CN211998812U - Methanol steam and hydrogen mixed gas integrated high-pressure hydrogen production system - Google Patents
Methanol steam and hydrogen mixed gas integrated high-pressure hydrogen production system Download PDFInfo
- Publication number
- CN211998812U CN211998812U CN201921827367.5U CN201921827367U CN211998812U CN 211998812 U CN211998812 U CN 211998812U CN 201921827367 U CN201921827367 U CN 201921827367U CN 211998812 U CN211998812 U CN 211998812U
- Authority
- CN
- China
- Prior art keywords
- hydrogen
- carbon dioxide
- reaction cavity
- residual gas
- water
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 251
- 239000001257 hydrogen Substances 0.000 title claims abstract description 251
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 188
- 239000007789 gas Substances 0.000 title claims abstract description 163
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 125
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 58
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 267
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 137
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 131
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 72
- 238000002407 reforming Methods 0.000 claims abstract description 42
- 239000007788 liquid Substances 0.000 claims abstract description 40
- 238000000926 separation method Methods 0.000 claims abstract description 39
- 238000001816 cooling Methods 0.000 claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims description 77
- 238000003860 storage Methods 0.000 claims description 19
- 238000005984 hydrogenation reaction Methods 0.000 claims description 17
- 239000000945 filler Substances 0.000 claims description 13
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 229910052726 zirconium Inorganic materials 0.000 claims description 6
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 45
- 229910002091 carbon monoxide Inorganic materials 0.000 description 45
- 239000012071 phase Substances 0.000 description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 21
- 239000000446 fuel Substances 0.000 description 12
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 description 12
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 7
- 238000006057 reforming reaction Methods 0.000 description 7
- 238000009826 distribution Methods 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- 230000002441 reversible effect Effects 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 238000007086 side reaction Methods 0.000 description 4
- 239000003345 natural gas Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000001651 catalytic steam reforming of methanol Methods 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000009434 installation Methods 0.000 description 2
- 239000003595 mist Substances 0.000 description 2
- 238000010248 power generation Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000007792 gaseous phase Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
Images
Landscapes
- Hydrogen, Water And Hydrids (AREA)
Abstract
The utility model relates to a methanol vapor and hydrogen mixed gas integrated high-pressure hydrogen production system, which comprises a three-phase heat exchange device, a reforming device, a hydrogen separation device, a steam trap, a water-cooling heat exchanger, a refrigerator and a carbon dioxide liquefaction device; the pump pressure of the liquid pump is 18-50 MPa. 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 high 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 high-pressure hydrogen production system is provided, and the problem that the hydrogen production system is complicated due to the fact that a reformer and water gas reforming of the methanol steam 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 high-pressure hydrogen production system comprises a three-phase heat exchange device, a reforming device, a hydrogen separation device, a steam trap, a water-cooled heat exchanger, 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 water-cooling heat exchanger and a carbon dioxide liquefaction device, the carbon dioxide liquefaction device is connected with the carbon dioxide outlet pipe and a hydrogen mixed residual gas outlet pipe, the hydrogen mixed residual gas outlet pipe is connected with a second inlet, and an air pump used 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 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 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 ℃.
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 using the 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 device, carrying out reforming reaction on the methanol steam in the upper reaction cavity of the reforming device to generate a mixed gas of hydrogen, carbon dioxide and carbon monoxide, and feeding the mixed gas of the hydrogen, the carbon dioxide and the carbon monoxide into a hydrogen separation 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 device, 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 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 pressure of the liquid pump is controlled to be 18-50 MPa, and the temperature controlled by 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 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 high 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 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.
In the high-pressure hydrogen production system of the utility model, a high-pressure (18-50 MPa) hydrogen production environment is provided by the liquid pump, so that when the whole hydrogen production system is used for treating the 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 the 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 of the liquefying work for the carbon dioxide mixed residual gas), compared with the medium-pressure hydrogen production system, the traditional refrigerator can be changed into the existing water-cooling heat exchanger to carry out temperature control, the water-cooling heat exchanger and the water-cooling, 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.
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 water-cooled heat exchanger, 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 component in the hydrogen mixed residual gas by controlling the pressure and the temperature during separation, so that the molar ratio of the carbon dioxide in the hydrogen mixed residual gas is lower than 26%, and the hydrogen mixed residual gas is prepared for the subsequent reformed mixed gas; and finally, reforming the hydrogen mixed residual gas through water gas water distribution, reducing carbon monoxide in the hydrogen mixed residual gas from 3-9% originally to 0.5-1.5%, and reforming the gas phase components of the mixed gas: 62-77% of hydrogen, 22-27% of carbon dioxide and 0.5-1.5% of carbon monoxide; the gas phase component of the reformed mixed gas is close to the mixed gas component of the hydrogen, the carbon dioxide and the carbon monoxide prepared by the reformer, the reformed mixed gas and the mixed gas can be mixed and then enter the membrane separation and purification device for hydrogen purification and separation to prepare hydrogen, the gas in the system is circularly purified, the theoretical yield can reach 100 percent, and the hydrogen yield is more than or equal to 95 percent.
Meanwhile, the hydrogen station system for preparing hydrogen by using methanol directly consumes customers, saves freight compared with factory hydrogen in selling price, recovers the hydrogen in the carbon dioxide residual gas, can realize the yield of 100 percent theoretically, is actually more than 90 to 99 percent, and simultaneously recovers CO2The theoretical yield is 100 percent, and the actual yield is 90-99 percent. The process is combined with a hydrogenation station, so that high yield of hydrogen can be realized, and more CO can be recovered2And economic benefit is obtained, safety (high-pressure hydrogen storage is reduced), economy (methanol transportation cost is much lower than that of hydrogen) and CO recovery are really realized2And zero emission is realized.
On the one hand, hydrogen production is harmless and zero-state emission; on the other hand, the carbon dioxide emission reduction is made into methanol, greenhouse gas is changed into useful methanol liquid fuel, the methanol liquid fuel is taken as a hydrogenation station, the solar fuel has rich sources, light, wind, water and nuclear energy are all available, the carbon dioxide hydrogenation is used for preparing the methanol, and the methanol can be transported, stored and transported. The problems of manufacture, storage, transportation, installation and the like are solved in the whole view,
firstly, the liquid sunlight hydrogen station solves the safety problem of the high-pressure hydrogen station; secondly, the problems of storage, transportation and safety of hydrogen are solved; thirdly, hydrogen can be used as renewable energy to realize the aim of cleaning the whole process; fourthly, the liquid sunlight hydrogenation station can recover carbon dioxide, so that carbon dioxide emission reduction is realized, no further carbon dioxide is generated, and the carbon dioxide is always circulated therein; fifthly, the liquid sunlight hydrogenation station technology can be expanded to other chemical synthesis fields and can also be used for chemical hydrogenation; sixth, the system can be shared with a gas station and a methanol adding station. The system is particularly suitable for community distributed thermoelectric combined energy supply and the existing gas stations.
Drawings
The present invention will be further explained with reference to the accompanying drawings.
FIG. 1 is a schematic diagram of a high 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 device comprises a liquid pump 1, a three-phase heat exchange device 2, a reforming device 3, a heating cavity 31, an upper reaction cavity, a lower reaction cavity 32, a heating cavity 33, a hydrogen separation device 4, a water-cooling heat exchanger 5, a carbon dioxide liquefaction device 6, a steam trap 7, a steam trap 8 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 methanol-steam-hydrogen mixed gas integrated high-pressure hydrogen production system comprises a three-phase heat exchange device 2, a reforming device 3, a steam trap 7, a hydrogen separation device 4, a water-cooled heat exchanger 5, a refrigerator and a carbon dioxide liquefaction device 6.
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 chamber 31 is filled with copper-based filler or zirconium-based filler, the lower reaction chamber 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 water-cooling heat exchanger 5 and a carbon dioxide liquefaction device 6, the carbon dioxide liquefaction device 6 is connected with the 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 an air pump 8 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 and the pure hydrogen outlet pipe are both connected with the three-phase heat exchange device 2;
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 18-50 MPa; the water-cooling heat exchanger 5 is connected with a water-cooling tower, and the operation temperature of the water-cooling heat exchanger 5 is 18-30.8 ℃.
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. 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 18-50 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；
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 of the carbon dioxide mixed residual gas is controlled by a hydraulic pump, the temperature is controlled by a water-cooled heat exchanger 5, so that the carbon dioxide mixed residual gas and the carbon dioxide separation device carry out liquefaction separation, separated liquid carbon dioxide is collected, separated hydrogen mixed residual gas is sent into the lower reaction cavity 32 of the reforming device 3, the hydrogen mixed residual gas is changed into reformed mixed gas after water gas reforming in the lower reaction cavity 32, 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 the 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 high-pressure hydrogen production system is improved.
The utility model discloses a high 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 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.
In the high-pressure hydrogen production system of the utility model, a high-pressure reforming reaction environment is provided by the liquid pump 1, the pressure provided by the liquid pump 1 is 18-50 MPa, when the whole hydrogen production system is used for treating the carbon dioxide mixed residual gas, only a water-cooling heat exchanger 5 is needed to be configured to control the temperature (18-30.8 ℃) of the carbon dioxide mixed residual gas in the carbon dioxide liquefying device 6, the pressure of the carbon dioxide mixed residual gas in the carbon dioxide liquefying device 6 is directly controlled from the source by the liquid pump 1, the high-pressure hydrogen production system is compared with low-pressure hydrogen production, an air compressor (the low-pressure hydrogen production system needs to be separately configured to provide the pressure of liquefaction work for the carbon dioxide mixed residual gas) can be saved, compared with a medium-pressure hydrogen production system, the traditional refrigerator can be changed into the existing water-cooling heat exchanger 5 for temperature control, the operation temperature of the carbon dioxide mixed residual gas entering a carbon dioxide separator, 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
In another aspect, a high pressure hydrogen production method is provided, and the high pressure hydrogen production system includes the following steps:
s1, the liquid pump 1 sends 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 a reaction cavity 31 on a reforming device 3, the methanol steam carries out reforming reaction in the reaction cavity 31 on the reforming device 3 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 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 device 4, 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 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 6 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 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 high pressure hydrogen manufacturing method, rely on methanol steam and hydrogen mixer 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 reformer 3's last reaction chamber 31 in, 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 directly export the collection, 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 preparation 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 later 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 high-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 water-cooling heat exchanger, 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 water-cooling heat exchanger and a carbon dioxide liquefaction device, the carbon dioxide liquefaction device is connected with the carbon dioxide outlet pipe and a hydrogen mixed residual gas outlet pipe, the hydrogen mixed residual gas outlet pipe is connected with a second inlet, and an air pump used 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 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 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 ℃.
2. The system of 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 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 |
|---|---|---|---|
| CN201921827367.5U CN211998812U (en) | 2019-10-28 | 2019-10-28 | Methanol steam and hydrogen mixed gas integrated high-pressure hydrogen production system |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201921827367.5U CN211998812U (en) | 2019-10-28 | 2019-10-28 | Methanol steam and hydrogen mixed gas integrated high-pressure hydrogen production system |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN211998812U true CN211998812U (en) | 2020-11-24 |
Family
ID=73411768
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201921827367.5U Active CN211998812U (en) | 2019-10-28 | 2019-10-28 | Methanol steam and hydrogen mixed gas integrated high-pressure hydrogen production system |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN211998812U (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110835094A (en) * | 2019-10-28 | 2020-02-25 | 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 ultrahigh pressure hydrogen production system and method thereof |
| CN110921622A (en) * | 2019-10-28 | 2020-03-27 | 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 high-pressure hydrogen production system and method thereof |
-
2019
- 2019-10-28 CN CN201921827367.5U patent/CN211998812U/en active Active
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110835094A (en) * | 2019-10-28 | 2020-02-25 | 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 ultrahigh pressure hydrogen production system and method thereof |
| CN110921622A (en) * | 2019-10-28 | 2020-03-27 | 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 high-pressure hydrogen production system and method thereof |
| CN110921622B (en) * | 2019-10-28 | 2023-06-30 | 中科液态阳光(苏州)氢能科技发展有限公司 | High pressure hydrogen production process |
| CN110835094B (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 | Ultrahigh pressure hydrogen production method |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110775941A (en) | Methanol-water high-pressure hydrogen production system and hydrogen production method thereof | |
| CN110921622B (en) | High pressure hydrogen production process | |
| CN110790229B (en) | Methanol water ultrahigh pressure hydrogen production system and hydrogen production method thereof | |
| CN110921623A (en) | Hydrogen separation and water gas reforming integrated high-pressure hydrogen production system and method thereof | |
| CN211998812U (en) | Methanol steam and hydrogen mixed gas integrated high-pressure hydrogen production system | |
| CN211998804U (en) | Methanol steam and hydrogen mixed gas integrated ultrahigh pressure hydrogen production system | |
| CN110835094B (en) | Ultrahigh pressure hydrogen production method | |
| CN110937572B (en) | Reforming and separating integrated low-pressure hydrogen production system and hydrogen production method thereof | |
| CN110835095B (en) | Methanol steam reforming and hydrogen separation integrated high-pressure hydrogen preparation system and method thereof | |
| CN110835093A (en) | Methanol steam reforming and hydrogen separation integrated medium-pressure hydrogen production system and method thereof | |
| CN211998801U (en) | Hydrogen separation and water gas reforming integrated high-pressure hydrogen production system | |
| CN213112522U (en) | Reforming and separating integrated high-pressure hydrogen production system | |
| CN211998803U (en) | Methanol steam and hydrogen mixer integrated low-pressure hydrogen production system | |
| CN211998813U (en) | Methanol steam and hydrogen mixed gas integrated medium-pressure hydrogen production system | |
| CN211998802U (en) | Hydrogen separation and water gas reforming integrated medium-pressure hydrogen production system | |
| CN211998808U (en) | Hydrogen separation and water gas reforming integrated ultrahigh pressure hydrogen production system | |
| CN211998810U (en) | Reforming and separating integrated low-pressure hydrogen production system | |
| CN211998811U (en) | Reforming and separating integrated medium-pressure hydrogen production system | |
| CN211998806U (en) | Methanol steam reforming and hydrogen separation integrated medium-pressure hydrogen production system | |
| CN110817798B (en) | Medium pressure hydrogen production method | |
| CN211998800U (en) | Methanol water medium pressure hydrogen production system | |
| CN110817794B (en) | Hydrogen separation and water gas reforming integrated ultrahigh pressure hydrogen production system and method thereof | |
| CN110817799B (en) | Reforming and separating integrated ultrahigh pressure hydrogen production system and hydrogen production method thereof | |
| CN110817797B (en) | Reforming and separating integrated high-pressure hydrogen production system and hydrogen production method thereof | |
| CN110817796B (en) | Methanol steam reforming and hydrogen separation integrated low-pressure hydrogen preparation system and method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| GR01 | Patent grant | ||
| GR01 | Patent grant |