CN110817795A - Hydrogen separation and water gas reforming integrated medium-pressure hydrogen production system and method - Google Patents
Hydrogen separation and water gas reforming integrated medium-pressure hydrogen production system and method Download PDFInfo
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Abstract
The invention relates to a hydrogen separation and water gas reforming integrated medium-pressure hydrogen production system, which comprises a reformer, a three-phase heat exchange device, a steam trap, a refrigerator, a carbon dioxide liquefaction device and a hydrogen separation and water gas reforming integrated device; the pump pressure of the liquid pump is 7-18 MPa, and the temperature controlled by the refrigerator is-25-18 ℃. A medium-pressure hydrogen production method comprises the steps that methanol steam is subjected to reforming reaction in a reformer to generate mixed gas of hydrogen, carbon dioxide and carbon monoxide, and hydrogen mixed residual gas is sent into a water gas reforming cavity of a water gas reforming integrated device and is distributed with water to prepare reformed mixed gas; the reformed mixed gas enters a hydrogen separation cavity to be mixed with the mixed gas of hydrogen, carbon dioxide and carbon monoxide, and the mixed gas is subjected to hydrogen separation operation in the hydrogen separation cavity; 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 invention relates to a hydrogen separation and water gas reforming integrated medium-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.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: the defects of the prior art are overcome, the hydrogen separation and water gas reforming integrated medium-pressure hydrogen production system is provided, and the problem that the hydrogen production system is numerous and complicated due to a split structure between the water gas reforming and hydrogen separation devices in the conventional hydrogen production system is solved;
meanwhile, a medium-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 technical scheme adopted by the invention for solving the technical problems is as follows:
a hydrogen separation and water gas reforming integrated medium-pressure hydrogen production system comprises a reformer, a three-phase heat exchange device, a steam trap, a refrigerator, a carbon dioxide liquefaction device and a hydrogen separation and water gas reforming integrated device;
the reformer is connected with a methanol steam inlet pipe and a mixed gas outlet pipe; the reformer is suitable for preparing the methanol steam into a mixed gas of hydrogen, carbon dioxide and carbon monoxide;
the water gas reforming integrated device comprises a reaction cavity, wherein a heating cavity is arranged outside the reaction cavity and is suitable for providing reaction temperature for the reaction cavity; a hydrogen separation cavity and a water gas reforming cavity are arranged in the reaction cavity, the hydrogen separation cavity is positioned above the water gas reforming cavity, and the hydrogen separation cavity is communicated with the water gas reforming cavity; the hydrogen separation cavity is provided with a mixed gas inlet and a carbon dioxide mixed residual gas outlet, a hydrogen absorption pipe is inserted into the hydrogen separation cavity and is suitable for separating pure hydrogen, and the hydrogen absorption pipe is connected with a pure hydrogen outlet pipe; the water gas reforming cavity is provided with a catalyst filler, and the water gas reforming cavity is provided with a hydrogen mixed residual gas inlet;
the mixed gas outlet pipe is connected with a mixed gas inlet, the carbon dioxide mixed residual gas outlet is connected with a carbon dioxide mixed residual gas outlet pipe, the carbon dioxide mixed residual gas outlet pipe is sequentially connected with a steam trap, a refrigerator and a carbon dioxide liquefying device, the carbon dioxide liquefying device is connected with a liquid carbon dioxide outlet pipe and a hydrogen mixed residual gas outlet pipe, the hydrogen mixed residual gas outlet pipe is connected with a hydrogen mixed residual gas inlet, and an air pump for providing hydrogen mixed residual gas conveying pressure is arranged on the hydrogen mixed residual gas outlet pipe;
the methanol steam inlet pipe is connected with a liquid pump, the pump pressure of the liquid pump is 7-18 MPa, and the temperature controlled by the refrigerator is-25-18 ℃.
Further, the carbon dioxide mixed residual gas outlet pipe and the pure hydrogen outlet pipe are both connected with a three-phase heat exchange device.
Further, the hydrogen absorption pipe is a niobium pipe, the catalyst filler is a copper-based filler, and the operating temperature of the reaction cavity is 200-350 ℃;
or the catalyst filler is a zirconium-based filler, and the operating temperature of the reaction chamber is 350-550 ℃.
Further, the hydrogen absorption tube is a palladium membrane tube or a palladium alloy membrane tube, the catalyst filler is a zirconium-based filler, and the operating temperature of the reaction chamber 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 sending pure hydrogen into the hydrogen storage tank, and the hydrogen storage tank is connected with a hydrogenation machine.
In another aspect, a medium-pressure hydrogen production method using the medium-pressure hydrogen production system comprises the following steps:
s1, feeding methanol water into a methanol steam pipe inlet pipe by a liquid pump, wherein the pump pressure is 7-18 MPa, heating and vaporizing the methanol water to form methanol steam, feeding the methanol steam into a reformer, carrying out a reforming reaction on the methanol steam in the reformer to generate a mixed gas of hydrogen, carbon dioxide and carbon monoxide, and feeding the mixed gas of the hydrogen, the carbon dioxide and the carbon monoxide into a hydrogen separation cavity of the water gas reforming integrated device;
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 in the hydrogen separation cavity, 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 hydrogen separation cavity, the pressure of the carbon dioxide mixed residual gas is controlled by a liquid pump, 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 control pressure of the liquid pump is 7-18 MPa, and the control temperature of the refrigerator is-25-18 ℃;
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 cavity of the water gas reforming integrated device, 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;
water is distributed in the water gas reforming cavity to reform the fed hydrogen mixed residual gas into reformed mixed gas, 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, the reforming mixed gas enters the hydrogen separation cavity to be mixed with the mixed gas of hydrogen, carbon dioxide and carbon monoxide, and the reforming mixed gas and the mixed gas of hydrogen, carbon dioxide and carbon monoxide are subjected to hydrogen separation operation in the hydrogen separation cavity.
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 invention has the beneficial effects that:
according to the hydrogen production system, the water gas reforming and hydrogen separation devices in the traditional hydrogen production system are combined into one device, so that the hydrogen mixing residual gas and water gas reforming operation and the mixed gas separation reaction of hydrogen, carbon dioxide and carbon monoxide are operated in the reaction cavity at the temperature, the hydrogen production efficiency of the hydrogen production system is improved, the structure of the whole hydrogen production system is optimized and simplified, and the hydrogen production system can be made into small-sized hydrogen production equipment.
In the hydrogen production system, a medium-pressure (7-18 MPa) reaction environment is provided by the liquid pump, so that the whole hydrogen production system can operate more safely and stably. And providing the working pressure and temperature of the output carbon dioxide mixed residual gas in a carbon dioxide liquefying device through a liquid pump 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 a liquid pump 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, 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.
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 CO2The theoretical yield is 100 percent, and the actual yield is 90-99 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 further expanded to other theories of chemical trip and can be used for hydrogenation to do the same; the liquid sunlight hydrogenation station technology can also be expanded to other chemical synthesis fields and can also be used for chemical hydrogenation; sixth, there may be a gasoline station, a methanol station, and so on. Is particularly suitable for communities and the existing gas stations. Can be co-located 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 invention is further described below with reference to the accompanying drawings.
FIG. 1 is a schematic diagram of a hydrogen separation and water gas reforming integrated medium pressure hydrogen production system of the present invention;
FIG. 2 is a schematic of a water gas reforming integrated unit;
the device comprises a liquid pump 1, a three-phase heat exchange device 2, a water gas reforming integrated device 3, a water gas reforming integrated device 31, a water gas reforming cavity 32, a hydrogen separation cavity 33, a hydrogen absorption pipe 34, a heating cavity 4, a reformer 5, a refrigerator 6, a carbon dioxide liquefying device 7, a steam trap 8 and an air pump.
Detailed Description
The invention will now be further described with reference to specific examples. These drawings are simplified schematic diagrams only illustrating the basic structure of the present invention in a schematic manner, and thus show only the constitution related to the present invention.
Example one
As shown in fig. 1 and fig. 2, a hydrogen separation and water gas reforming integrated medium-pressure hydrogen production system comprises a reformer 4, a three-phase heat exchange device 2, a steam trap 7, a refrigerator 5, a carbon dioxide liquefaction device 6 and a hydrogen separation and water gas reforming integrated device 3.
The reformer 4 is connected with a methanol steam inlet pipe and a mixed gas outlet pipe; the methanol steam inlet pipe is connected with the three-phase heat exchange device 2, and the reformer 4 is suitable for preparing the methanol steam into mixed gas of hydrogen, carbon dioxide and carbon monoxide;
the water gas reforming integrated device 3 comprises a reaction cavity, wherein a heating cavity 34 is arranged outside the reaction cavity and is suitable for providing reaction temperature for the reaction cavity; a hydrogen separation cavity 32 and a water gas reforming cavity 31 are arranged in the reaction cavity, the hydrogen separation cavity 32 is positioned above the water gas reforming cavity 31, and the hydrogen separation cavity 32 is communicated with the water gas reforming cavity 31; the hydrogen separation cavity 32 is provided with a mixed gas inlet and a carbon dioxide mixed residual gas outlet, a hydrogen absorption pipe 33 is inserted into the hydrogen separation cavity 32 and is suitable for separating pure hydrogen, and the hydrogen absorption pipe 33 is connected with a pure hydrogen outlet pipe; the water gas reforming cavity 31 is provided with a catalyst filler, and the water gas reforming cavity 31 is provided with a hydrogen mixing residual gas inlet;
the mixed gas exit tube and gas mixture access connection, the mixed residual gas exit linkage carbon dioxide mixed residual gas exit tube of carbon dioxide, the mixed residual gas exit tube of carbon dioxide connects gradually steam trap 7, refrigerator 5 and carbon dioxide liquefying plant 6, carbon dioxide liquefying plant 6 connects liquid carbon dioxide exit tube and the mixed residual gas exit tube of hydrogen, the mixed residual gas exit tube of hydrogen and the mixed residual gas access connection of hydrogen.
And the hydrogen mixed residual gas outlet pipe is provided with an air pump 8 for providing hydrogen mixed residual gas conveying pressure.
The methanol steam inlet pipe is connected with the liquid pump 1, the pump pressure of the liquid pump 1 is 7-18 MPa, and the temperature controlled by the refrigerator 5 is-25-18 ℃.
The steam trap 7 is used for discharging moisture in the carbon dioxide mixed residual gas and then carrying out carbon dioxide liquefaction.
Specifically, three-phase heat transfer device 2 is all connected to carbon dioxide mixture residual gas exit tube and pure hydrogen exit tube, and pure hydrogen and carbon dioxide mixture residual gas all carry out the heat transfer cooling then export with three-phase heat transfer device 2, and the heat that trades provides methanol steam and advances the pipe for carry out the vaporization operation to methanol-water.
Specifically, in this embodiment, the hydrogen absorption pipe 33 is a niobium pipe, the catalyst filler is a copper-based filler, and the operating temperature of the reaction chamber is 200-; or the catalyst filler is a zirconium-based filler, and the operating temperature of the reaction chamber is 350-550 ℃.
Or, the hydrogen absorption pipe 33 is a palladium membrane pipe or a palladium alloy membrane pipe, the catalyst filler is a zirconium-based filler, and the operating temperature of the reaction chamber is 250-550 ℃.
The copper-based filler or the zirconium-based filler corresponds to two different catalytic temperatures, the catalytic temperature corresponding to the copper-based filler is lower than that of the zirconium-based filler, the catalytic reaction temperature of the copper-based filler is 350 ℃ in the temperature range of 200 ℃ and the catalytic reaction temperature of the zirconium-based filler is 550 ℃ in the temperature range of 350 ℃.
The hydrogen outlet pipe is connected with a hydrogen storage tank, a compressor is arranged on the hydrogen outlet pipe and is suitable for sending 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.
The hydrogen production system combines the water gas reforming and hydrogen separation devices in the traditional hydrogen production system into one device, so that the hydrogen mixed residual gas and water gas reforming operation and the mixed gas separation reaction of hydrogen, carbon dioxide and carbon monoxide are operated in the reaction cavity at the same temperature, and the whole hydrogen production system is optimized.
During operation, methanol water is conveyed by the liquid pump 1 and vaporized into methanol steam by the three-phase heat exchange device 2, the pump pressure of the liquid pump 1 is 7-18 MPa, the methanol steam enters the reformer 4, and the methanol steam is subjected to catalytic reaction in the reformer 4, so that the system is a multi-component and multi-reaction gas-solid catalytic reaction system;
the reaction equation is: CH (CH)3OH→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 is sent into a hydrogen separation cavity 32 of the water gas reforming integrated device 3 through a mixed gas outlet pipe, a hydrogen absorption pipe 33 is used for absorbing and separating the mixed gas of hydrogen, carbon dioxide and carbon monoxide, and the separated pure hydrogen is output from a pure hydrogen outlet pipe; the separated carbon dioxide mixed residual gas is output from a carbon dioxide mixed residual gas outlet pipe, the temperature of the carbon dioxide mixed residual gas is controlled by a refrigerator 5, the pressure of the carbon dioxide mixed residual gas is controlled at the source by a liquid pump 1, the pressure is 7-18 MPa, the carbon dioxide mixed residual gas and carbon dioxide separation device is used for carrying out liquefaction separation, the separated liquid carbon dioxide is collected, the separated hydrogen mixed residual gas is sent into a water gas reforming cavity 31 of a water gas reforming integrated device 3, the hydrogen mixed residual gas is changed into a reformed mixed gas after water gas reforming, the proportion of gas phase components of the reformed mixed gas and the mixed gas components of hydrogen, carbon dioxide and carbon monoxide generated by reforming reaction is approximate, the reformed mixed gas in the water gas reforming cavity 31 directly enters a hydrogen separation cavity 32 and is mixed with the mixed gas of the hydrogen, the carbon dioxide and the carbon monoxide, and the hydrogen is circularly absorbed and separated through the hydrogen absorption pipe 33 again, so that the hydrogen yield of the whole medium-pressure hydrogen production system is improved.
The medium-pressure hydrogen production system combines hydrogen separation and water gas reforming in the traditional hydrogen production system into one device, so that hydrogen separation reaction of mixed gas of hydrogen, carbon dioxide and carbon monoxide and water gas reforming reaction of mixed residual gas of hydrogen are carried out in one reaction cavity, the hydrogen production efficiency of the hydrogen production system is improved, the structure of the whole hydrogen production system is optimized and simplified, and the small-sized hydrogen production device can be manufactured by means of the hydrogen production system.
In the hydrogen production system, the liquid pump 1 is used for providing a medium-pressure reforming reaction environment, the pressure provided by the liquid pump 1 is 7-18 MPa, so that when the whole hydrogen production system is used for treating the carbon dioxide mixed residual gas, only the refrigerator 5 is needed to control the temperature (-25-18 ℃) of the carbon dioxide mixed residual gas in the carbon dioxide liquefying device 6, and the pressure of the carbon dioxide mixed residual gas in the carbon dioxide liquefying device 6 is directly controlled from the source by the liquid pump 1, so that the medium-pressure hydrogen production system can produce hydrogen compared with low-pressure hydrogen, an air compressor (an air compressor is needed to be independently configured for providing the pressure for liquefying the carbon dioxide mixed residual gas) can be omitted, and the medium-pressure hydrogen production system is simplified and optimized.
The output carbon dioxide mixed residual gas is provided with the working pressure and temperature in the carbon dioxide liquefying device 6 through the liquid pump 1 and the refrigerating machine 5, so that the carbon dioxide mixed residual gas is separated into hydrogen mixed residual gas with a preset molar ratio, and then the hydrogen mixed residual gas is prepared into reformed mixed gas through the water gas reforming device. The air pump 8 arranged on the hydrogen mixed residual gas outlet pipe is used for providing the conveying pressure of the hydrogen mixed residual gas, so that the hydrogen mixed residual gas can enter the water gas reforming cavity 31.
Example two
In another aspect, a medium pressure hydrogen production method, which uses a medium pressure hydrogen production system, comprises the following steps:
s1, the liquid pump 1 sends methanol water into a methanol steam pipe inlet pipe, the pump pressure is 7-18 MPa, the methanol water is heated and vaporized into methanol steam which enters a reformer 4, the methanol steam carries out reforming reaction in the reformer 4 to generate mixed gas of hydrogen, carbon dioxide and carbon monoxide, and the methanol steam carries out catalytic reaction at corresponding temperature and catalyst filler, so that the system is a multi-component and multi-reaction gas-solid catalytic reaction system;
the reaction equation is: CH (CH)3OH→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 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;
then the mixed gas of hydrogen, carbon dioxide and carbon monoxide is sent into the hydrogen separation chamber 32 of the water gas reforming integrated device 3;
s2, separating the mixed gas of hydrogen, carbon dioxide and carbon monoxide by the hydrogen absorption pipe 33 in the hydrogen separation cavity 32, and outputting the separated pure hydrogen from the hydrogen absorption pipe 33 to be collected; the residual carbon dioxide mixed residual gas is output from the hydrogen separation cavity 32, the pressure of the carbon dioxide mixed residual gas is controlled by the liquid pump 1, the temperature of the carbon dioxide mixed residual gas is controlled by the refrigerator 5, 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 liquid pump 1 is 7-18 MPa, and the temperature controlled by the refrigerator 5 is-25-18 ℃;
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 component 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 6 during working is shown in the following table:
s4, feeding the hydrogen mixed residual gas into a water gas reforming cavity 31 of the water gas reforming integrated device 3, 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 formula is as follows: CO + H2O→CO2+H2；
The water gas reforming reaction device reforms the fed hydrogen mixed residual gas into 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, the reforming mixed gas enters the hydrogen separation cavity 32 to be mixed with the mixed gas of the hydrogen, the carbon dioxide and the carbon monoxide, and the reforming mixed gas and the mixed gas of the hydrogen, the carbon dioxide and the carbon monoxide are subjected to hydrogen separation operation in the hydrogen separation cavity 32.
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.
According to the medium-pressure hydrogen production method, by means of the hydrogen separation and water gas reforming integrated medium-pressure hydrogen production system in the first embodiment, methanol water is used as a hydrogen production raw material, medium pressure (7-18 MPa) is provided by the liquid pump 1 from the source, the methanol water is pumped into the reformer 4 and reacts to generate mixed gas of hydrogen, carbon dioxide and carbon monoxide, then the mixed gas of the hydrogen, the carbon dioxide and the carbon monoxide is sent into the hydrogen separation cavity 32 of the water gas reforming integrated device 3 and directly reacts with the hydrogen absorption pipe 33 in the hydrogen separation cavity 32 to absorb hydrogen, pure hydrogen can be directly output and collected, and hydrogen production efficiency is greatly improved. Then conveying the generated carbon dioxide mixed residual gas, controlling the temperature by a refrigerator 5, indirectly controlling the pressure of the carbon dioxide mixed residual gas by a liquid pump 1, controlling the pressure and the temperature of the carbon dioxide mixed residual gas in a carbon dioxide separation device, liquefying and separating the carbon dioxide in the carbon dioxide separation device, controlling the components of the separated hydrogen mixed residual gas, and making the molar ratio of the carbon dioxide in the hydrogen mixed residual gas lower than 26 percent so as to prepare the hydrogen mixed residual gas for the subsequent reforming mixed gas; the hydrogen mixed residual gas is sent into a water gas reforming cavity 31 of the water gas reforming integrated device 3, the operation temperature of the hydrogen mixed residual gas and the water gas reforming is the same as the hydrogen separation operation temperature of a hydrogen absorption pipe 33, carbon monoxide in the hydrogen mixed residual gas is reduced to 0.5-1.5% from 3-9% originally through water gas water distribution reforming, and the gas phase component of the reformed mixed gas is: 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 hydrogen, carbon dioxide and carbon monoxide prepared by the reformer 4, the reformed mixed gas directly enters the hydrogen separation cavity 32 from the water gas reforming cavity 31, is mixed with the mixed gas of hydrogen, carbon dioxide and carbon monoxide, and is subjected to circular hydrogen absorption separation through the hydrogen absorption pipe 33 again, so that the gas in the system is circularly purified, the theoretical yield can reach 100%, and the hydrogen yield is more than or equal to 95%.
In light of the foregoing description of the preferred embodiment of the present invention, many modifications and variations will be apparent to those skilled in the art 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 (8)
1. A hydrogen separation and water gas reforming integrated medium-pressure hydrogen production system is characterized by comprising a reformer, a three-phase heat exchange device, a steam trap, a refrigerator, a carbon dioxide liquefaction device and a hydrogen separation and water gas reforming integrated device;
the reformer is connected with a methanol steam inlet pipe and a mixed gas outlet pipe; the reformer is suitable for preparing the methanol steam into a mixed gas of hydrogen, carbon dioxide and carbon monoxide;
the water gas reforming integrated device comprises a reaction cavity, wherein a heating cavity is arranged outside the reaction cavity and is suitable for providing reaction temperature for the reaction cavity; a hydrogen separation cavity and a water gas reforming cavity are arranged in the reaction cavity, the hydrogen separation cavity is positioned above the water gas reforming cavity, and the hydrogen separation cavity is communicated with the water gas reforming cavity; the hydrogen separation cavity is provided with a mixed gas inlet and a carbon dioxide mixed residual gas outlet, a hydrogen absorption pipe is inserted into the hydrogen separation cavity and is suitable for separating pure hydrogen, and the hydrogen absorption pipe is connected with a pure hydrogen outlet pipe; the water gas reforming cavity is provided with a catalyst filler, and the water gas reforming cavity is provided with a hydrogen mixed residual gas inlet;
the mixed gas outlet pipe is connected with a mixed gas inlet, the carbon dioxide mixed residual gas outlet is connected with a carbon dioxide mixed residual gas outlet pipe, the carbon dioxide mixed residual gas outlet pipe is sequentially connected with a steam trap, a refrigerator and a carbon dioxide liquefying device, the carbon dioxide liquefying device is connected with a liquid carbon dioxide outlet pipe and a hydrogen mixed residual gas outlet pipe, the hydrogen mixed residual gas outlet pipe is connected with a hydrogen mixed residual gas inlet, and an air pump for providing hydrogen mixed residual gas conveying pressure is arranged on the hydrogen mixed residual gas outlet pipe;
the methanol steam inlet pipe is connected with a liquid pump, the pump pressure of the liquid pump is 7-18 MPa, and the temperature controlled by the refrigerator is-25-18 ℃.
2. The hydrogen separation and water gas reforming integrated medium-pressure hydrogen production system according to claim 1, wherein the carbon dioxide mixed residual gas outlet pipe and the pure hydrogen gas outlet pipe are both connected with a three-phase heat exchange device.
3. The hydrogen separation and water gas reforming integrated medium-pressure hydrogen production system as claimed in claim 1, wherein the hydrogen absorption pipe is a niobium pipe, the catalyst filler is a copper-based filler, and the operating temperature of the reaction chamber is 200-350 ℃;
or the catalyst filler is a zirconium-based filler, and the operating temperature of the reaction chamber is 350-550 ℃.
4. The hydrogen separation and water gas reforming integrated medium-pressure hydrogen production system as claimed in claim 1, wherein the hydrogen absorption tube is a palladium membrane tube or a palladium alloy membrane tube, the catalyst filler is a zirconium-based filler, and the operating temperature of the reaction chamber is 250-550 ℃.
5. The hydrogen separation and water gas reforming integrated medium-pressure hydrogen production system according to claim 1, 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 feeding pure hydrogen gas into the hydrogen storage tank, and the hydrogen storage tank is connected with a hydrogenation machine.
6. A medium-pressure hydrogen production method is characterized in that the medium-pressure hydrogen production system adopting any one of the above 1-5 comprises the following steps:
s1, feeding methanol water into a methanol steam pipe inlet pipe by a liquid pump, wherein the pump pressure is 7-18 MPa, heating and vaporizing the methanol water to form methanol steam, feeding the methanol steam into a reformer, carrying out a reforming reaction on the methanol steam in the reformer to generate a mixed gas of hydrogen, carbon dioxide and carbon monoxide, and feeding the mixed gas of the hydrogen, the carbon dioxide and the carbon monoxide into a hydrogen separation cavity of the water gas reforming integrated device;
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 in the hydrogen separation cavity, 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 hydrogen separation cavity, the pressure of the carbon dioxide mixed residual gas is controlled by a liquid pump, 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 control pressure of the liquid pump is 7-18 MPa, and the control temperature of the refrigerator is-25-18 ℃;
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 cavity of the water gas reforming integrated device, 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;
water is distributed in the water gas reforming cavity to reform the fed hydrogen mixed residual gas into reformed mixed gas, 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, the reforming mixed gas enters the hydrogen separation cavity to be mixed with the mixed gas of hydrogen, carbon dioxide and carbon monoxide, and the reforming mixed gas and the mixed gas of hydrogen, carbon dioxide and carbon monoxide are subjected to hydrogen separation operation in the hydrogen separation cavity.
7. The method for producing hydrogen from methanol water under medium pressure as claimed in claim 6, wherein the mixed residual gas of pure hydrogen and carbon dioxide is outputted after being subjected to heat exchange and temperature reduction by a three-phase heat exchange device, and the methanol water is subjected to heat exchange and vaporization by the three-phase heat exchange device to form methanol steam.
8. The method for producing hydrogen by methanol-water medium pressure as claimed in claim 6, wherein the methanol-water is replaced by natural gas.
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