CN110921623A - Hydrogen separation and water gas reforming integrated high-pressure hydrogen production system and method thereof - Google Patents
Hydrogen separation and water gas reforming integrated high-pressure hydrogen production system and method thereof Download PDFInfo
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- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 345
- 239000001257 hydrogen Substances 0.000 title claims abstract description 345
- 239000007789 gas Substances 0.000 title claims abstract description 291
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 218
- 150000002431 hydrogen Chemical class 0.000 title claims abstract description 134
- 229910001868 water Inorganic materials 0.000 title claims abstract description 106
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 97
- 238000002407 reforming Methods 0.000 title claims abstract description 82
- 238000000926 separation method Methods 0.000 title claims abstract description 82
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 69
- 238000000034 method Methods 0.000 title description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 345
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 176
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 170
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 101
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 68
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 68
- 239000007788 liquid Substances 0.000 claims abstract description 48
- 238000001816 cooling Methods 0.000 claims abstract description 20
- 238000009826 distribution Methods 0.000 claims abstract description 9
- 238000006057 reforming reaction Methods 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims description 44
- 239000000945 filler Substances 0.000 claims description 27
- 238000010521 absorption reaction Methods 0.000 claims description 26
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 claims description 20
- 238000003860 storage Methods 0.000 claims description 16
- 238000005984 hydrogenation reaction Methods 0.000 claims description 14
- 239000003054 catalyst Substances 0.000 claims description 12
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 10
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical group [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 9
- 229910052726 zirconium Inorganic materials 0.000 claims description 9
- 239000012528 membrane Substances 0.000 claims description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-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 4
- 239000003345 natural gas Substances 0.000 claims description 4
- 229910001252 Pd alloy Inorganic materials 0.000 claims description 3
- 229910052758 niobium Inorganic materials 0.000 claims description 3
- 239000010955 niobium Substances 0.000 claims description 3
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 230000009467 reduction Effects 0.000 claims description 3
- 238000009834 vaporization Methods 0.000 claims description 2
- 230000008016 vaporization Effects 0.000 claims description 2
- 239000012071 phase Substances 0.000 description 24
- 239000000446 fuel Substances 0.000 description 12
- 230000002441 reversible effect Effects 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- 238000007086 side reaction Methods 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000009434 installation Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000010248 power generation Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 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
- 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
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/323—Catalytic reaction of gaseous or liquid organic compounds other than hydrocarbons with gasifying agents
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
- C01B3/12—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of water vapour with carbon monoxide
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/50—Carbon dioxide
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
- C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
- C01B2203/0233—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a steam reforming step
Abstract
The invention relates to a hydrogen separation and water gas reforming integrated high-pressure hydrogen production system, which comprises a reformer, a three-phase heat exchange device, a steam trap, a water-cooling heat exchanger, a carbon dioxide liquefaction device and a hydrogen separation and water gas reforming integrated device; the pump pressure of the liquid pump is 18-50 Mpa, and the operation temperature of the water-cooling heat exchanger is 18-30.8 ℃. A high-pressure hydrogen production method, methanol steam carries on the reforming reaction in the reformer and produces the mixed gas of hydrogen, carbon dioxide and carbon monoxide, the hydrogen mixes the residual gas and sends into the water gas of the reforming integrated device of water gas, water distribution makes and reforms the mixed gas; the reformed mixed gas enters a hydrogen separation cavity to be mixed with the mixed gas of hydrogen, carbon dioxide and carbon monoxide, and the mixed gas is subjected to hydrogen separation operation in the hydrogen separation cavity; the gas in the system is circularly purified, the theoretical yield can reach 100 percent, and the yield of the hydrogen is more than or equal to 95 percent.
Description
Technical Field
The invention relates to a hydrogen separation and water gas reforming integrated high-pressure hydrogen production system and a method thereof.
Background
The hydrogen energy is the most ideal energy in the 21 st century, is used as automobile fuel, is easy to start at low temperature, has small corrosion effect on an engine, and can prolong the service life of the engine. Because the hydrogen and the air can be uniformly mixed, a carburetor used on a common automobile can be completely omitted, and the structure of the existing automobile can be simplified. It is more interesting to add only 4% hydrogen to the gasoline. When it is used as fuel of automobile engine, it can save oil by 40%, and has no need of making great improvement on gasoline engine. A hydrogen fuel cell serves as a power generation system.
No pollution, and no pollution to environment caused by fuel cell. It is through electrochemical reaction, rather than combustion (gasoline, diesel) or energy storage (battery) -the most typical traditional backup power scheme. Combustion releases pollutants like COx, NOx, SOx gases and dust. As described above, the fuel cell generates only water and heat. If the hydrogen is generated by renewable energy sources (photovoltaic panels, wind power generation, etc.), the whole cycle is a complete process without generating harmful emissions.
No noise, quiet fuel cell operation, about only 55dB noise, which corresponds to the level of normal human conversation. This makes the fuel cell suitable for a wide range of applications, including indoor installations, or where there is a limit to noise outdoors.
The efficiency is high, the generating efficiency of the fuel cell can reach more than 50%, which is determined by the conversion property of the fuel cell, chemical energy is directly converted into electric energy without intermediate conversion of heat energy and mechanical energy (a generator), and the efficiency is reduced once more because of once more energy conversion. .
At present, the main source of hydrogen of a hydrogen energy source hydrogenation station is that an energy storage tank is transported back from outside, and the whole hydrogenation station needs to store a large amount of hydrogen; research finds that hydrogen in the hydrogen energy industry comprises four links, namely hydrogen preparation, hydrogen storage, hydrogen transportation and hydrogen addition (adding hydrogen into a hydrogen energy vehicle), wherein the two links of hydrogen preparation and hydrogen addition are safe at present, accidents easily occur in the hydrogen storage link, the cost of the hydrogen transportation link is high, and the characteristics of the hydrogen are related; the problems of explosion of the hydrogenation station and the reason of high hydrogenation cost frequently occur in the current news.
Therefore, in order to reduce the problem of large amount of hydrogen storage in the existing hydrogen refueling station and shorten or reduce the high cost of the hydrogen transportation link, a hydrogen refueling station system needs to be redesigned.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: the defects of the prior art are overcome, the hydrogen separation and water gas reforming integrated high-pressure hydrogen production system is provided, and the problem that the hydrogen production system is numerous and complicated due to a split structure between the water gas reforming and hydrogen separation devices in the conventional hydrogen production system is solved;
meanwhile, a high-pressure hydrogen production method is provided, and the problems that the existing hydrogen production process is complex and the circular hydrogen production cannot be realized are solved.
The technical scheme adopted by the invention for solving the technical problems is as follows:
a hydrogen separation and water gas reforming integrated high-pressure hydrogen production system comprises a reformer, a three-phase heat exchange device, a steam trap, a water-cooling heat exchanger, a carbon dioxide liquefaction device and a hydrogen separation and water gas reforming integrated device;
the reformer is connected with a methanol steam inlet pipe and a mixed gas outlet pipe; the reformer is suitable for preparing the methanol steam into a mixed gas of hydrogen, carbon dioxide and carbon monoxide;
the water gas reforming integrated device comprises a reaction cavity, wherein a heating cavity is arranged outside the reaction cavity and is suitable for providing reaction temperature for the reaction cavity; a hydrogen separation cavity and a water gas reforming cavity are arranged in the reaction cavity, the hydrogen separation cavity is positioned above the water gas reforming cavity, and the hydrogen separation cavity is communicated with the water gas reforming cavity; the hydrogen separation cavity is provided with a mixed gas inlet and a carbon dioxide mixed residual gas outlet, a hydrogen absorption pipe is inserted into the hydrogen separation cavity and is suitable for separating pure hydrogen, and the hydrogen absorption pipe is connected with a pure hydrogen outlet pipe; the water gas reforming cavity is provided with a catalyst filler, and the water gas reforming cavity is provided with a hydrogen mixed residual gas inlet;
the mixed gas outlet pipe is connected with the mixed gas inlet, the carbon dioxide mixed residual gas outlet is connected with the carbon dioxide mixed residual gas outlet pipe, the carbon dioxide mixed residual gas outlet pipe is sequentially connected with the steam trap, the water-cooled heat exchanger and the carbon dioxide liquefying device, the carbon dioxide liquefying device is connected with the liquid carbon dioxide outlet pipe and the hydrogen mixed residual gas outlet pipe, and the hydrogen mixed residual gas outlet pipe is connected with the hydrogen mixed residual gas inlet; the hydrogen mixed residual gas outlet pipe is provided with an air pump for providing hydrogen mixed residual gas conveying pressure;
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 carbon dioxide mixed residual gas outlet pipe and the pure hydrogen outlet pipe are both connected with a three-phase heat exchange device.
Further, the hydrogen absorption pipe is a niobium pipe, the catalyst filler is a copper-based filler, and the operating temperature of the reaction cavity is 200-350 ℃;
or the catalyst filler is a zirconium-based filler, and the operating temperature of the reaction chamber is 350-550 ℃.
Further, the hydrogen absorption tube is a palladium membrane tube or a palladium alloy membrane tube, the catalyst filler is a zirconium-based filler, and the operating temperature of the 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, and the hydrogen storage tank is connected with a 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, the methanol water is heated and vaporized into methanol steam which enters a reformer, the methanol steam is subjected to reforming reaction in the reformer to generate a 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 fed into a hydrogen separation cavity of the water gas reforming integrated 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 the hydrogen absorption pipe to be collected; the residual carbon dioxide mixed residual gas is output from the hydrogen separation cavity, 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-cooled 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 water gas reforming cavity of the water gas reforming integrated device, preparing a reformed 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 water gas reforming cavity 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 the hydrogen, the carbon dioxide and the carbon monoxide in the reforming mixed gas corresponds to the proportion of the hydrogen, the carbon dioxide and the carbon monoxide in the mixed gas of the hydrogen, the carbon dioxide and the carbon monoxide;
and S5, the reforming mixed gas enters the hydrogen separation cavity 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 subjected to hydrogen separation operation in the hydrogen separation cavity.
Further, the pure hydrogen of output and carbon dioxide mixed residual gas are all exported after three-phase heat transfer device heat transfer cooling, methanol-water is vaporized into methanol-water vapour through three-phase heat transfer device heat transfer.
Further, the methanol water is replaced by natural gas.
The invention has the beneficial effects that:
according to the high-pressure hydrogen production system, the water gas reforming and hydrogen separation devices in the traditional hydrogen production system are combined into one device, so that the water gas reforming operation of the hydrogen mixed residual gas and the separation reaction of the mixed gas of hydrogen, carbon dioxide and carbon monoxide are operated in the reaction cavity at the temperature, the hydrogen production efficiency of the hydrogen production system is improved, the structure of the whole hydrogen production system is optimized and simplified, and the hydrogen production system can be made into small-sized hydrogen production equipment.
In the hydrogen production system, the liquid pump provides a high-pressure (18-50 MPa) hydrogen production environment, so that the whole hydrogen production system only needs to be provided with a water-cooling heat exchanger to control the temperature of the carbon dioxide mixed residual gas in the carbon dioxide liquefying device when the carbon dioxide mixed residual gas is treated, 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 a high-pressure hydrogen production system, the high-pressure hydrogen production system can save an air compressor (the low-pressure hydrogen production system needs to be provided with the air compressor alone 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 control the temperature, and the water-cooling heat exchanger and a water-cooling tower are used for controlling the operating temperature of the carbon, 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 toolThe technology 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 invention is further described below with reference to the accompanying drawings.
FIG. 1 is a schematic diagram of a hydrogen separation and water gas reforming integrated high pressure hydrogen production system of the present invention;
FIG. 2 is a schematic of a water gas reforming integrated unit;
the device comprises a liquid pump 1, a three-phase heat exchange device 2, a water gas reforming integrated device 3, a water gas reforming integrated device 31, a water gas reforming cavity 32, a hydrogen separation cavity 33, a hydrogen absorption pipe 34, a heating cavity 4, a reformer 5, a water-cooling heat exchanger 6, a carbon dioxide liquefying device 7, a steam trap 8 and an air pump.
Detailed Description
The invention will now be further described with reference to specific examples. These drawings are simplified schematic diagrams only illustrating the basic structure of the present invention in a schematic manner, and thus show only the constitution related to the present invention.
Example one
As shown in fig. 1 and fig. 2, a hydrogen separation and water gas reforming integrated high-pressure hydrogen production system comprises a reformer 4, a three-phase heat exchange device 2, a steam trap 7, a water-cooled heat exchanger 5, a carbon dioxide liquefaction device 6 and a hydrogen separation and water gas reforming integrated device 3;
the reformer 4 is connected with a methanol steam inlet pipe and a mixed gas outlet pipe; the methanol steam inlet pipe is connected with the three-phase heat exchange device 2, and the reformer 4 is suitable for preparing the methanol steam into mixed gas of hydrogen, carbon dioxide and carbon monoxide;
the water gas reforming integrated device 3 comprises a reaction cavity, wherein a heating cavity 34 is arranged outside the reaction cavity and is suitable for providing reaction temperature for the reaction cavity; a hydrogen separation cavity 32 and a water gas reforming cavity 31 are arranged in the reaction cavity, the hydrogen separation cavity 32 is positioned above the water gas reforming cavity 31, and the hydrogen separation cavity 32 is communicated with the water gas reforming cavity 31; the hydrogen separation cavity 32 is provided with a mixed gas inlet and a carbon dioxide mixed residual gas outlet, a hydrogen absorption pipe 33 is inserted into the hydrogen separation cavity 32 and is suitable for separating pure hydrogen, and the hydrogen absorption pipe 33 is connected with a pure hydrogen outlet pipe; the water gas reforming cavity 31 is provided with a catalyst filler, and the water gas reforming cavity 31 is provided with a hydrogen mixing residual gas inlet;
the mixed gas outlet pipe is connected with the mixed gas inlet, the carbon dioxide mixed residual gas outlet is connected with the carbon dioxide mixed residual gas outlet pipe, the carbon dioxide mixed residual gas outlet pipe is sequentially connected with the steam trap 7, the water-cooled heat exchanger 5 and the carbon dioxide liquefying device 6, the carbon dioxide liquefying device 6 is connected with the liquid carbon dioxide outlet pipe and the hydrogen mixed residual gas outlet pipe, and the hydrogen mixed residual gas outlet pipe is connected with the hydrogen mixed residual gas inlet; the hydrogen mixed residual gas outlet pipe is provided with an air pump 8 for providing hydrogen mixed residual gas conveying pressure;
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, three-phase heat transfer device 2 is all connected to carbon dioxide mixture residual gas exit tube and pure hydrogen exit tube, and pure hydrogen and carbon dioxide mixture residual gas all carry out the heat transfer cooling then export with three-phase heat transfer device 2, and the heat that trades provides methanol steam and advances the pipe for carry out the vaporization operation to methanol-water.
Specifically, in this embodiment, the hydrogen absorption pipe 33 is a niobium pipe, the catalyst filler is a copper-based filler, and the operating temperature of the reaction chamber is 200-; or the catalyst filler is a zirconium-based filler, and the operating temperature of the reaction chamber is 350-550 ℃.
Or, the hydrogen absorption pipe 33 is a palladium membrane pipe or a palladium alloy membrane pipe, the catalyst filler is a zirconium-based filler, and the operating temperature of the reaction chamber is 250-550 ℃.
The copper-based filler or the zirconium-based filler corresponds to two different catalytic temperatures, the catalytic temperature corresponding to the copper-based filler is lower than that of the zirconium-based filler, the catalytic reaction temperature of the copper-based filler is 350 ℃ in the temperature range of 200 ℃ and the catalytic reaction temperature of the zirconium-based filler is 550 ℃ in the temperature range of 350 ℃.
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, 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.
According to the high-pressure hydrogen production system, the water gas reforming and hydrogen separation devices in the traditional hydrogen production system are combined into one device, so that the hydrogen mixed residual gas and water gas reforming operation and the mixed gas separation reaction of hydrogen, carbon dioxide and carbon monoxide are operated in the reaction cavity at the same temperature, and the whole hydrogen production system is optimized.
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 pump pressure of the liquid pump 1 is 18-50 Mpa, the methanol steam enters the reformer 4, and the methanol steam is subjected to catalytic reaction in the reformer 4, so that 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);
the reforming reaction generates a mixed gas of hydrogen, carbon dioxide and carbon monoxide. The mixed gas of hydrogen, carbon dioxide and carbon monoxide is sent into a hydrogen separation cavity 32 of the water gas reforming integrated device 3 through a mixed gas outlet pipe, a hydrogen absorption pipe 33 is used for absorbing and separating 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 temperature of the carbon dioxide mixed residual gas is controlled by a water-cooled heat exchanger 5, the temperature is controlled at 18-30.8 ℃, the pressure of the carbon dioxide mixed residual gas is controlled at the source by a liquid pump 1, the pressure is 18-50 Mpa, the carbon dioxide mixed residual gas and the carbon dioxide separation device are subjected to liquefaction separation, the separated liquid carbon dioxide is collected, the separated hydrogen mixed residual gas is sent into a water gas reforming cavity 31 of a water gas reforming integrated device 3, the conveying pressure of the hydrogen mixed residual gas is provided by an air pump 8, the hydrogen mixed residual gas is changed into reformed mixed gas after water gas reforming, the gas phase component of the reformed mixed gas is close to the mixed gas component of hydrogen, carbon dioxide and carbon monoxide generated by reforming reaction, the reformed mixed gas component in the water gas reforming cavity 31 directly enters a hydrogen separation cavity 32, and the mixed gas is mixed with the mixed gas of hydrogen, carbon dioxide and carbon monoxide, and the mixed gas is subjected to circular hydrogen absorption separation through the hydrogen absorption pipe 33 again, so that the hydrogen yield of the whole high-pressure hydrogen production system is improved.
The high-pressure hydrogen production system combines hydrogen separation and water gas reforming in the traditional hydrogen production system into one device, so that hydrogen separation reaction of mixed gas of hydrogen, carbon dioxide and carbon monoxide and water gas reforming reaction of mixed residual gas of hydrogen are carried out in one reaction cavity, the hydrogen production efficiency of the hydrogen production system is improved, the structure of the whole hydrogen production system is optimized and simplified, and the hydrogen production system can be made into small-sized hydrogen production equipment.
In the hydrogen production system, the liquid pump 1 is used for providing high-pressure (18-50 MPa) hydrogen production pressure, so that when the whole hydrogen production system is used for treating the carbon dioxide mixed residual gas, only the 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 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, compared with the high-pressure hydrogen production system, 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 the medium-pressure hydrogen production system, the traditional refrigerator can be changed into the existing water-cooling heat exchanger 5 for temperature control, and the water-cooling heat exchanger 5 and a water-cooling tower are used for controlling the operation, 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
The high-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 18-50 Mpa, the methanol water is heated and vaporized into methanol steam which enters a reformer 4, the methanol steam carries out reforming reaction in the reformer 4 to generate mixed gas of hydrogen, carbon dioxide and carbon monoxide, and the mixed gas is a multi-component and multi-reaction gas-solid catalytic reaction system;
the reaction equation is: CH (CH)3OH→CO+2H2(ii) a (reversible reaction)
H2O+CO→CO2+H2(ii) a (reversible reaction)
CH3OH+H2O→CO2+3H2(ii) a (reversible reaction)
2CH3OH→CH3OCH3+H2O; (side reaction)
CO+3H2→CH4+H2O; (side reaction);
the gas phase component of the mixed gas of hydrogen, carbon dioxide and carbon monoxide is 65-75% of hydrogen, 20-26% of carbon dioxide and 0.3-3% of carbon monoxide;
then the mixed gas of hydrogen, carbon dioxide and carbon monoxide is sent into the hydrogen separation chamber 32 of the water gas reforming integrated device 3;
s2, separating the mixed gas of hydrogen, carbon dioxide and carbon monoxide by the hydrogen absorption pipe 33 in the hydrogen separation cavity 32, and outputting the separated pure hydrogen from the hydrogen absorption pipe 33 to be collected; the residual carbon dioxide mixed residual gas is output from the hydrogen separation cavity 32, the pressure of the carbon dioxide mixed residual gas is controlled by the liquid pump 1, the temperature of the carbon dioxide mixed residual gas is controlled by the 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.) |
| |
18 | 18 |
| |
25 | 25 |
| |
50 | 30.8 |
S4, feeding the hydrogen mixed residual gas into a water gas reforming cavity 31 of the water gas reforming integrated device 3, preparing a reformed 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 water gas reforming cavity 31 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 the hydrogen, the carbon dioxide and the carbon monoxide in the reforming mixed gas corresponds to the proportion of the hydrogen, the carbon dioxide and the carbon monoxide in the mixed gas of the hydrogen, the carbon dioxide and the carbon monoxide;
and S5, the reforming mixed gas enters the hydrogen separation cavity 32 to be mixed with the mixed gas of the hydrogen, the carbon dioxide and the carbon monoxide, and the reforming mixed gas and the mixed gas of the hydrogen, the carbon dioxide and the carbon monoxide are subjected to hydrogen separation operation in the hydrogen separation cavity 32.
Specifically, the mixed residual gas of pure hydrogen and carbon dioxide of output all exports after 2 heat transfer cooling of three-phase heat transfer device, the methanol-water vaporizes into methanol-water vapour through 2 heat transfer of three-phase heat transfer device.
In this embodiment, the methanol-water may be replaced by natural gas, and hydrogen is produced from natural gas to obtain a mixed gas of hydrogen, carbon dioxide and carbon monoxide.
According to the high-pressure hydrogen production method, by means of the hydrogen separation and water gas reforming integrated high-pressure hydrogen production system in the first embodiment, methanol water is used as a hydrogen production raw material, high pressure (18-50 MPa) is provided by the liquid pump 1 from the source to pump the methanol water into the reformer 4, mixed gas of hydrogen, carbon dioxide and carbon monoxide is generated through reaction, then the mixed gas of the hydrogen, the carbon dioxide and the carbon monoxide is sent into the hydrogen separation cavity 32 of the water gas reforming integrated device 3 and directly reacts with the hydrogen absorption pipe 33 in the hydrogen separation cavity 32 to absorb hydrogen, pure hydrogen can be directly output and collected, and hydrogen production efficiency is greatly improved. Then conveying the generated carbon dioxide mixed residual gas, controlling the temperature by a water-cooling heat exchanger 5, indirectly controlling the pressure of the carbon dioxide mixed residual gas by a liquid pump 1, controlling the pressure and the temperature of the carbon dioxide mixed residual gas in a carbon dioxide separation device, wherein the pressure is 18-50 MPa, the temperature is 18-30.8 ℃ by the water-cooling heat exchanger 5, liquefying and separating the carbon dioxide in the carbon dioxide mixed residual gas, controlling the components of the separated hydrogen mixed residual gas, and making the molar ratio of the carbon dioxide in the hydrogen mixed residual gas lower than 26% so as to prepare the hydrogen mixed residual gas for the subsequent reforming mixed gas; the hydrogen mixed residual gas is sent into a water gas reforming cavity 31 of the water gas reforming integrated device 3, the operation temperature of the hydrogen mixed residual gas and the water gas reforming is the same as the hydrogen separation operation temperature of a hydrogen absorption pipe 33, carbon monoxide in the hydrogen mixed residual gas is reduced to 0.5-1.5% from 3-9% originally through water gas water distribution reforming, 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 4, the reformed mixed gas directly enters the hydrogen separation cavity 32 from the water gas reforming cavity 31, 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 33 again, so that the gas in the system is circularly purified, the theoretical yield can reach 100%, and the hydrogen yield is more than or equal to 95%.
In light of the foregoing description of the preferred embodiment of the present invention, many modifications and variations will be apparent to those skilled in the art without departing from the spirit and scope of the invention. The technical scope of the present invention is not limited to the content of the specification, and must be determined according to the scope of the claims.
Claims (8)
1. A hydrogen separation and water gas reforming integrated high-pressure hydrogen production system is characterized by comprising a reformer, a three-phase heat exchange device, a steam trap, a water-cooling heat exchanger, a carbon dioxide liquefaction device and a hydrogen separation and water gas reforming integrated device;
the reformer is connected with a methanol steam inlet pipe and a mixed gas outlet pipe; the reformer is suitable for preparing the methanol steam into a mixed gas of hydrogen, carbon dioxide and carbon monoxide;
the water gas reforming integrated device comprises a reaction cavity, wherein a heating cavity is arranged outside the reaction cavity and is suitable for providing reaction temperature for the reaction cavity; a hydrogen separation cavity and a water gas reforming cavity are arranged in the reaction cavity, the hydrogen separation cavity is positioned above the water gas reforming cavity, and the hydrogen separation cavity is communicated with the water gas reforming cavity; the hydrogen separation cavity is provided with a mixed gas inlet and a carbon dioxide mixed residual gas outlet, a hydrogen absorption pipe is inserted into the hydrogen separation cavity and is suitable for separating pure hydrogen, and the hydrogen absorption pipe is connected with a pure hydrogen outlet pipe; the water gas reforming cavity is provided with a catalyst filler, and the water gas reforming cavity is provided with a hydrogen mixed residual gas inlet;
the mixed gas outlet pipe is connected with the mixed gas inlet, the carbon dioxide mixed residual gas outlet is connected with the carbon dioxide mixed residual gas outlet pipe, the carbon dioxide mixed residual gas outlet pipe is sequentially connected with the steam trap, the water-cooled heat exchanger and the carbon dioxide liquefying device, the carbon dioxide liquefying device is connected with the liquid carbon dioxide outlet pipe and the hydrogen mixed residual gas outlet pipe, and the hydrogen mixed residual gas outlet pipe is connected with the hydrogen mixed residual gas inlet; the hydrogen mixed residual gas outlet pipe is provided with an air pump for providing hydrogen mixed residual gas conveying pressure;
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 hydrogen separation and water gas reforming integrated high-pressure hydrogen production system according to claim 1, wherein the carbon dioxide mixed residual gas outlet pipe and the pure hydrogen gas outlet pipe are both connected to a three-phase heat exchange device.
3. The hydrogen separation and water gas reforming integrated high-pressure hydrogen production system as claimed in claim 1, wherein the hydrogen absorption pipe is a niobium pipe, the catalyst filler is a copper-based filler, and the operating temperature of the reaction chamber is 200-350 ℃;
or the catalyst filler is a zirconium-based filler, and the operating temperature of the reaction chamber is 350-550 ℃.
4. The hydrogen separation and water gas reforming integrated high-pressure hydrogen production system as claimed in claim 1, wherein the hydrogen absorption tube is a palladium membrane tube or a palladium alloy membrane tube, the catalyst filler is a zirconium-based filler, and the operating temperature of the reaction chamber is 250-550 ℃.
5. The hydrogen separation and water gas reforming 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 pressure of a liquid pump, and the hydrogen storage tank is connected with a hydrogenation machine.
6. A high-pressure hydrogen production method is characterized in that the high-pressure hydrogen production system adopting any one of the above 1-5 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, the methanol water is heated and vaporized into methanol steam which enters a reformer, the methanol steam is subjected to reforming reaction in the reformer to generate a 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 fed into a hydrogen separation cavity of the water gas reforming integrated 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 the hydrogen absorption pipe to be collected; the residual carbon dioxide mixed residual gas is output from the hydrogen separation cavity, 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-cooled 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 water gas reforming cavity of the water gas reforming integrated device, preparing a reformed 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 water gas reforming cavity 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 the hydrogen, the carbon dioxide and the carbon monoxide in the reforming mixed gas corresponds to the proportion of the hydrogen, the carbon dioxide and the carbon monoxide in the mixed gas of the hydrogen, the carbon dioxide and the carbon monoxide;
and S5, the reforming mixed gas enters the hydrogen separation cavity 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 subjected to hydrogen separation operation in the hydrogen separation cavity.
7. The method for producing hydrogen from methanol water under high pressure as claimed in claim 6, wherein the mixed residual gas of pure hydrogen and carbon dioxide is outputted after being subjected to heat exchange and temperature reduction by a three-phase heat exchange device, and the methanol water is subjected to heat exchange and vaporization by the three-phase heat exchange device to form methanol steam.
8. The method for producing hydrogen from methanol-water under high pressure as claimed in claim 6, wherein the methanol-water is replaced by natural gas.
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