CN110937572A - Reforming and separating integrated low-pressure hydrogen production system and hydrogen production method thereof - Google Patents
Reforming and separating integrated low-pressure hydrogen production system and hydrogen production method thereof Download PDFInfo
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- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
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- C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
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- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
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- C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
- C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
- C01B2203/0233—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a steam reforming step
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- C01B2203/12—Feeding the process for making hydrogen or synthesis gas
- C01B2203/1205—Composition of the feed
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- C01B2203/1205—Composition of the feed
- C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
- C01B2203/1235—Hydrocarbons
- C01B2203/1241—Natural gas or methane
Abstract
The invention relates to a reforming and separating 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 and a carbon dioxide liquefying device, wherein the three-phase heat exchange device is connected with the air compressor; the pumping 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 ℃. A low-pressure hydrogen production method, methanol vapor carries on the reforming reaction in the upper reaction chamber, then the hydrogen absorption pipe carries on the hydrogen separation to the gas mixture; the carbon dioxide mixed residual gas is prepared into liquid carbon dioxide and hydrogen mixed residual gas in a carbon dioxide separator, and the proportion of the reformed mixed gas is close to the proportion of the mixed gas of hydrogen, carbon dioxide and carbon monoxide; the hydrogen absorption pipe performs hydrogen separation operation on the reformed mixed gas and the mixed gas of hydrogen, carbon dioxide and carbon monoxide. 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 reforming and separating integrated low-pressure hydrogen production system and a hydrogen production 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 reforming and separation integrated reaction device is provided, and the problem that a hydrogen production system is numerous and complicated due to the fact that a reformer of methanol steam, hydrogen separation and water gas reforming are three independent devices in the prior art 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 technical scheme adopted by the invention for solving the technical problems is as follows:
a reforming and separating 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 and a carbon dioxide liquefying device;
the reforming separation device comprises an upper reaction cavity and a lower reaction cavity, the upper reaction cavity is communicated with the lower reaction cavity, the upper reaction cavity is filled with a first catalytic filler, and the lower reaction cavity is filled with a second catalytic filler;
the upper reaction cavity is provided with a first inlet for inputting methanol steam and a first outlet for outputting carbon dioxide mixed residual gas, a hydrogen absorption pipe is inserted into the upper reaction cavity, and the hydrogen absorption pipe performs hydrogen absorption and separation on the mixed gas in the upper reaction cavity and outputs the absorbed hydrogen from the hydrogen absorption pipe; the lower reaction cavity is provided with a second inlet for inputting the hydrogen mixed residual gas;
the first inlet is connected with a methanol steam inlet pipe, the outlet of the hydrogen absorption pipe is connected with a pure hydrogen gas outlet pipe, the first outlet is connected with a carbon dioxide mixed residual gas outlet pipe, the methanol steam inlet pipe, the pure hydrogen gas outlet pipe and the carbon dioxide mixed residual gas outlet pipe are all connected with a three-phase heat exchange device, the carbon dioxide mixed residual gas outlet pipe is sequentially connected with an air compressor, a steam trap, a refrigerator and a carbon dioxide liquefying device, the carbon dioxide liquefying device is connected with a hydrogen mixed residual gas outlet pipe, and the hydrogen mixed residual gas outlet pipe is connected with a second inlet of the reforming and separating 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 hydrogen absorption pipe is a niobium pipe, the first catalytic filler is a copper-based filler or a zirconium-based filler, the second catalytic filler is a copper-based filler or a zirconium-based filler, and the temperature of the heating cavity operation is 200-500 ℃.
Further, the hydrogen absorption pipe is a palladium membrane pipe or a palladium alloy membrane pipe, the first catalytic filler is a copper-based filler or a zirconium-based filler, the second catalytic filler is a copper-based filler or a zirconium-based filler, and the temperature of the heating cavity operation is 250-550 ℃.
Further, the pure hydrogen gas outlet pipe is connected with a hydrogen storage tank, a compressor is arranged on the pure hydrogen gas outlet pipe and suitable for sending the pure hydrogen gas into the hydrogen storage tank, and the hydrogen storage tank is connected with a hydrogenation machine.
In another aspect, a low-pressure hydrogen production method using the reforming and separation integrated low-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 2-5 MPa, heating and vaporizing the methanol water to form methanol steam, feeding the methanol steam into an upper reaction cavity of a reforming and separating device, carrying out reforming reaction on the methanol steam in the upper reaction cavity to generate mixed gas of hydrogen, carbon dioxide and carbon monoxide, and then carrying out hydrogen separation on the generated mixed gas of the hydrogen, the carbon dioxide and the carbon monoxide by a hydrogen absorption pipe;
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 a carbon dioxide mixed residual gas outlet pipe, 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 lower reaction cavity of a reforming separation device, preparing reforming 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 lower reaction chamber 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, enabling the reformed mixed gas to enter the upper reaction cavity to be mixed with the mixed gas of hydrogen, carbon dioxide and carbon monoxide, and carrying out hydrogen separation operation on the reformed mixed gas and the mixed gas of hydrogen, carbon dioxide and carbon monoxide by the hydrogen absorption pipe.
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 low-pressure hydrogen production system, methanol steam reforming, hydrogen absorption and separation of mixed gas and hydrogen mixed residual gas reforming are integrated in a reaction cavity at the same operation temperature, so that the methanol water reforming device, the hydrogen separation device and the water gas reformer are integrated, the layout structure of the whole hydrogen production system is optimized, and the hydrogen production system can be made into small hydrogen production equipment.
The invention relates to a low-pressure hydrogen production method, wherein methanol steam reforming separation and hydrogen absorption separation of a hydrogen absorption pipe are carried out in an upper reaction cavity, separated hydrogen is collected and collected, separated carbon dioxide mixed residual gas is recycled, the pressure and temperature of the separated liquid carbon dioxide are controlled by an air compressor and a refrigerator aiming at the carbon dioxide mixed residual gas, the hydrogen mixed residual gas and the liquid carbon dioxide are separated from the carbon dioxide mixed residual gas by a carbon dioxide liquefying device, the liquid carbon dioxide can be stored, and the gas-phase component in the hydrogen mixed residual gas is controlled by controlling the pressure and the temperature when the carbon dioxide liquefying device separates, so that the molar ratio of the carbon dioxide in the hydrogen mixed residual gas is lower than 26 percent, and the hydrogen mixed residual gas is prepared for the subsequent reforming mixed gas; and (3) reforming the hydrogen mixed residual gas by water gas water distribution in the reaction cavity at last, 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 enter the upper reaction chamber again, the mixed gas is mixed with the mixed gas of the hydrogen, the carbon dioxide and the carbon monoxide, the hydrogen absorption pipe performs hydrogen purification and separation to prepare hydrogen again, 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 realized2And zero emission is realized.
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 invention is further described below with reference to the accompanying drawings.
FIG. 1 is a reforming, separation integrated low pressure hydrogen production system;
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 and separating device 3, an upper reaction cavity 31, a lower reaction cavity 32, a heating cavity 33, a heating cavity 34, a hydrogen absorption pipe 4, a carbon dioxide liquefying device 5, a refrigerating machine 6, an air compressor 7 and a steam trap.
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 reforming and separating integrated low-pressure hydrogen production system comprises a reforming and separating device 3, a three-phase heat exchange device 2, an air compressor, a steam trap, a refrigerator 5 and a carbon dioxide liquefying device 4.
The reforming separation device 3 comprises an upper reaction cavity 31 and a lower reaction cavity 32, the upper reaction cavity 31 is communicated with the lower reaction cavity 32, the upper reaction cavity 31 is filled with a first catalytic filler, and the lower reaction cavity 32 is filled with a second catalytic filler;
the upper reaction cavity 31 is provided with a first inlet for inputting methanol steam and a first outlet for outputting carbon dioxide mixed residual gas, a hydrogen absorption pipe 34 is inserted into the upper reaction cavity 31, and the hydrogen absorption pipe 34 performs hydrogen absorption and separation on the mixed gas in the upper reaction cavity 31 and outputs the absorbed hydrogen from the hydrogen absorption pipe 34; the lower reaction cavity 32 is provided with a second inlet for inputting the hydrogen mixed residual gas;
the first inlet is connected with a methanol steam inlet pipe, the outlet of the hydrogen absorption pipe 34 is connected with a pure hydrogen gas outlet pipe, the first outlet is connected with a carbon dioxide mixed residual gas outlet pipe, the methanol steam inlet pipe, the pure hydrogen gas outlet pipe and the carbon dioxide mixed residual gas outlet pipe are all connected with the three-phase heat exchange device 2, the carbon dioxide mixed residual gas outlet pipe is sequentially connected with an air compressor 6, a steam trap 7, a refrigerator 5 and a carbon dioxide liquefying device 4, the carbon dioxide liquefying device 4 is connected with a hydrogen mixed residual gas outlet pipe, and the hydrogen mixed residual gas outlet pipe is connected with a second inlet of the reforming and separating device 3;
the steam trap 7 is used for removing moisture in the carbon dioxide mixed residual gas, and the carbon dioxide mixed residual gas is liquefied by carbon dioxide after controlling the moisture.
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 6 is 5-30 MPa, and the temperature controlled by the refrigerator 5 is-35-30.8 ℃.
Specifically, the hydrogen absorption pipe 34 is a niobium pipe, the first catalytic filler is a copper-based filler or a zirconium-based filler, the second catalytic filler is a copper-based filler or a zirconium-based filler, and the operation temperature of the heating cavity 33 is 200-500 ℃.
The hydrogen absorption pipe 34 may also be a palladium membrane pipe or a palladium alloy membrane pipe, the first catalytic filler is a copper-based filler or a zirconium-based filler, the second catalytic filler is a copper-based filler or a zirconium-based filler, and the operation temperature of the heating cavity 33 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.
The pure hydrogen gas outlet pipe is connected with a hydrogen storage tank, a compressor is arranged on the pure hydrogen gas outlet pipe and is suitable for sending the pure hydrogen gas 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 upper reaction cavity 31 of the reforming separation device 3, the heating cavity 33 is heated to control the temperature in the upper reaction cavity 31, and the methanol steam carries out catalytic reaction under the corresponding temperature and catalyst filler, so that the multi-component and multi-reaction gas-solid catalytic reaction system is formed;
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.
A hydrogen absorption pipe 34 in the upper reaction cavity 31 absorbs hydrogen from a mixed gas of hydrogen, carbon dioxide and carbon monoxide, the hydrogen absorption pipe 34 separates hydrogen in the mixed gas, pure hydrogen is collected into a hydrogen storage tank after being output through the hydrogen absorption pipe 34, the residual carbon dioxide mixed residual gas is output from a carbon dioxide mixed residual gas outlet pipe of the upper reaction cavity 31, 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 the carbon dioxide separation device are controlled through an air compressor 6 and a refrigerator 5, then the carbon dioxide mixed residual gas and the carbon dioxide separation device carry out liquefaction separation, the separated liquid carbon dioxide is collected, the separated hydrogen mixed residual gas is sent into a lower reaction cavity 32 of a reforming separation device 3 for water gas water distribution reforming, and 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 is close to that of the mixed gas component of hydrogen, carbon dioxide and carbon monoxide generated by reforming reaction, the reformed mixed gas enters the upper reaction chamber 31 from the lower reaction chamber 32 and is mixed with the mixed gas of hydrogen, carbon dioxide and carbon monoxide, and the hydrogen absorption pipe 34 continuously absorbs and separates the mixed gas, so that the hydrogen yield of the whole low-pressure hydrogen production system is improved.
According to the low-pressure hydrogen production system, the reforming and separating device 3 integrates the functions of methanol steam reforming, hydrogen separation and water gas reforming, the hydrogen production system is optimized, and small hydrogen production equipment can be manufactured by means of the hydrogen production system. The pressure provided by the liquid pump 1 is 2-5 MPa, the whole hydrogen production system runs in a low-pressure state, and the hydrogen production operation is safer.
Example two
The method for producing hydrogen at low pressure comprises the following steps:
s1, the liquid pump 1 sends methanol water into a methanol steam pipe inlet pipe, the pump pressure is 2-5 MPa, the methanol water is heated and vaporized into methanol steam which enters an upper reaction cavity 31 of a reforming separation device 3, and the methanol steam carries out reforming reaction in the upper reaction cavity 31 to generate mixed gas of hydrogen, carbon dioxide and carbon monoxide, which 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 hydrogen absorption pipe 34 performs hydrogen separation on the generated mixed gas of hydrogen, carbon dioxide and carbon monoxide;
s2, inserting the hydrogen absorption tube 34 in the upper reaction chamber 31 to separate the mixed gas of hydrogen, carbon dioxide and carbon monoxide, and outputting the separated pure hydrogen from the hydrogen absorption tube 34 to be collected; the residual carbon dioxide mixed residual gas is output from a carbon dioxide mixed residual gas outlet pipe, the pressure of the carbon dioxide mixed residual gas is controlled by an air compressor 6, the temperature of the carbon dioxide mixed residual gas is controlled by a 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 air compressor 6 is 5-30 MPa, and the temperature controlled by the refrigerator 5 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;
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 4 during working is shown in the following table:
s4, feeding the hydrogen mixed residual gas into a lower reaction cavity 32 of a reforming separation device 3, uniformly controlling the working temperature of the lower reaction cavity 32 and the working temperature of an upper reaction cavity 31 by a heating cavity 33, distributing water to the hydrogen mixed residual gas to prepare reformed mixed gas, distributing water according to the content of carbon monoxide, wherein the ratio of the water distribution (carbon monoxide: water) is 1: 1-20;
the water gas reforming reaction formula is as follows: CO + H2O→CO2+H2；
Water is distributed in the lower reaction cavity 32 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;
s5, the reforming mixed gas enters the upper reaction cavity 31 to be mixed with the mixed gas of hydrogen, carbon dioxide and carbon monoxide, and the hydrogen absorption pipe 34 carries out hydrogen separation operation on the reforming mixed gas and the mixed gas of hydrogen, carbon dioxide and carbon monoxide.
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 low-pressure hydrogen production method, by means of the reforming and separation integrated low-pressure hydrogen production system in the first embodiment, methanol water is used as a hydrogen production raw material, the liquid pump 1 provides low pressure (2-5 MPa) at the source to pump the methanol water into the upper reaction cavity 31 of the reforming and separation device 3, a mixed gas of hydrogen, carbon dioxide and carbon monoxide is generated through reaction, then the hydrogen absorption pipe 34 reacts with the mixed gas of the hydrogen, the carbon dioxide and the carbon monoxide to absorb hydrogen, pure hydrogen can be directly output and collected, and the hydrogen production efficiency is greatly improved. Then, conveying the generated carbon dioxide mixed residual gas, controlling the pressure and the temperature of the carbon dioxide mixed residual gas in a carbon dioxide separation device through a gas preparation compressor 6 and a cold machine 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; the hydrogen mixed residual gas is sent into the lower reaction cavity 32 of the reforming separation device 3, the working temperature of the lower reaction cavity 32 and the upper reaction cavity 31 and the working temperature of the hydrogen absorption pipe 34 are uniformly controlled by the heating cavity 33, the hydrogen mixed residual gas is reformed by water gas water distribution, carbon monoxide in the hydrogen mixed residual gas is reduced to 0.5-1.5% from 3-9% originally, 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, the reformed mixed gas directly enters the upper reaction chamber 31 from the lower reaction chamber 32, 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 34 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 (7)
1. A reforming and separating 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 and a carbon dioxide liquefying device;
the reforming separation device comprises an upper reaction cavity and a lower reaction cavity, the upper reaction cavity is communicated with the lower reaction cavity, the upper reaction cavity is filled with a first catalytic filler, and the lower reaction cavity is filled with a second catalytic filler;
the upper reaction cavity is provided with a first inlet for inputting methanol steam and a first outlet for outputting carbon dioxide mixed residual gas, a hydrogen absorption pipe is inserted into the upper reaction cavity, and the hydrogen absorption pipe performs hydrogen absorption and separation on the mixed gas in the upper reaction cavity and outputs the absorbed hydrogen from the hydrogen absorption pipe; the lower reaction cavity is provided with a second inlet for inputting the hydrogen mixed residual gas;
the first inlet is connected with a methanol steam inlet pipe, the outlet of the hydrogen absorption pipe is connected with a pure hydrogen gas outlet pipe, the first outlet is connected with a carbon dioxide mixed residual gas outlet pipe, the methanol steam inlet pipe, the pure hydrogen gas outlet pipe and the carbon dioxide mixed residual gas outlet pipe are all connected with a three-phase heat exchange device, the carbon dioxide mixed residual gas outlet pipe is sequentially connected with an air compressor, a steam trap, a refrigerator and a carbon dioxide liquefying device, the carbon dioxide liquefying device is connected with a hydrogen mixed residual gas outlet pipe, and the hydrogen mixed residual gas outlet pipe is connected with a second inlet of the reforming and separating 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 reforming and separation integrated low-pressure hydrogen production system according to claim 1, wherein the hydrogen absorption pipe is a niobium pipe, the first catalytic filler is a copper-based filler or a zirconium-based filler, the second catalytic filler is a copper-based filler or a zirconium-based filler, and the temperature of the heating chamber operation is 200-500 ℃.
3. The reforming and separation integrated low-pressure hydrogen production system according to claim 1, wherein the hydrogen absorption pipe is a palladium film pipe or a palladium alloy film pipe, the first catalytic filler is a copper-based filler or a zirconium-based filler, the second catalytic filler is a copper-based filler or a zirconium-based filler, and the operating temperature of the heating chamber is 250-550 ℃.
4. The reforming and separation integrated low-pressure hydrogen production system according to claim 1, wherein the pure hydrogen gas outlet pipe is connected with a hydrogen storage tank, a compressor is arranged on the pure 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.
5. A low-pressure hydrogen production method is characterized in that the reforming and separation integrated low-pressure hydrogen production system of any one of claims 1 to 4 is adopted, and 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 an upper reaction cavity of a reforming and separating device, carrying out reforming reaction on the methanol steam in the upper reaction cavity to generate mixed gas of hydrogen, carbon dioxide and carbon monoxide, and then carrying out hydrogen separation on the generated mixed gas of the hydrogen, the carbon dioxide and the carbon monoxide by a hydrogen absorption pipe;
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 a carbon dioxide mixed residual gas outlet pipe, 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 lower reaction cavity of a reforming separation device, preparing reforming 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 lower reaction chamber 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, enabling the reformed mixed gas to enter the upper reaction cavity to be mixed with the mixed gas of hydrogen, carbon dioxide and carbon monoxide, and carrying out hydrogen separation operation on the reformed mixed gas and the mixed gas of hydrogen, carbon dioxide and carbon monoxide by the hydrogen absorption pipe.
6. The low-pressure hydrogen production method according to claim 5, wherein the output pure hydrogen and carbon dioxide mixed residual gas are output after being subjected to heat exchange and temperature reduction through a three-phase heat exchange device, and the methanol water is subjected to heat exchange and vaporization through the three-phase heat exchange device to form methanol steam.
7. The low pressure hydrogen production process according to claim 5, wherein the methanol water is replaced with natural gas.
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