CN211998811U - Reforming and separating integrated medium-pressure hydrogen production system - Google Patents
Reforming and separating integrated medium-pressure hydrogen production system Download PDFInfo
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- CN211998811U CN211998811U CN201921827366.0U CN201921827366U CN211998811U CN 211998811 U CN211998811 U CN 211998811U CN 201921827366 U CN201921827366 U CN 201921827366U CN 211998811 U CN211998811 U CN 211998811U
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Abstract
The utility model relates to a reforming and separating integrated medium-pressure hydrogen production system, which comprises a reforming and separating device, a three-phase heat exchange device, a steam trap, a refrigerator and a carbon dioxide liquefying device; the methanol steam inlet pipe is connected with a liquid pump, and the pump pressure of the liquid pump is 7-18 MPa; the temperature controlled by the refrigerator is-25-18 ℃. 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 reforming and separating integrated medium-pressure hydrogen production system.
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 reforming and separation integrated medium-pressure hydrogen production system is provided, and the problem that the conventional methanol steam reformer, hydrogen separation and water gas reforming are three independent devices, so that the hydrogen production system is complicated is solved.
The utility model provides a technical scheme that its technical problem adopted is:
a reforming and separating integrated medium-pressure hydrogen production system comprises a reforming and separating device, a three-phase heat exchange device, 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 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, the hydrogen mixed residual gas outlet pipe is connected with a second inlet of the reforming and separating device, and an air pump for increasing the conveying pressure of the hydrogen mixed residual gas in the pipe is arranged on the hydrogen mixed residual gas outlet pipe;
the methanol steam inlet pipe is connected with a liquid pump, and the pump pressure of the liquid pump is 7-18 MPa;
the temperature controlled by the refrigerator is-25-18 ℃.
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 operating temperature of the upper reaction chamber and the lower reaction chamber 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 operating temperature of the upper reaction chamber and the lower reaction chamber 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 medium-pressure hydrogen production method using the reforming and separation integrated 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 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 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;
controlling the temperature of the refrigerator to be-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 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 utility model has the advantages that:
the utility model discloses a middling pressure hydrogen manufacturing system inhales hydrogen separation, hydrogen mixing residual gas reforming with methanol steam reforming, mist and all integrates and go on under a reaction chamber, same operating temperature, makes and realizes methanol-water reforming device, hydrogen separator, water gas reformer integration, optimizes the overall arrangement structure of whole hydrogen manufacturing system to rely on this hydrogen manufacturing system to make miniature hydrogen manufacturing equipment.
The utility model discloses among the middling pressure hydrogen manufacturing system, provide the reforming reaction environment of middling pressure through the liquid pump, the pressure that the liquid pump provided is 7 ~ 18MPa, make whole hydrogen manufacturing system when to handling carbon dioxide mixed residual gas, only need dispose a refrigerator and control the temperature (-25 ~ 18 ℃) of carbon dioxide mixed residual gas in the carbon dioxide liquefying plant, the pressure of carbon dioxide mixed residual gas in the carbon dioxide liquefying plant is direct to be controlled from the source by the liquid pump, make middling pressure hydrogen manufacturing system compare low pressure hydrogen manufacturing, can save an air compressor machine (low pressure hydrogen manufacturing need dispose an air compressor machine alone and provide the pressure of liquefaction work for carbon dioxide mixed residual gas), make middling pressure hydrogen manufacturing system obtain simplifying the optimization.
The utility model discloses medium-pressure hydrogen production method, methanol steam reforming separation and the hydrogen absorption separation of hydrogen absorption pipe are all gone on in last reaction chamber, the hydrogen of separation is gathered and is collected, the mixed residual gas of carbon dioxide who separates carries out recovery processing, through liquid pump and refrigerator control to carbon dioxide mixed residual gas the pressure and the temperature of separating liquid carbon dioxide, pass through carbon dioxide liquefying plant with carbon dioxide mixed residual gas and separate hydrogen mixed residual gas and liquid carbon dioxide, liquid carbon dioxide can be saved, carbon dioxide liquefying plant is in the separation, through control pressure and temperature, the gas phase component in the mixed residual gas of hydrogen has been controlled, make the carbon dioxide molar ratio in the mixed residual gas of hydrogen be less than 26%, make the mixed residual gas of hydrogen make ready for the reforming mixture in back; and (3) reforming the hydrogen mixed residual gas by water gas water distribution in the reaction cavity, 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 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 reforming, separation integrated medium 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 chamber 31, a lower reaction chamber 32, a heating chamber 33, a heating chamber 34, a hydrogen absorption pipe 4, a carbon dioxide liquefying device 5, a refrigerating machine 6, a steam trap 7 and an air pump.
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 reforming and separation integrated medium-pressure hydrogen production system comprises a reforming and separation device 3, a three-phase heat exchange device 2, a steam trap 6, a refrigerator 5 and a carbon dioxide liquefaction 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 chamber 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 a three-phase heat exchange device 2, the carbon dioxide mixed residual gas outlet pipe is sequentially connected with a steam trap 6, 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, the hydrogen mixed residual gas outlet pipe is connected with a second inlet of the reforming and separating device 3, and an air pump 7 for increasing the conveying pressure of the hydrogen mixed residual gas in the pipe is arranged on the hydrogen mixed residual gas outlet pipe;
the steam trap 6 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 7-18 MPa; the temperature controlled by the refrigerator 5 is-25 to 18 ℃.
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 operating temperature of the upper reaction chamber 31 and the lower reaction chamber 32 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 operating temperature of the upper reaction chamber 31 and the lower reaction chamber 32 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 chamber 31 absorbs hydrogen from the 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 rest carbon dioxide mixed residual gas is output from a carbon dioxide mixed residual gas outlet pipe of the upper reaction chamber 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 a hydraulic pump 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 chamber 32 of a reforming separation device 3 for water gas distribution reforming, the hydrogen mixed residual gas is changed into reformed mixed gas after water gas reforming, and the gas phase component of the reformed mixed gas reacts with the reforming reaction to generate hydrogen, The component proportion of the mixed gas of carbon dioxide and carbon monoxide is approximate, the reformed mixed gas enters the upper reaction cavity 31 from the lower reaction cavity 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 medium-pressure hydrogen production system is improved.
The utility model discloses a middling pressure hydrogen manufacturing system, 3 integrated methanol-steam reforming of reforming separator, hydrogen separation, water gas reforming three functions optimize hydrogen manufacturing system, rely on this hydrogen manufacturing system to make miniature hydrogen manufacturing equipment. The pressure provided by the liquid pump 1 is 2-5 MPa, the whole hydrogen production system runs in a medium-pressure state, and the hydrogen production operation is safer.
The utility model discloses among the middling pressure hydrogen manufacturing system, provide the reforming reaction environment of middling pressure through liquid pump 1, the pressure that liquid pump 1 provided is 7 ~ 18MPa, make whole hydrogen manufacturing system when to handling carbon dioxide mixed residual gas, only need dispose a refrigerator 5 and control the temperature (-25 ~ 18 ℃) of carbon dioxide mixed residual gas in carbon dioxide liquefying plant 4, the pressure of carbon dioxide mixed residual gas in carbon dioxide liquefying plant 4 is direct to be controlled from the source by liquid pump 1, make middling pressure hydrogen manufacturing system compare low pressure hydrogen manufacturing, can save an air compressor machine (low pressure hydrogen manufacturing need dispose an air compressor machine alone and provide the pressure of liquefaction work for carbon dioxide mixed residual gas), make middling pressure hydrogen manufacturing system obtain simplifying the optimization.
Example two
A medium-pressure hydrogen production method adopts the reforming and separation integrated medium-pressure hydrogen production system, and comprises the following steps:
s1, the liquid pump 1 sends the 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 an upper reaction cavity 31 of the reforming separation device 3, the methanol steam carries out reforming reaction in the upper reaction cavity 31 to generate mixed gas of hydrogen, carbon dioxide and carbon monoxide,
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);
then the hydrogen absorption pipe 34 performs hydrogen separation on the generated 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 34, and collecting the separated pure hydrogen output from the hydrogen absorption pipe 34; 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 a liquid pump 1, 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 temperature controlled by the refrigerator 5 is-25 to 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 4 during working is shown in the following table:
| scheme(s) | Pressure (Mpa) | Temperature (. degree.C.) |
| |
7 | -25 |
| |
10 | -10 |
| |
15 | 0 |
| |
18 | 18 |
S4, feeding the hydrogen mixed residual gas into a lower reaction cavity 32 of a reforming separation device 3, 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;
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.
The utility model discloses a middling pressure hydrogen manufacturing method relies on reforming in the embodiment one, separation integral type middling pressure hydrogen manufacturing system, regard methanol water as the hydrogen manufacturing raw materials, liquid pump 1 provides middling pressure (7 ~ 18MPa) at the source and pumps methanol water into reforming separation device 3's last reaction chamber 31 in, the reaction generates hydrogen, the mist of carbon dioxide and carbon monoxide, then inhale hydrogen pipe 34 and inhale hydrogen to the mist reaction of hydrogen, carbon dioxide and carbon monoxide, pure hydrogen can direct output and gather, hydrogen manufacturing efficiency improves greatly. 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 liquid pump 1 and a refrigerator 5 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%.
According to the hydrogen production method, a medium-pressure reforming reaction environment is provided through the liquid pump 1, the pressure provided by the liquid pump 1 is 7-18 MPa, 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 4, and the pressure of the carbon dioxide mixed residual gas in the carbon dioxide liquefying device 4 is directly controlled from the source through the liquid pump 1, so that the medium-pressure hydrogen production system is compared with low-pressure hydrogen production, an air compressor (an air compressor is needed to be independently configured for low-pressure hydrogen production to provide the pressure for liquefying work of the carbon dioxide mixed residual gas) can be omitted, and the medium-pressure hydrogen production system is simplified and optimized.
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 (4)
1. A reforming and separating integrated medium-pressure hydrogen production system is characterized by comprising a reforming and separating device, a three-phase heat exchange device, 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 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, the hydrogen mixed residual gas outlet pipe is connected with a second inlet of the reforming and separating device, and an air pump for increasing the conveying pressure of the hydrogen mixed residual gas in the pipe is arranged on the hydrogen mixed residual gas outlet pipe;
the methanol steam inlet pipe is connected with a liquid pump, and the pump pressure of the liquid pump is 7-18 MPa;
the temperature controlled by the refrigerator is-25-18 ℃.
2. The reforming and separation integrated medium-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 operating temperature of the upper reaction chamber and the lower reaction chamber is 200-500 ℃.
3. The reforming and separation integrated medium-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 upper reaction chamber and the lower reaction chamber is 250-550 ℃.
4. The reforming and separation integrated medium-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.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111017876A (en) * | 2019-10-28 | 2020-04-17 | 中科液态阳光(苏州)氢能科技发展有限公司 | Reforming and separating integrated medium-pressure hydrogen production system and hydrogen production method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111017876A (en) * | 2019-10-28 | 2020-04-17 | 中科液态阳光(苏州)氢能科技发展有限公司 | Reforming and separating integrated medium-pressure hydrogen production system and hydrogen production method thereof |
| CN111017876B (en) * | 2019-10-28 | 2023-08-01 | 中科液态阳光(苏州)氢能科技发展有限公司 | Reforming and separating integrated medium-pressure hydrogen production system and hydrogen production method thereof |
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