steam inlet pipe is connected with a liquid pump, and the pump pressure of the liquid pump is 2-5 MPa;
the pressure controlled by the air compressor is 5-30 MPa, and the temperature controlled by the refrigerator is-35-30.8 ℃.
2. The methanol steam reforming and hydrogen separation integrated low-pressure hydrogen production system according to claim 1, wherein the reforming and separating device comprises a reaction chamber, and a heating chamber is arranged outside the reaction chamber and is suitable for providing reaction temperature for the reaction chamber; the reaction cavity comprises a methanol steam inlet and a carbon dioxide mixed residual gas outlet;
catalyst filler is filled in the reaction cavity, methanol steam is input into the reaction cavity from a methanol steam inlet to perform catalytic reaction, and mixed gas of hydrogen, carbon dioxide and carbon monoxide is generated;
a hydrogen absorption pipe is inserted into the catalyst filler of the reaction cavity, and the hydrogen absorption pipe is suitable for separating the generated mixed gas of hydrogen, carbon dioxide and carbon monoxide into pure hydrogen and carbon dioxide mixed residual gas; pure hydrogen is output and collected from the outlet of the hydrogen absorption pipe, and carbon dioxide mixed residual gas is output from the outlet of the carbon dioxide mixed residual gas.
3. The methanol steam reforming and hydrogen separation integrated low-pressure hydrogen production system according to claim 2, wherein the hydrogen absorption pipe is a niobium pipe, the catalyst filler comprises an inner layer catalytic filler and an outer layer catalytic filler, the niobium pipe is inserted into the inner layer catalytic filler, and the outer layer catalytic filler wraps the inner layer catalytic filler;
the inner layer catalytic filler is a copper-based filler, and the outer layer catalytic filler is a zirconium-based filler;
the temperature of the methanol vapor for catalytic reaction is 200-500 ℃, and the temperature of the niobium tube for hydrogen separation is 200-500 ℃.
4. The methanol steam reforming and hydrogen separation integrated low-pressure hydrogen production system according to claim 2, wherein the hydrogen absorption pipe is a palladium membrane pipe or a palladium alloy membrane pipe, the catalyst filler comprises an inner layer catalytic filler and an outer layer catalytic filler, the palladium membrane pipe or the palladium alloy membrane pipe is inserted into the inner layer catalytic filler, and the outer layer catalytic filler wraps the inner layer catalytic filler;
the inner layer catalytic filler is a copper-based filler, and the outer layer catalytic filler is a zirconium-based filler;
the temperature of the methanol steam for catalytic reaction is 200-500 ℃, and the temperature of the palladium membrane tube or the palladium alloy membrane tube for hydrogen separation is 250-550 ℃.
5. The methanol steam reforming and hydrogen separation integrated low-pressure hydrogen production system according to claim 2, wherein the hydrogen gas outlet pipe is connected with a hydrogen storage tank, a compressor is arranged on the hydrogen gas outlet pipe and is suitable for pressing pure hydrogen gas into the hydrogen storage tank, and the hydrogen storage tank is connected with a hydrogenation machine.
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