CN213112522U - Reforming and separating integrated high-pressure hydrogen production system - Google Patents
Reforming and separating integrated high-pressure hydrogen production system Download PDFInfo
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- CN213112522U CN213112522U CN201921827368.XU CN201921827368U CN213112522U CN 213112522 U CN213112522 U CN 213112522U CN 201921827368 U CN201921827368 U CN 201921827368U CN 213112522 U CN213112522 U CN 213112522U
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Abstract
The utility model relates to a reforming and separating integrated high-pressure hydrogen production system, which comprises a reforming and separating device, a three-phase heat exchange device, a steam trap, a water-cooling heat exchanger and a carbon dioxide liquefying device; the pump pressure of the liquid pump is 18-50 Mpa, the water-cooling heat exchanger is connected with the water-cooling tower, and the operating temperature of the water-cooling heat exchanger is 18-30.8 ℃. The gas in the system is circularly purified, the theoretical yield can reach 100 percent, and the yield of the hydrogen is more than or equal to 95 percent.
Description
Technical Field
The utility model relates to a reforming and separating integrated high-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 high-pressure hydrogen production system is provided, and the problem that the hydrogen production system is complicated due to the fact that a reformer for methanol steam, hydrogen separation and water gas reforming are three independent devices in the prior art is solved.
The utility model provides a technical scheme that its technical problem adopted is:
a reforming and separating integrated high-pressure hydrogen production system comprises a reforming and separating device, a three-phase heat exchange device, a steam trap, a water-cooling heat exchanger 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 water-cooling heat exchanger 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 improving the conveying pressure of the hydrogen mixed residual gas in the pipe is arranged on the hydrogen mixed residual gas;
the methanol steam inlet pipe is connected with a liquid pump, the pump pressure of the liquid pump is 18-50 Mpa, the water-cooled heat exchanger is connected with a water-cooled tower, and the operating temperature of the water-cooled heat exchanger is 18-30.8 ℃.
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 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, the pure hydrogen gas is pumped into the hydrogen storage tank under the pressure of a liquid pump, the hydrogen storage tank is connected with a hydrogenation machine, and the hydrogen storage tank is connected with the hydrogenation machine.
In another aspect, a high-pressure hydrogen production method, which adopts the reforming and separation integrated high-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 18-50 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 water-cooling heat exchanger, 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 18-50 Mpa, and the control temperature of the water-cooling heat exchanger is 18-30.8 ℃;
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 utility model has the advantages that:
the utility model discloses a high pressure hydrogen manufacturing system inhales hydrogen separation, hydrogen mixing residual gas reforming with methanol steam reforming, mist and all carries out under a reaction chamber, same operating temperature, makes realization methanol water reforming device, hydrogen separator, water gas reformer integration, optimizes whole hydrogen manufacturing system's overall arrangement structure to rely on this hydrogen manufacturing system to make miniature hydrogen manufacturing equipment.
In the hydrogen production system of the utility model, high pressure (18-50 MPa) hydrogen production pressure is provided by the liquid pump, so that when the whole hydrogen production system is used for treating carbon dioxide mixed residual gas, only a water-cooling heat exchanger is needed to be configured to control the temperature of the carbon dioxide mixed residual gas in the carbon dioxide liquefying device, the pressure of the carbon dioxide mixed residual gas in the carbon dioxide liquefying device is directly controlled by the liquid pump from the source, compared with low-pressure hydrogen production, the high-pressure hydrogen production system can save an air compressor (the low-pressure hydrogen production system needs to be separately configured with an air compressor to provide the pressure for liquefying the carbon dioxide mixed residual gas), compared with a medium-pressure hydrogen production system, the traditional refrigerator can be changed into the existing water-cooling heat exchanger to carry out temperature control, the operation temperature of the carbon dioxide mixed residual gas entering a carbon dioxide separator is controlled by the, the temperature is controlled to be 18-30.8 ℃, and the water-cooled heat exchanger and the water-cooled tower control the temperature, so that the method has the advantages of low cost and stable and reliable operation, and is suitable for installing the hydrogen production system in the region with the outdoor temperature of 18-30.8 ℃ throughout the year.
The utility model discloses high pressure hydrogen manufacturing method, methanol steam reforming separation and 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, the pressure and the temperature of separating liquid carbon dioxide to the mixed residual gas of carbon dioxide through liquid pump and refrigerator control, separate out mixed residual gas of hydrogen and liquid carbon dioxide through carbon dioxide liquefying plant with the mixed residual gas of carbon dioxide, liquid carbon dioxide can be stored, carbon dioxide liquefying plant is in the separation, through control pressure and temperature, gaseous 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 of back end; 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, and safety (high-pressure hydrogen storage is reduced) and economy (due to the fact that the hydrogen storage tank A is safe and economical) are really realizedAlcohol transportation cost much lower than that of hydrogen), and also recover CO2And 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 present invention will be further explained with reference to the accompanying drawings.
FIG. 1 is a reforming, separation integrated high 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 water-cooling heat exchanger 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 separating integrated high-pressure hydrogen production system comprises a reforming and separating device 3, a three-phase heat exchange device 2, a steam trap 6, a water-cooling heat exchanger 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 a three-phase heat exchange device 2, the carbon dioxide mixed residual gas outlet pipe is sequentially connected with a steam trap 6, a water-cooled heat exchanger 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 improving the conveying pressure of the hydrogen mixed residual gas in the pipe is arranged on the hydrogen mixed residual gas;
the steam trap 6 is used for removing water in the carbon dioxide mixed residual gas, and the carbon dioxide mixed residual gas is liquefied by carbon dioxide after controlling the water.
The methanol steam inlet pipe is connected with a liquid pump 1, the pump pressure of the liquid pump 1 is 18-50 Mpa, the water-cooled heat exchanger 5 is connected with a water-cooled tower, and the operation temperature of the water-cooled heat exchanger 5 is 18-30.8 ℃.
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 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, the pure hydrogen gas is pumped into the hydrogen storage tank under the pump pressure of the liquid pump 1, the hydrogen storage tank is connected with a hydrogenation machine, and the hydrogen storage tank is connected with the 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 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 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 carbon dioxide mixed residual gas entering the carbon dioxide separation device are controlled through a hydraulic pump and a water-cooled heat exchanger 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 water distribution reforming, and the hydrogen mixed residual gas is changed into a 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 high-pressure hydrogen production system is improved.
The utility model discloses a high pressure hydrogen manufacturing system, reforming separator 3 integrated methanol-steam reforming, hydrogen separation, water gas reforming three function 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 under a high-pressure state, and the hydrogen production operation is safer.
In the hydrogen production system of the utility model, high pressure (18-50 MPa) hydrogen production pressure is provided by the liquid pump 1, when the whole hydrogen production system is used for treating carbon dioxide mixed residual gas, only one water-cooling heat exchanger 5 is needed to be configured to control the temperature of the carbon dioxide mixed residual gas in the carbon dioxide liquefying device 4, the pressure of the carbon dioxide mixed residual gas in the carbon dioxide liquefying device 4 is directly controlled from the source by the liquid pump 1, compared with low-pressure hydrogen production, the high-pressure hydrogen production system can save an air compressor (the low-pressure hydrogen production needs to be configured with an air compressor alone to provide the pressure for the carbon dioxide mixed residual gas to liquefy the carbon dioxide), compared with a medium-pressure hydrogen production system, the traditional refrigerator can be changed into the existing water-cooling heat exchanger 5 to control the temperature, the operation temperature of the carbon dioxide mixed residual gas entering the carbon dioxide separator is controlled by the water, the temperature is controlled to be 18-30.8 ℃, and the water-cooled heat exchanger 5 and the water-cooled tower control the temperature, so that the method has the advantages of low cost and stable and reliable operation, and is suitable for installing the hydrogen production system in the region with the outdoor temperature of 18-30.8 ℃ throughout the year.
Example two
A high-pressure hydrogen production method adopts the reforming and separation integrated high-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 18-50 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 water-cooled heat exchanger 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 18-50 Mpa, and the temperature controlled by the water-cooled heat exchanger 5 is 18-30.8 ℃;
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:
| scheme(s) | Pressure (Mpa) | Temperature (. degree.C.) |
| Scheme 1 | 18 | 18 |
| |
25 | 25 |
| |
50 | 30.8 |
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.
Utility model's high-pressure hydrogen manufacturing method relies on reforming, separation integral type high-pressure hydrogen manufacturing system in embodiment one, regard methanol water as the hydrogen manufacturing raw materials, liquid pump 1 provides high pressure (18 ~ 50MPa) at the source and goes into reforming separation device 3's last reaction chamber 31 with methanol water pump in, the mixed gas of reaction formation hydrogen, carbon dioxide and carbon monoxide, then inhale hydrogen pipe 34 and inhale hydrogen to the gas mixture reaction of hydrogen, carbon dioxide and carbon monoxide, pure hydrogen can direct output 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 water-cooled heat exchanger 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%.
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 high-pressure hydrogen production system is characterized by comprising a reforming and separating device, a three-phase heat exchange device, a steam trap, a water-cooling heat exchanger 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 water-cooling heat exchanger 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 improving the conveying pressure of the hydrogen mixed residual gas in the pipe is arranged on the hydrogen mixed residual gas;
the methanol steam inlet pipe is connected with a liquid pump, the pump pressure of the liquid pump is 18-50 Mpa, the water-cooled heat exchanger is connected with a water-cooled tower, and the operating temperature of the water-cooled heat exchanger is 18-30.8 ℃.
2. The reforming and separation integrated high-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 high-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 high-pressure hydrogen production system according to claim 1, wherein the pure hydrogen gas outlet pipe is connected with a hydrogen storage tank, the pure hydrogen gas is pumped into the hydrogen storage tank under the pump pressure of a liquid pump, the hydrogen storage tank is connected with a hydrogenation machine, and the hydrogen storage tank is connected with the hydrogenation machine.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201921827368.XU CN213112522U (en) | 2019-10-28 | 2019-10-28 | Reforming and separating integrated high-pressure hydrogen production system |
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| CN110817797B (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 high-pressure hydrogen production system and hydrogen production method thereof |
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