CN211998813U - Methanol steam and hydrogen mixed gas integrated medium-pressure hydrogen production system - Google Patents
Methanol steam and hydrogen mixed gas integrated medium-pressure hydrogen production system Download PDFInfo
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- CN211998813U CN211998813U CN201921827369.4U CN201921827369U CN211998813U CN 211998813 U CN211998813 U CN 211998813U CN 201921827369 U CN201921827369 U CN 201921827369U CN 211998813 U CN211998813 U CN 211998813U
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Abstract
The utility model relates to a methanol steam and hydrogen mixed gas integrated medium-pressure hydrogen production system, which comprises a three-phase heat exchange device, a reforming device, a hydrogen separation device, a steam trap, a refrigerator and a carbon dioxide liquefaction device; the temperature controlled by the refrigerator is-25-18 ℃. The hydrogen production efficiency of the hydrogen production system is improved, and the structure of the whole hydrogen production system is optimized and simplified, so that the hydrogen production system can be made into small-sized hydrogen production equipment.
Description
Technical Field
The utility model relates to a methanol vapor and hydrogen gas mixture integral type middling pressure hydrogen manufacturing 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 methanol steam and hydrogen mixed gas integrated reforming device is provided, and the problem that a hydrogen production system is numerous and complicated due to the fact that a reformer of the methanol steam and water gas reforming are two independent devices in the prior art is solved.
The utility model provides a technical scheme that its technical problem adopted is:
a methanol steam and hydrogen mixed gas integrated medium-pressure hydrogen production system comprises a three-phase heat exchange device, a reforming device, a hydrogen separation device, a steam trap, a refrigerator and a carbon dioxide liquefaction device;
the reforming device comprises a reaction cavity, and a heating cavity is arranged outside the reaction cavity; the reaction cavity comprises an upper reaction cavity and a lower reaction cavity, the upper reaction cavity is suitable for reforming methanol steam, the lower reaction cavity is suitable for reforming hydrogen mixed residual gas, and the upper reaction cavity is communicated with the lower reaction cavity;
copper-based filler or zirconium-based filler is filled in the upper reaction cavity, and copper-based filler or zirconium-based filler is filled in the lower reaction cavity; the upper reaction cavity is provided with a first inlet and a first outlet, and the lower reaction cavity is provided with a second inlet;
the first inlet is connected with a methanol steam inlet pipe, the first outlet is connected with an inlet of a hydrogen separation device, the hydrogen separation device is connected with a pure hydrogen gas outlet pipe and a carbon dioxide mixed residual gas outlet pipe, the carbon dioxide mixed residual gas outlet pipe is sequentially connected with a three-phase heat exchange device, a steam trap, a refrigerator and a carbon dioxide liquefaction device, the carbon dioxide liquefaction device is connected with a carbon dioxide outlet pipe and a hydrogen mixed residual gas outlet pipe, and the hydrogen mixed residual gas outlet pipe is connected with a second inlet; the hydrogen mixed residual gas outlet pipe is provided with an air pump for increasing the conveying pressure of the hydrogen mixed residual gas in the pipe; the methanol steam inlet pipe and the pure hydrogen outlet pipe are both connected with a three-phase heat exchange device;
the methanol steam inlet pipe is connected with a liquid pump, and the pump pressure of the liquid pump is 7-18 MPa;
the temperature controlled by the refrigerator is-25-18 ℃.
Further, the pure hydrogen gas outlet pipe is connected with a hydrogen storage tank, a compressor is arranged on the 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 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 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 feeding the mixed gas of the hydrogen, the carbon dioxide and the carbon monoxide into a hydrogen separation cavity of a hydrogen separation device;
the gas phase component of the mixed gas of hydrogen, carbon dioxide and carbon monoxide is 65-75% of hydrogen, 20-26% of carbon dioxide and 0.3-3% of carbon monoxide;
s2, separating the mixed gas of hydrogen, carbon dioxide and carbon monoxide by a hydrogen absorption pipe in the hydrogen separation cavity, and outputting the separated pure hydrogen from a pure hydrogen outlet 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;
the control pressure of the liquid pump is 7-18 MPa, and the control temperature of the refrigerator is-25-18 ℃;
s3, preparing the carbon dioxide mixed residual gas into liquid carbon dioxide and hydrogen mixed residual gas in a carbon dioxide separator, and outputting and collecting the liquid carbon dioxide;
the components of the hydrogen mixed residual gas comprise 65-75% of hydrogen, 20-26% of carbon dioxide and 3-9% of carbon monoxide;
s4, feeding the hydrogen mixed residual gas into a lower reaction cavity of a reforming 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 after the reformed mixed gas and the mixed gas of hydrogen, carbon dioxide and carbon monoxide are mixed in the upper reaction cavity, sending the mixed gas into the hydrogen separation device together to perform hydrogen separation operation again.
Further, the pure hydrogen of output and carbon dioxide mixed residual gas are all exported after three-phase heat transfer device heat transfer cooling, methanol-water is vaporized into methanol-water vapour through three-phase heat transfer device heat transfer.
Further, the methanol water is replaced by natural gas.
The utility model has the advantages that:
the utility model discloses a hydrogen manufacturing system makes equipment with the equipment of the reforming of methanol steam among the traditional hydrogen manufacturing system and the equipment to the reforming of hydrogen mixing residual gas, makes the reforming of methanol steam reforming and hydrogen mixing residual gas can concentrate on the reaction chamber of same temperature and go on, promotes hydrogen manufacturing system's hydrogen manufacturing efficiency, also makes whole hydrogen manufacturing system structure obtain optimizing retrench to rely on this hydrogen manufacturing system to make miniature hydrogen manufacturing equipment.
The utility model discloses among the hydrogen manufacturing system, provide the reaction environment of middling pressure (7 ~ 18MPa) through the liquid pump, make whole hydrogen manufacturing system can be more safe and stable's operation. And providing the working pressure and temperature of the output carbon dioxide mixed residual gas in a carbon dioxide liquefying device through a liquid pump and a refrigerating machine, separating the carbon dioxide mixed residual gas into hydrogen mixed residual gas with a preset molar ratio, and then preparing the hydrogen mixed residual gas into reformed mixed gas through a water gas reforming device.
Secondly, the carbon dioxide mixed residual gas generated in the hydrogen production system is recycled, the pressure and the temperature of the liquid carbon dioxide separated from the carbon dioxide mixed residual gas are controlled by a liquid pump and a refrigerator, the carbon dioxide mixed residual gas is separated into hydrogen mixed residual gas and liquid carbon dioxide by a carbon dioxide liquefying device, the liquid carbon dioxide can be stored, and the carbon dioxide liquefying device controls the gas-phase components in the hydrogen mixed residual gas by controlling the pressure and the temperature during separation, so that the molar ratio of the carbon dioxide in the hydrogen mixed residual gas is lower than 26%, and the hydrogen mixed residual gas is prepared for the subsequent reformed mixed gas; and finally, reforming the hydrogen mixed residual gas through water gas water distribution, reducing carbon monoxide in the hydrogen mixed residual gas from 3-9% originally to 0.5-1.5%, and reforming the gas phase components of the mixed gas: 62-77% of hydrogen, 22-27% of carbon dioxide and 0.5-1.5% of carbon monoxide; the gas phase component of the reformed mixed gas is close to the mixed gas component of the hydrogen, the carbon dioxide and the carbon monoxide prepared by the reformer, the reformed mixed gas and the mixed gas can be mixed and then enter a hydrogen separation device for hydrogen purification and separation to prepare hydrogen, the gas in the system is circularly purified, the theoretical yield can reach 100 percent, and the hydrogen yield is more than or equal to 95 percent.
Meanwhile, the hydrogen station system for preparing hydrogen by using methanol directly consumes customers, saves freight compared with factory hydrogen in selling price, recovers hydrogen in carbon dioxide residual gas, can realize the yield of 100% theoretically, is actually more than 90-99%, 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 schematic diagram of a medium pressure hydrogen production system of the present invention;
FIG. 2 is a schematic view of a methanol steam and hydrogen mixed gas integrated reforming apparatus;
the system comprises a liquid pump 1, a three-phase heat exchange device 2, a reforming device 3, a heating cavity 31, an upper reaction cavity 32, a lower reaction cavity 33, a heating cavity 4, a hydrogen separation device 5, a refrigerator 6, a carbon dioxide liquefaction device 7 and a steam trap.
Detailed Description
The invention will now be further described with reference to specific embodiments. The drawings are simplified schematic diagrams only illustrating the basic structure of the present invention in a schematic manner, and thus show only the components related to the present invention.
Example one
As shown in fig. 1 and fig. 2, a methanol-steam and hydrogen mixed gas integrated medium-pressure hydrogen production system comprises a three-phase heat exchange device 2, a reforming device 3, a hydrogen separation device 4, a steam trap 7, a refrigerator 5 and a carbon dioxide liquefaction device.
The reforming device 3 comprises a reaction cavity, and a heating cavity 33 is arranged outside the reaction cavity; the reaction cavity comprises an upper reaction cavity 31 suitable for reforming reaction of methanol steam and a lower reaction cavity 32 suitable for reforming hydrogen mixed residual gas, and the upper reaction cavity 31 is communicated with the lower reaction cavity 32;
the upper reaction cavity 31 is filled with copper-based filler or zirconium-based filler, and the lower reaction cavity 32 is filled with copper-based filler or zirconium-based filler; the upper reaction chamber 31 is provided with a first inlet and a first outlet, and the lower reaction chamber 32 is provided with a second inlet;
the first inlet is connected with a methanol steam inlet pipe, the first outlet is connected with an inlet of a hydrogen separation device 4, the hydrogen separation device 4 is connected with a pure hydrogen gas outlet pipe and a carbon dioxide mixed residual gas outlet pipe, the carbon dioxide mixed residual gas outlet pipe is sequentially connected with a three-phase heat exchange device 2, a steam trap 7, a refrigerator 5 and a carbon dioxide liquefaction device 6, the carbon dioxide liquefaction device 6 is connected with a carbon dioxide outlet pipe and a hydrogen mixed residual gas outlet pipe, the hydrogen mixed residual gas outlet pipe is connected with the second inlet, and the methanol steam inlet pipe and the pure hydrogen gas outlet pipe are both connected with the three-phase heat exchange device 2;
the hydrogen mixed residual gas outlet pipe is provided with an air pump for increasing the conveying pressure of the hydrogen mixed residual gas in the pipe;
the steam trap 7 is provided to reduce moisture in the carbon dioxide mixed residual gas and prevent excessive moisture from entering the carbon dioxide liquefaction device 6.
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 ℃.
The pure hydrogen gas outlet pipe is connected with a hydrogen storage tank, a compressor is arranged on the hydrogen gas outlet pipe and is suitable for 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 conveyed by the liquid pump 1 and vaporized into methanol steam by the three-phase heat exchange device 2, the working pressure of the liquid pump 1 is 7-18 MPa, the methanol steam enters the upper reaction cavity 31 of the reforming device 3, and the methanol steam is subjected to catalytic reaction in the reformer, 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. The mixed gas of hydrogen, carbon dioxide and carbon monoxide enters a hydrogen separation device 4 to carry out hydrogen separation operation, a hydrogen absorption pipe in the hydrogen separation device 4 carries out hydrogen absorption separation on the mixed gas of hydrogen, carbon dioxide and carbon monoxide, and the separated pure hydrogen is output from a pure hydrogen outlet pipe; the separated carbon dioxide mixed residual gas is output from a carbon dioxide mixed residual gas outlet pipe, the pressure and the temperature of the carbon dioxide mixed residual gas are controlled by an air compressor and a refrigerator 5 in sequence, a carbon dioxide mixed residual gas and carbon dioxide separation device carries 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 device 3, the hydrogen mixed residual gas is changed into a reformed mixed gas after water gas reforming, the proportion of gas phase components of the reformed mixed gas and mixed gas components of hydrogen, carbon dioxide and carbon monoxide generated by reforming reaction is approximate, the reformed mixed gas in the lower reaction cavity 32 directly enters an upper reaction cavity 31, and the mixed gas is mixed with the mixed gas of hydrogen, carbon dioxide and carbon monoxide and enters the hydrogen separation device 4 again for circular hydrogen absorption separation, 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 makes the equipment of the reforming of methanol-steam in traditional hydrogen manufacturing system and the equipment to the reforming of hydrogen mixing residual gas into one equipment, makes the reforming of methanol-steam reforming and hydrogen mixing residual gas can concentrate on the reaction chamber of same temperature and go on, promotes hydrogen manufacturing system's hydrogen manufacturing efficiency, also makes whole hydrogen manufacturing system structure obtain optimizing retrench to rely on this hydrogen manufacturing system can 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 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 6, the pressure of carbon dioxide mixed residual gas in carbon dioxide liquefying plant 6 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.
The output carbon dioxide mixed residual gas is provided with the working pressure and temperature in the carbon dioxide liquefying device 6 through the liquid pump 1 and the refrigerating machine 5, so that the carbon dioxide mixed residual gas is separated into hydrogen mixed residual gas with a preset molar ratio, and then the hydrogen mixed residual gas is prepared into reformed mixed gas through the water gas reforming device 3.
Example two
The medium-pressure hydrogen production method comprises the following steps:
s1, the liquid pump 1 sends methanol water into a methanol steam pipe inlet pipe, the pump pressure is 7-18 MPa, the methanol water is heated and vaporized into methanol steam which enters an upper reaction cavity 31 of a reforming 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, and then the mixed gas of the hydrogen, the carbon dioxide and the carbon monoxide is sent into a hydrogen separation cavity of a hydrogen separation device 4;
the methanol vapor carries out catalytic reaction at corresponding temperature and catalyst filler, 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;
s2, separating the mixed gas of hydrogen, carbon dioxide and carbon monoxide by a hydrogen absorption pipe in the hydrogen separation cavity, and outputting the separated pure hydrogen from a pure hydrogen outlet 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 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 pressure controlled by the liquid pump 1 is 7-18 MPa, and the temperature controlled by the refrigerator 5 is-25-18 ℃;
s3, preparing the carbon dioxide mixed residual gas into liquid carbon dioxide and hydrogen mixed residual gas in a carbon dioxide separator, and outputting and collecting the liquid carbon dioxide;
the components of the hydrogen mixed residual gas comprise 65-75% of hydrogen, 20-26% of carbon dioxide and 3-9% of carbon monoxide;
the molar ratio of carbon dioxide in the gaseous phase component of the hydrogen mixed residual gas is controlled to be 20-26%, and the selection of the pressure and the temperature of the carbon dioxide liquefying device 6 during working is shown in the following table:
s4, feeding the hydrogen mixed residual gas into the lower reaction cavity 32 of the reforming 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;
and 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 reforming mixed gas and the mixed gas of hydrogen, carbon dioxide and carbon monoxide are mixed in the upper reaction cavity 31 and then are sent into the hydrogen separation device 4 together to perform hydrogen separation again.
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, rely on methanol steam and hydrogen mixer integral type middling pressure hydrogen manufacturing system in embodiment one, regard methanol water as the hydrogen manufacturing raw materials, liquid pump 1 provides middling pressure (7 ~ 18MPa) at the source and goes into reformer 3's last reaction chamber 31 in with methanol water pump, the reaction generates hydrogen, the mist of carbon dioxide and carbon monoxide, then hydrogen, the mist of carbon dioxide and carbon monoxide sends into the hydrogen separation intracavity of hydrogen separator 4, hydrogen is inhaled in the hydrogen absorption pipe reaction of hydrogen separation intracavity, the pure hydrogen of collection can direct output gather, hydrogen manufacturing efficiency improves greatly. Then, the generated carbon dioxide mixed residual gas is conveyed, the pressure and the temperature of the carbon dioxide mixed residual gas in a carbon dioxide separation device are controlled through a liquid preparation pump 1 and a refrigerating machine 5, so that the carbon dioxide in the carbon dioxide mixed residual gas is liquefied and separated, the components of the separated hydrogen mixed residual gas are controlled, the molar ratio of the carbon dioxide in the hydrogen mixed residual gas is lower than 26%, and the hydrogen mixed residual gas is prepared for the subsequent reforming mixed gas; the mixed residual gas of hydrogen is sent into the lower reaction chamber 32 of the reforming device 3 again, and the lower reaction chamber 32 of the reforming device 3 is the same with the operation temperature of the upper reaction chamber 31, and through water gas water distribution reforming, the reformed mixed gas is generated, carbon monoxide in the mixed residual gas of hydrogen 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 enters the upper reaction chamber 31, is mixed with the mixed gas of hydrogen, carbon dioxide and carbon monoxide, and enters the hydrogen separation device 4 together again for circular hydrogen absorption separation, so that the gas in the system is circularly purified, the theoretical yield can reach 100%, and the yield of hydrogen 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 (2)
1. A methanol steam and hydrogen mixed gas integrated medium-pressure hydrogen production system is characterized by comprising a three-phase heat exchange device, a reforming device, a hydrogen separation device, a steam trap, a refrigerator and a carbon dioxide liquefaction device;
the reforming device comprises a reaction cavity, and a heating cavity is arranged outside the reaction cavity; the reaction cavity comprises an upper reaction cavity and a lower reaction cavity, the upper reaction cavity is suitable for reforming methanol steam, the lower reaction cavity is suitable for reforming hydrogen mixed residual gas, and the upper reaction cavity is communicated with the lower reaction cavity;
copper-based filler or zirconium-based filler is filled in the upper reaction cavity, and copper-based filler or zirconium-based filler is filled in the lower reaction cavity; the upper reaction cavity is provided with a first inlet and a first outlet, and the lower reaction cavity is provided with a second inlet;
the first inlet is connected with a methanol steam inlet pipe, the first outlet is connected with an inlet of a hydrogen separation device, the hydrogen separation device is connected with a pure hydrogen gas outlet pipe and a carbon dioxide mixed residual gas outlet pipe, the carbon dioxide mixed residual gas outlet pipe is sequentially connected with a three-phase heat exchange device, a steam trap, a refrigerator and a carbon dioxide liquefaction device, the carbon dioxide liquefaction device is connected with a carbon dioxide outlet pipe and a hydrogen mixed residual gas outlet pipe, and the hydrogen mixed residual gas outlet pipe is connected with a second inlet; the hydrogen mixed residual gas outlet pipe is provided with an air pump for increasing the conveying pressure of the hydrogen mixed residual gas in the pipe; the methanol steam inlet pipe and the pure hydrogen outlet pipe are both connected with a three-phase heat exchange device;
the methanol steam inlet pipe is connected with a liquid pump, and the pump pressure of the liquid pump is 7-18 MPa;
the temperature controlled by the refrigerator is-25-18 ℃.
2. The methanol steam and hydrogen mixed gas integrated medium-pressure hydrogen production system as claimed in claim 1, wherein the pure hydrogen gas outlet pipe is connected with a hydrogen storage tank, a compressor is arranged on the hydrogen gas outlet pipe and is suitable for feeding pure hydrogen gas into the hydrogen storage tank, and the hydrogen storage tank is connected with a hydrogenation machine.
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| CN110817798A (en) * | 2019-10-28 | 2020-02-21 | 中科液态阳光(苏州)氢能科技发展有限公司 | Methanol steam and hydrogen mixed gas integrated medium-pressure hydrogen production system and method thereof |
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| CN110817798A (en) * | 2019-10-28 | 2020-02-21 | 中科液态阳光(苏州)氢能科技发展有限公司 | Methanol steam and hydrogen mixed gas integrated medium-pressure hydrogen production system and method thereof |
| CN110817798B (en) * | 2019-10-28 | 2023-08-22 | 中科液态阳光(苏州)氢能科技发展有限公司 | Medium pressure hydrogen production method |
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