CN110817799B - Reforming and separating integrated ultrahigh pressure hydrogen production system and hydrogen production method thereof - Google Patents
Reforming and separating integrated ultrahigh pressure hydrogen production system and hydrogen production method thereof Download PDFInfo
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- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 335
- 239000001257 hydrogen Substances 0.000 title claims abstract description 335
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 265
- 238000002407 reforming Methods 0.000 title claims abstract description 67
- 238000004519 manufacturing process Methods 0.000 title claims description 52
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 322
- 239000007789 gas Substances 0.000 claims abstract description 200
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 161
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 161
- 238000006243 chemical reaction Methods 0.000 claims abstract description 82
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 70
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 69
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 60
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 60
- 238000000926 separation method Methods 0.000 claims abstract description 54
- 239000007788 liquid Substances 0.000 claims abstract description 53
- 238000010521 absorption reaction Methods 0.000 claims abstract description 48
- 238000001816 cooling Methods 0.000 claims abstract description 37
- 238000003860 storage Methods 0.000 claims abstract description 26
- 238000005086 pumping Methods 0.000 claims abstract description 16
- 238000006057 reforming reaction Methods 0.000 claims abstract description 7
- 239000000945 filler Substances 0.000 claims description 43
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 claims description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 32
- 230000003197 catalytic effect Effects 0.000 claims description 18
- 238000005984 hydrogenation reaction Methods 0.000 claims description 17
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 12
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 12
- 229910052802 copper Inorganic materials 0.000 claims description 12
- 239000010949 copper Substances 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 12
- 229910052726 zirconium Inorganic materials 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- 238000009826 distribution Methods 0.000 claims description 10
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical group C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 8
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 6
- 239000012528 membrane Substances 0.000 claims description 6
- 239000003345 natural gas Substances 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 230000009467 reduction Effects 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
- 230000008016 vaporization Effects 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 abstract description 6
- 239000000446 fuel Substances 0.000 description 14
- 230000002441 reversible effect Effects 0.000 description 6
- 238000007086 side reaction Methods 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 108010063955 thrombin receptor peptide (42-47) Proteins 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 2
- 238000001651 catalytic steam reforming of methanol Methods 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000010248 power generation Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 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
- 238000004880 explosion Methods 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
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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
- C01B3/32—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
- C01B3/34—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 by reaction of hydrocarbons with gasifying agents
- C01B3/38—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 by reaction of hydrocarbons with gasifying agents using catalysts
-
- 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
- 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
-
- 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
- C01B2203/06—Integration with other chemical processes
- C01B2203/061—Methanol production
-
- 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
- C01B2203/12—Feeding the process for making hydrogen or synthesis gas
- C01B2203/1205—Composition of the feed
- C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
- C01B2203/1217—Alcohols
- C01B2203/1223—Methanol
-
- 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
- C01B2203/12—Feeding the process for making hydrogen or synthesis gas
- C01B2203/1205—Composition of the feed
- C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
- C01B2203/1235—Hydrocarbons
- C01B2203/1241—Natural gas or methane
Abstract
The invention relates to a reforming and separating integrated ultrahigh-pressure hydrogen system, which comprises a reforming and separating device, a three-phase heat exchange device, a steam trap, a water-cooling heat exchanger and a carbon dioxide liquefying device; the pumping pressure of the liquid pump is 18-50 Mpa, the water-cooling heat exchanger is connected with the water-cooling tower, the operation temperature of the water-cooling heat exchanger is less than or equal to 30.8 ℃, and pure hydrogen is sent into the hydrogen storage tank under the pumping pressure of the liquid pump. The ultrahigh pressure hydrogen preparation process includes the reforming reaction of methanol vapor in the upper reaction cavity and the hydrogen separation of the mixed gas in the hydrogen absorbing pipe; the proportion of the reforming mixed gas is close to that of the mixed gas of hydrogen, carbon dioxide and carbon monoxide; the hydrogen absorption pipe performs hydrogen separation operation on the reformed mixed gas and the mixed gas of hydrogen, carbon dioxide and carbon monoxide. 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%.
Description
Technical Field
The invention relates to a reforming and separating integrated ultrahigh pressure hydrogen production system and a hydrogen production method thereof.
Background
The hydrogen energy is used as 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 the 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 traditional automobile can be simplified. Of further interest is the addition of only 4% hydrogen to the gasoline. The fuel can save fuel by 40% when used as fuel of automobile engine, and does not need to improve the gasoline engine. The hydrogen fuel cell serves as a power generation system.
The fuel cell has no pollution to the environment. It is by electrochemical reaction, rather than by combustion (gasoline, diesel) or energy storage (battery) means-most typically conventional back-up power schemes. Combustion releases contaminants such as COx, NOx, SOx gas and dust. As described above, the fuel cell generates only water and heat. If hydrogen is generated by renewable energy sources (photovoltaic panels, wind power generation and the like), the whole cycle is a complete process without harmful substance emission.
The fuel cell operates quietly without noise, which is only about 55dB, corresponding to the level of normal human conversation. This makes the fuel cell suitable for a wider range including indoor installation or where noise is limited outdoors.
The high efficiency, the generating efficiency of the fuel cell can reach more than 50%, which is determined by the conversion property of the fuel cell, directly converts chemical energy into electric energy without intermediate conversion of heat energy and mechanical energy (generator), because the efficiency is reduced once more by one energy conversion.
At present, the main source of hydrogen in a hydrogen energy hydrogenation station is that an energy storage tank is used for transporting the hydrogen back from the outside, and the whole hydrogenation station needs to store a large amount of hydrogen; the research shows that the 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, namely the hydrogen preparation and the hydrogen addition, are safer at present, the hydrogen storage link is easier to generate accidents, and the cost of the hydrogen transportation link is higher, so that the hydrogen transportation link is related to the characteristics of the hydrogen; at present, the problem of explosion of a hydrogenation station and the reason of high hydrogenation cost often occur in news.
Therefore, in order to reduce the problem of hydrogen storage in large quantities in the conventional hydrogen adding station, the high cost of hydrogen transportation links is shortened or reduced, and a hydrogen adding station system needs to be redesigned.
Disclosure of Invention
The invention aims to solve the technical problems that: the system overcomes the defects of the prior art, provides a reforming and separation integrated ultrahigh-pressure hydrogen production system, and solves the problem that the existing reformer for methanol vapor, hydrogen separation and water gas reforming are three independent devices, so that the hydrogen production system is complicated.
Meanwhile, the ultrahigh-pressure hydrogen production method solves the problems that the existing hydrogen production process is complex and the cyclic hydrogen production cannot be realized.
The technical scheme adopted for solving the technical problems is as follows:
a reforming and separating integrated ultrahigh-pressure hydrogen system comprises a reforming and separating device, a three-phase heat exchange device, a steam trap, a water-cooling heat exchanger and a carbon dioxide liquefying device;
the reforming separation device comprises an upper reaction cavity and a lower reaction cavity, wherein the upper reaction cavity is communicated with the lower reaction cavity, the upper reaction cavity is filled with a first catalytic filler, and the lower reaction cavity is filled with a second catalytic filler;
the upper reaction cavity is provided with a first inlet for inputting methanol vapor and a first outlet for outputting carbon dioxide mixed residual gas, a hydrogen absorption pipe is inserted into the upper reaction cavity, the hydrogen absorption pipe carries out hydrogen absorption separation on the mixed gas in the upper reaction cavity, and the absorbed hydrogen is output from the hydrogen absorption pipe; the lower reaction cavity is provided with a second inlet for inputting hydrogen mixed residual gas;
the first inlet is connected with a methanol vapor inlet pipe, the outlet of the hydrogen absorption pipe is connected with a pure hydrogen outlet pipe, the first outlet is connected with a carbon dioxide mixed residual gas outlet pipe, the methanol vapor inlet pipe, the pure hydrogen outlet pipe and the carbon dioxide mixed residual gas outlet pipe are all connected with a three-phase heat exchange device, the carbon dioxide mixed residual gas outlet pipe is sequentially connected with a steam trap, a water-cooling heat exchanger and a carbon dioxide liquefying device, the carbon dioxide liquefying device is connected with a hydrogen mixed residual gas outlet pipe, the hydrogen mixed residual gas outlet pipe is connected with a second inlet of the reforming separation device, and an air pump for conveying pressure of hydrogen mixed residual gas in the riser is arranged on the hydrogen mixed residual gas outlet pipe;
the methanol vapor inlet pipe is connected with a liquid pump, the pumping pressure of the liquid pump is 40-100 Mpa, the water-cooling heat exchanger is connected with a water-cooling tower, the operation temperature of the water-cooling heat exchanger is less than or equal to 30.8 ℃, and pure hydrogen in the hydrogen outlet pipe is sent into a hydrogen storage tank under the pumping pressure of the liquid pump.
Further, the hydrogen absorption tube is a niobium tube, the first catalytic filler is copper-based filler or zirconium-based filler, the second catalytic filler is copper-based filler or zirconium-based filler, and the operation temperature of the heating cavity is 200-500 ℃.
Further, the hydrogen absorption tube is a palladium membrane tube or a palladium alloy membrane tube, the first catalytic filler is copper-based filler or zirconium-based filler, the second catalytic filler is copper-based filler or zirconium-based filler, and the operation temperature of the heating cavity is 250-550 ℃.
Further, the pure hydrogen outlet pipe is connected with the hydrogen storage tank, pure hydrogen is sent into the hydrogen storage tank under the pumping pressure of the liquid pump, the hydrogen storage tank is connected with the hydrogenation machine, and the hydrogen storage tank is connected with the hydrogenation machine.
In yet another aspect, an ultrahigh pressure hydrogen production method, which adopts the reforming and separation integrated ultrahigh pressure hydrogen production system, comprises the following steps:
s1, feeding methanol water into a methanol-water vapor pipe inlet pipe by a liquid pump, wherein the pumping pressure is 40-100 Mpa, heating and vaporizing the methanol water into methanol water vapor, feeding the methanol water vapor into an upper reaction cavity of a reforming and separating device, performing reforming reaction on the methanol water vapor in the upper reaction cavity to generate mixed gas of hydrogen, carbon dioxide and carbon monoxide, and then performing hydrogen separation on the generated mixed gas of hydrogen, carbon dioxide and carbon monoxide by a hydrogen absorbing pipe;
the gas phase components of the mixed gas of the hydrogen, the carbon dioxide and the carbon monoxide are 65-75% of the hydrogen, 20-26% of the carbon dioxide and 0.3-3% of the carbon monoxide;
s2, separating mixed gas of hydrogen, carbon dioxide and carbon monoxide by a hydrogen absorption pipe, outputting and collecting the separated pure hydrogen from the hydrogen absorption pipe, and sending the pure hydrogen into a hydrogen storage tank under the pumping pressure of a liquid pump; outputting the residual carbon dioxide mixed residual gas from a carbon dioxide mixed residual gas outlet pipe, controlling the pressure of the carbon dioxide mixed residual gas by a liquid pump, controlling the temperature of the carbon dioxide mixed residual gas by a water-cooling heat exchanger, and then sending the carbon dioxide mixed residual gas 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 is 40-100 Mpa, and the temperature controlled by the water-cooling heat exchanger is less than or equal to 30.8 ℃;
s3, preparing liquid carbon dioxide and hydrogen mixed residual gas in a carbon dioxide separator from the carbon dioxide mixed residual gas, and outputting and collecting the liquid carbon dioxide;
the components of the hydrogen mixed residual gas are 65-75% of hydrogen, 20-26% of carbon dioxide and 3-9% of carbon monoxide;
s4, delivering the hydrogen mixed residual gas into a lower reaction cavity of the reforming separation device, and preparing reformed mixed gas by water distribution, wherein the water distribution ratio (carbon monoxide: water) is 1:1-20;
the fed hydrogen mixed residual gas is subjected to water distribution reforming in a lower reaction cavity to form reforming mixed gas, wherein the gas phase components of the reforming mixed gas are 62-77% of hydrogen, 22-27% of carbon dioxide and 0.5-1.5% of carbon monoxide;
the ratio of the hydrogen, the carbon dioxide and the carbon monoxide in the reforming mixed gas is close to the ratio of the hydrogen, the carbon dioxide and the carbon monoxide in the mixed gas of the hydrogen, the carbon dioxide and the carbon monoxide;
s5, the reforming mixed gas enters an upper reaction cavity and is mixed with the mixed gas of hydrogen, carbon dioxide and carbon monoxide, and a hydrogen absorption pipe carries out hydrogen separation operation on the reforming mixed gas and the mixed gas of hydrogen, carbon dioxide and carbon monoxide.
Furthermore, the output pure hydrogen and carbon dioxide mixed residual gas are output after being subjected to heat exchange and temperature reduction through the three-phase heat exchange device, and the methanol water is vaporized into methanol water vapor through the heat exchange of the three-phase heat exchange device.
Further, the methanol water is replaced by natural gas.
The beneficial effects of the invention are as follows:
the ultrahigh pressure hydrogen production system adopts methanol water as raw material, the operation pressure of the hydrogen production system is controlled by the liquid pump, hydrogen production is controlled under the ultrahigh pressure (40-100 MPa) environment, and the operation temperature of carbon dioxide mixed residual gas entering the carbon dioxide separator is controlled by the water cooling heat exchanger and the water cooling tower, and the temperature is controlled to be less than or equal to 30.8 ℃, so that the water cooling heat exchanger and the water cooling tower have the advantages of low cost and stable and reliable operation.
The invention has high hydrogen production efficiency, realizes the circular purification of the gas in the system, has the theoretical yield reaching 100 percent and realizes the hydrogen yield more than or equal to 95 percent.
The working method of the methanol-water ultrahigh pressure hydrogen production system is characterized in that the pressure of the methanol water pumped by the liquid pump is controlled at the source of the hydrogen production system and controlled at the ultrahigh pressure (40-100 MPa), the whole hydrogen production system can operate in the ultrahigh pressure range, the whole hydrogen production system does not need to be provided with equipment such as an air compressor or a compressor for additionally increasing the working pressure of the system, the working pressure of the whole hydrogen production system can be controlled by the liquid pump at the inlet, and the pure hydrogen conveying pressure for the separated pure hydrogen and the pure hydrogen output in the output pipe can be provided by the liquid pump in the ultrahigh pressure (40-100 MPa) environment, so that the inconvenience that the compressor is required to be arranged on the pure hydrogen output pipe to collect the pure hydrogen in the past is avoided.
The ultrahigh-pressure hydrogen production system integrates the methanol steam reforming, the hydrogen absorption separation of mixed gas and the hydrogen mixed residual gas reforming into one reaction cavity at the same operation temperature, so that the integration of a methanol water reforming device, a hydrogen separation device and a water gas reformer is realized, the layout structure of the whole hydrogen production system is optimized, and small-sized hydrogen production equipment can be manufactured by means of the hydrogen production system.
According to the ultrahigh-pressure hydrogen preparation method, the reforming separation of methanol and water vapor and the hydrogen absorption separation of a hydrogen absorption pipe are carried out in an upper reaction cavity, separated hydrogen is collected, separated carbon dioxide mixed residual gas is recycled, the pressure and the temperature for separating liquid carbon dioxide from the carbon dioxide mixed residual gas are controlled by a liquid pump and a refrigerator, the carbon dioxide mixed residual gas is separated into hydrogen mixed residual gas and liquid carbon dioxide by a carbon dioxide liquefying device, the liquid carbon dioxide can be stored, and when the carbon dioxide liquefying device is separated, the pressure and the temperature are controlled, so that the gas phase components in the hydrogen mixed residual gas are controlled, the carbon dioxide mole ratio in the hydrogen mixed residual gas is lower than 26%, and the hydrogen mixed residual gas is prepared for the reforming mixed gas of a subsequent process; the hydrogen mixed residual gas is reformed by water gas distribution in the reaction chamber, so that the carbon monoxide in the hydrogen mixed residual gas is reduced to 0.5-1.5% from original 3-9%, and the gas phase component of the reformed mixed gas is as follows: 62-77% of hydrogen, 22-27% of carbon dioxide and 0.5-1.5% of carbon monoxide; the gas phase component of the reforming mixed gas is close to the mixed gas component of the hydrogen, the carbon dioxide and the carbon monoxide prepared by the reformer, so that the two components can be mixed and enter the upper reaction cavity again, and are mixed with the mixed gas of the hydrogen, the carbon dioxide and the carbon monoxide, and the hydrogen absorption pipe performs hydrogen purification and separation hydrogen production operation 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%.
Meanwhile, the hydrogen station system for preparing hydrogen by utilizing methanol aims at direct consumption customers, and the selling price of hydrogen is saved compared with the factory hydrogen, so that the hydrogen in the carbon dioxide residual gas is recovered, the theoretical 100 percent yield can be realized, the actual yield is more than 90-99 percent, and the CO is recovered simultaneously 2 The 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 CO can be recovered more 2 And economic benefit is obtained, thus realizing safety (reducing high-pressure hydrogen storage), economy (because the transportation cost of methanol is much lower than that of hydrogen), and recovering CO 2 Zero emission is realized, and ecological benefits are obtained.
On the one hand, hydrogen production is harmless, and zero-state emission is realized; on the other hand, the emission of carbon dioxide is reduced to be made into methanol, the greenhouse gas is changed into useful methanol liquid fuel, the methanol liquid fuel is taken as a hydrogenation station, the source of solar fuel is very rich, light, wind, water and nuclear energy can be all used, the methanol can be prepared by hydrogenating the carbon dioxide, and the storage and transportation of the methanol are not problems. Solves the problems of manufacturing, storing, transporting, installing and the like in the whole,
firstly, the liquid sunlight hydrogenation station solves the safety problem of the high-pressure hydrogenation station; secondly, the problems of hydrogen storage, transportation and safety are solved; thirdly, hydrogen can be used as a renewable energy source to realize the aim of full-flow cleaning; fourthly, the liquid state sunlight hydrogenation station can recycle carbon dioxide, so that carbon dioxide emission reduction is realized, carbon dioxide is not further generated, and the carbon dioxide circulates at the position all the time; fifth, the liquid sunlight hydrogenation station technology can be extended to other chemical synthesis fields, and can also be used for chemical hydrogenation; sixth, the system can be multi-element co-station with a gas station or a methanol adding station. The system is particularly suitable for energy supply and current gas stations for community distributed combined heat and power.
Drawings
The invention is further described below with reference to the accompanying drawings.
FIG. 1 is a reforming, separation integrated ultra-high pressure hydrogen system;
FIG. 2 is a schematic diagram of a reforming separation device;
wherein, 1, a liquid pump, 2, a three-phase heat exchange device, 3, a reforming separation device, 31, an upper reaction cavity, 32 and a lower reaction cavity, 33, a heating cavity, 34, a hydrogen absorption pipe, 4, a carbon dioxide liquefying device, 5, a water-cooling heat exchanger, 6, a steam trap, 7 and an air pump.
Detailed Description
The invention will now be further described with reference to specific examples. These drawings are simplified schematic views illustrating the basic structure of the present invention by way of illustration only, and thus show only the constitution related to the present invention.
Example 1
As shown in fig. 1 and 2, a reforming and separation integrated ultrahigh pressure hydrogen system comprises a reforming and separation device 3, a three-phase heat exchange device 2, a steam trap 6, a water-cooling heat exchanger 5 and a carbon dioxide liquefying device 4;
the reforming separation device 3 comprises an upper reaction cavity 31 and a lower reaction cavity 32, wherein the upper reaction cavity 31 is communicated with the lower reaction cavity 32, the upper reaction cavity 31 is filled with a first catalytic filler, and the lower reaction cavity 32 is filled with a second catalytic filler;
the upper reaction chamber 31 is provided with a first inlet for inputting methanol vapor and a first outlet for outputting carbon dioxide mixed residual gas, a hydrogen absorption pipe 34 is inserted into the upper reaction chamber 31, the hydrogen absorption pipe 34 performs hydrogen absorption separation on the mixed gas in the upper reaction chamber 31, and the absorbed hydrogen is output from the hydrogen absorption pipe 34; the lower reaction chamber 32 is provided with a second inlet for inputting hydrogen mixed residual gas;
the first inlet is connected with a methanol vapor inlet pipe, the outlet of the hydrogen absorption pipe 34 is connected with a pure hydrogen outlet pipe, the first outlet is connected with a carbon dioxide mixed residual gas outlet pipe, the methanol vapor inlet pipe, the pure hydrogen outlet pipe and the carbon dioxide mixed residual gas outlet pipe are all connected with the three-phase heat exchange device 2, the carbon dioxide mixed residual gas outlet pipe is sequentially connected with the steam trap 6, the water-cooling heat exchanger 5 and the carbon dioxide liquefying device 4, the carbon dioxide liquefying device 4 is connected with a hydrogen mixed residual gas outlet pipe, the hydrogen mixed residual gas outlet pipe is connected with the second inlet of the reforming separation device 3, and the hydrogen mixed residual gas outlet pipe is provided with an air pump 7 for conveying pressure of hydrogen mixed residual gas in the riser;
the steam trap 6 is used for removing water from the carbon dioxide mixed residual gas, and the carbon dioxide mixed residual gas is liquefied by carbon dioxide after controlling the water.
The methanol vapor inlet pipe is connected with a liquid pump 1, the pumping pressure of the liquid pump 1 is 40-100 Mpa, the water-cooling heat exchanger 5 is connected with a water-cooling tower, the operation temperature of the water-cooling heat exchanger 5 is less than or equal to 30.8 ℃, and pure hydrogen in the hydrogen outlet pipe is sent into a hydrogen storage tank under the pumping pressure of the liquid pump 1.
Specifically, the hydrogen absorption tube 34 is a niobium tube, the first catalytic filler is a copper-based filler or a zirconium-based filler, the second catalytic filler is a copper-based filler or a zirconium-based filler, and the operation temperature of the heating cavity 33 is 200-500 ℃.
The hydrogen absorption tube 34 can also adopt a palladium membrane tube or a palladium alloy membrane tube, the first catalytic filler is copper-based filler or zirconium-based filler, the second catalytic filler is copper-based filler or zirconium-based filler, and the operation temperature of the heating cavity 33 is 250-550 ℃.
The mixed gas of hydrogen, carbon dioxide and carbon monoxide generated in the reaction cavity is subjected to hydrogen absorption separation, pure hydrogen output is collected, and the rest carbon dioxide mixed residual gas is output in addition for recovery operation.
The pure hydrogen outlet pipe is connected with the hydrogen storage tank, pure hydrogen is fed into the hydrogen storage tank under the pumping pressure of the liquid pump 1, the hydrogen storage tank is connected with the hydrogenation machine, and the hydrogen storage tank is connected with the hydrogenation machine. The hydrogen production system realizes on-site hydrogen production, directly stores the prepared hydrogen into the hydrogen storage tank, and then directly adds the prepared pure hydrogen into the hydrogen vehicle through the hydrogenation machine.
During operation, methanol water is vaporized into methanol water vapor through the three-phase heat exchange device 2, the methanol water vapor enters the upper reaction cavity 31 of the reforming separation device 3, the heating cavity 33 heats and controls the temperature in the upper reaction cavity 31, and the methanol water vapor carries out catalytic reaction under the corresponding temperature and catalyst filler, so that the gas-solid catalytic reaction system with multiple components and multiple reactions is provided;
the reaction equation is: CH (CH) 3 OH→CO+2H 2 The method comprises the steps of carrying out a first treatment on the surface of the (reversible reaction)
H 2 O+CO→CO 2 +H 2 The method comprises the steps of carrying out a first treatment on the surface of the (reversible reaction);
CH 3 OH+H 2 O→CO 2 +3H 2 the method comprises the steps of carrying out a first treatment on the surface of the (reversible reaction);
2CH 3 OH→CH 3 OCH 3 +H 2 o; (side reaction)
CO+3H 2 →CH 4 +H 2 O; (side reactions);
the reforming reaction produces a mixed gas of hydrogen, carbon dioxide and carbon monoxide.
The hydrogen absorption tube 34 in the upper reaction cavity 31 carries out hydrogen absorption operation on the mixed gas of hydrogen, carbon dioxide and carbon monoxide, the hydrogen absorption tube 34 separates the hydrogen in the mixed gas, pure hydrogen is collected into a hydrogen storage tank after being output by the hydrogen absorption tube 34, the residual carbon dioxide mixed residual gas is output from a carbon dioxide mixed residual gas outlet tube of the upper reaction cavity 31, the carbon dioxide mixed residual gas is cooled by the three-phase heat exchange device 2, the pressure and the temperature of the carbon dioxide mixed residual gas entering the carbon dioxide separation device are controlled by the hydraulic pump and the water-cooling heat exchanger 5, then the carbon dioxide mixed residual gas and the carbon dioxide are liquefied and separated, the separated liquid carbon dioxide is collected, the separated hydrogen mixed residual gas is sent into a lower reaction cavity 32 of a reforming separation device 3 for water gas distribution reforming, the hydrogen mixed residual gas is changed into reformed mixed gas after water gas reforming, the gas phase component of the reformed mixed gas is close to the component proportion of the mixed gas of hydrogen, carbon dioxide and carbon monoxide generated by reforming reaction, the reformed mixed gas enters an upper reaction cavity 31 from the lower reaction cavity 32 and is mixed with the mixed gas of hydrogen, carbon dioxide and carbon monoxide, and a hydrogen absorption pipe 34 continues to absorb and separate the mixed gas, so that the hydrogen yield of the whole ultrahigh-pressure hydrogen system is improved.
According to the ultrahigh pressure hydrogen production system, the reforming separation device 3 integrates the functions of methanol steam reforming, hydrogen separation and water gas reforming, so that the hydrogen production system is optimized, and small-sized hydrogen production equipment can be manufactured by means of the hydrogen production system. The pressure provided by the liquid pump 1 is 2-5 MPa, the whole hydrogen production system operates in an ultrahigh pressure state, and the hydrogen production operation is safer.
In the hydrogen production system, the liquid pump 1 is used for providing the hydrogen production pressure of ultrahigh pressure (40-100 Mpa), so that the whole hydrogen production system only needs to be provided with one water-cooling heat exchanger 5 to control the temperature of the carbon dioxide mixed residual gas in the carbon dioxide liquefying device 4 when the carbon dioxide mixed residual gas is treated, the pressure of the carbon dioxide mixed residual gas in the carbon dioxide liquefying device 4 is directly controlled by the liquid pump 1 from the source, compared with the low-pressure hydrogen production system, the ultrahigh-pressure hydrogen production system can omit an air compressor (the low-pressure hydrogen production needs to be provided with an air compressor to provide the pressure for liquefying the carbon dioxide mixed residual gas independently to work), compared with the medium-pressure hydrogen production system, the traditional refrigerator can be changed into the current water-cooling heat exchanger 5 to control the temperature, the operation temperature of the carbon dioxide mixed residual gas is controlled to be less than or equal to 30.8 ℃ by the water-cooling heat exchanger 5 and the water-cooling tower, and the water-cooling tower temperature control is stable and reliable.
Example two
The ultrahigh-pressure hydrogen preparation method adopts the reforming and separating integrated ultrahigh-pressure hydrogen preparation system and comprises the following steps of:
s1, a liquid pump 1 sends methanol water into a methanol water vapor pipe inlet pipe, the pumping pressure is 40-100 Mpa, the methanol water is heated and gasified into methanol water vapor which enters an upper reaction cavity 31 of a reforming separation device 3, the methanol water vapor carries out reforming reaction in the upper reaction cavity 31 to generate mixed gas of hydrogen, carbon dioxide and carbon monoxide,
the catalyst is a multi-component and multi-reaction gas-solid catalytic reaction system;
the reaction equation is: CH (CH) 3 OH→CO+2H 2 The method comprises the steps of carrying out a first treatment on the surface of the (reversible reaction)
H 2 O+CO→CO 2 +H 2 The method comprises the steps of carrying out a first treatment on the surface of the (reversible reaction)
CH 3 OH+H 2 O→CO 2 +3H 2 The method comprises the steps of carrying out a first treatment on the surface of the (reversible reaction)
2CH 3 OH→CH 3 OCH 3 +H 2 O; (side reaction)
CO+3H 2 →CH 4 +H 2 O; (side reactions);
then the hydrogen absorption pipe 34 separates the generated mixed gas of hydrogen, carbon dioxide and carbon monoxide;
the gas phase components of the mixed gas of the hydrogen, the carbon dioxide and the carbon monoxide are 65-75% of the hydrogen, 20-26% of the carbon dioxide and 0.3-3% of the carbon monoxide;
s2, separating the mixed gas of hydrogen, carbon dioxide and carbon monoxide by the hydrogen absorption pipe 34, outputting the separated pure hydrogen from the hydrogen absorption pipe 34, and sending the pure hydrogen into a hydrogen storage tank under the pump pressure of the liquid pump 1; outputting the residual carbon dioxide mixed residual gas from a carbon dioxide mixed residual gas outlet pipe, controlling the pressure of the carbon dioxide mixed residual gas by a liquid pump 1, controlling the temperature of the carbon dioxide mixed residual gas by a water-cooling heat exchanger 5, and then sending the carbon dioxide mixed residual gas 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 40-100 Mpa, and the temperature controlled by the water-cooling heat exchanger 5 is less than or equal to 30.8 ℃;
s3, preparing liquid carbon dioxide and hydrogen mixed residual gas in a carbon dioxide separator from the carbon dioxide mixed residual gas, and outputting and collecting the liquid carbon dioxide;
the components of the hydrogen mixed residual gas are 65-75% of hydrogen, 20-26% of carbon dioxide and 3-9% of carbon monoxide;
the molar ratio of carbon dioxide in the gas phase component of the hydrogen mixed residual gas is controlled to be 20-26%, the pressure of the carbon dioxide liquefying device 4 is 40-100 MPa when the device works, and the temperature is less than or equal to 30.8 ℃.
S4, delivering the hydrogen mixed residual gas into a lower reaction cavity 32 of the reforming separation device 3, and distributing water to prepare reforming mixed gas, wherein the water distribution ratio (carbon monoxide: water) is 1:1-20;
the water gas reforming reaction formula is: CO+H 2 O→CO 2 +H 2 ；
The fed hydrogen mixed residual gas is subjected to water distribution and reforming in the lower reaction cavity 32 to form reformed mixed gas, wherein 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;
the ratio of the hydrogen, the carbon dioxide and the carbon monoxide in the reforming mixed gas is close to the ratio of the hydrogen, the carbon dioxide and the carbon monoxide in the mixed gas of the hydrogen, the carbon dioxide and the carbon monoxide;
s5, the reformed mixed gas enters the upper reaction cavity 31 and is mixed with the mixed gas of hydrogen, carbon dioxide and carbon monoxide, and the hydrogen absorption pipe 34 carries out hydrogen separation operation on the reformed mixed gas and the mixed gas of hydrogen, carbon dioxide and carbon monoxide.
Specifically, the output pure hydrogen and carbon dioxide mixed residual gas are output after heat exchange and temperature reduction through the three-phase heat exchange device 2, and the methanol water is vaporized into methanol water vapor through heat exchange of the three-phase heat exchange device 2.
In this embodiment, the methanol water may be replaced by natural gas, and the mixed gas of hydrogen, carbon dioxide and carbon monoxide is obtained by hydrogen production from natural gas.
According to the ultrahigh pressure hydrogen production method, by means of the reforming and separation integrated ultrahigh pressure hydrogen production system in the first embodiment, methanol water is used as hydrogen production raw material, the liquid pump 1 provides ultrahigh pressure (40-100 Mpa) at the source to pump the methanol water into the upper reaction cavity 31 of the reforming and separation device 3, mixed gas of hydrogen, carbon dioxide and carbon monoxide is generated through reaction, then the hydrogen absorption tube 34 reacts and absorbs hydrogen to the mixed gas of the hydrogen, the pure hydrogen can be directly output and collected, and under the ultrahigh pressure (40-100 Mpa) environment, the pure hydrogen conveying pressure output in the separated pure hydrogen output tube can also be provided by the liquid pump 1, so that the inconvenience that a compressor is required to be arranged on the pure hydrogen output tube to collect the pure hydrogen in the past is avoided.
For the transportation of the generated carbon dioxide mixed residual gas, controlling the pressure and the temperature of the carbon dioxide mixed residual gas in a carbon dioxide separation device through a liquid pump 1 and a water-cooling 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, and enabling the molar ratio of the carbon dioxide in the hydrogen mixed residual gas to be lower than 26 percent so as to prepare the hydrogen mixed residual gas as a reforming mixed gas of a subsequent step; the mixed residual hydrogen is sent into the lower reaction cavity 32 of the reforming separation device 3, the working temperature of the lower reaction cavity 32 and the upper reaction cavity 31 and the working temperature of the hydrogen absorption pipe 34 are uniformly controlled by the heating cavity 33, the mixed residual hydrogen is reformed by water gas distribution, the carbon monoxide in the mixed residual hydrogen is reduced to 0.5-1.5% from original 3-9%, and the gas phase component of the reformed mixed gas is as follows: 62-77% of hydrogen, 22-27% of carbon dioxide and 0.5-1.5% of carbon monoxide; the gas phase component of the reforming mixed gas is close to the mixed gas component of the hydrogen, the carbon dioxide and the carbon monoxide prepared by the reformer, the reforming mixed gas directly enters the upper reaction chamber 31 from the lower reaction chamber 32, is mixed with the mixed gas of the hydrogen, the carbon dioxide and the carbon monoxide, and is subjected to circulating hydrogen absorption separation again through the hydrogen absorption pipe 34, 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%.
With the above-described preferred embodiments according to the present invention as an illustration, the above-described descriptions can be used by persons skilled in the relevant art to make various changes and modifications without departing from the scope of the technical idea of the present invention. The technical scope of the present invention is not limited to the description, but must be determined according to the scope of claims.
Claims (7)
1. The reforming and separating integrated ultrahigh-pressure hydrogen production system is characterized by comprising a reforming and separating device, a three-phase heat exchange device, a steam trap, a water-cooling heat exchanger and a carbon dioxide liquefying device;
the reforming separation device comprises an upper reaction cavity and a lower reaction cavity, wherein the upper reaction cavity is communicated with the lower reaction cavity, the upper reaction cavity is filled with a first catalytic filler, and the lower reaction cavity is filled with a second catalytic filler;
the upper reaction cavity is provided with a first inlet for inputting methanol vapor and a first outlet for outputting carbon dioxide mixed residual gas, a hydrogen absorption pipe is inserted into the upper reaction cavity, the hydrogen absorption pipe carries out hydrogen absorption separation on the mixed gas in the upper reaction cavity, and the absorbed hydrogen is output from the hydrogen absorption pipe; the lower reaction cavity is provided with a second inlet for inputting hydrogen mixed residual gas;
the first inlet is connected with a methanol vapor inlet pipe, the outlet of the hydrogen absorption pipe is connected with a pure hydrogen outlet pipe, the first outlet is connected with a carbon dioxide mixed residual gas outlet pipe, the methanol vapor inlet pipe, the pure hydrogen outlet pipe and the carbon dioxide mixed residual gas outlet pipe are all connected with a three-phase heat exchange device, the carbon dioxide mixed residual gas outlet pipe is sequentially connected with a steam trap, a water-cooling heat exchanger and a carbon dioxide liquefying device, the carbon dioxide liquefying device is connected with a hydrogen mixed residual gas outlet pipe, the hydrogen mixed residual gas outlet pipe is connected with a second inlet of the reforming separation device, and an air pump for conveying pressure of hydrogen mixed residual gas in the riser is arranged on the hydrogen mixed residual gas outlet pipe;
the methanol vapor inlet pipe is connected with a liquid pump, the pumping pressure of the liquid pump is 40-100 Mpa, the water-cooling heat exchanger is connected with a water-cooling tower, the operation temperature of the water-cooling heat exchanger is less than or equal to 30.8 ℃, and pure hydrogen in the hydrogen outlet pipe is sent into a hydrogen storage tank under the pumping pressure of the liquid pump;
the working temperature of the lower reaction cavity and the upper reaction cavity and the working temperature of the hydrogen absorption tube are uniformly controlled by the heating cavity.
2. The reforming and separation integrated ultrahigh-pressure hydrogen system according to claim 1, wherein the hydrogen absorption tube is a niobium tube, the first catalytic filler is a copper-based filler or a zirconium-based filler, the second catalytic filler is a copper-based filler or a zirconium-based filler, and the temperature of the heating cavity operation is 200-500 ℃.
3. The reforming and separation integrated ultrahigh-pressure hydrogen system according to claim 1, wherein the hydrogen absorption tube is a palladium membrane tube or a palladium alloy membrane tube, the first catalytic filler is a copper-based filler or a zirconium-based filler, the second catalytic filler is a copper-based filler or a zirconium-based filler, and the temperature of the heating cavity operation is 250-550 ℃.
4. The integrated reforming and separation ultrahigh-pressure hydrogen system according to claim 1, wherein the pure hydrogen outlet pipe is connected to a hydrogen storage tank, pure hydrogen is fed into the hydrogen storage tank under the pumping pressure of a liquid pump, and the hydrogen storage tank is connected to a hydrogenation machine.
5. An ultrahigh-pressure hydrogen production method, characterized in that the reforming and separation integrated ultrahigh-pressure hydrogen production system according to any one of claims 1 to 4 is adopted, comprising the following steps:
s1, feeding methanol water into a methanol-water vapor pipe inlet pipe by a liquid pump, wherein the pumping pressure is 40-100 Mpa, heating and vaporizing the methanol water into methanol water vapor, feeding the methanol water vapor into an upper reaction cavity of a reforming and separating device, performing reforming reaction on the methanol water vapor in the upper reaction cavity to generate mixed gas of hydrogen, carbon dioxide and carbon monoxide, and then performing hydrogen separation on the generated mixed gas of hydrogen, carbon dioxide and carbon monoxide by a hydrogen absorbing pipe;
the gas phase components of the mixed gas of the hydrogen, the carbon dioxide and the carbon monoxide are 65-75% of the hydrogen, 20-26% of the carbon dioxide and 0.3-3% of the carbon monoxide;
s2, separating mixed gas of hydrogen, carbon dioxide and carbon monoxide by a hydrogen absorption pipe, outputting and collecting the separated pure hydrogen from the hydrogen absorption pipe, and sending the pure hydrogen into a hydrogen storage tank under the pumping pressure of a liquid pump; outputting the residual carbon dioxide mixed residual gas from a carbon dioxide mixed residual gas outlet pipe, controlling the pressure of the carbon dioxide mixed residual gas by a liquid pump, controlling the temperature of the carbon dioxide mixed residual gas by a water-cooling heat exchanger, and then sending the carbon dioxide mixed residual gas 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 is 40-100 Mpa, and the temperature controlled by the water-cooling heat exchanger is less than or equal to 30.8 ℃;
s3, preparing liquid carbon dioxide and hydrogen mixed residual gas in a carbon dioxide separator from the carbon dioxide mixed residual gas, and outputting and collecting the liquid carbon dioxide;
the components of the hydrogen mixed residual gas are 65-75% of hydrogen, 20-26% of carbon dioxide and 3-9% of carbon monoxide;
s4, delivering the hydrogen mixed residual gas into a lower reaction cavity of the reforming separation device, preparing reformed mixed gas by water distribution, and distributing water and carbon monoxide according to the content of the carbon monoxide: water is 1:1-20;
the fed hydrogen mixed residual gas is subjected to water distribution reforming in a lower reaction cavity to form reforming mixed gas, wherein the gas phase components of the reforming mixed gas are 62-77% of hydrogen, 22-27% of carbon dioxide and 0.5-1.5% of carbon monoxide;
the ratio of the hydrogen, the carbon dioxide and the carbon monoxide in the reforming mixed gas is close to the ratio of the hydrogen, the carbon dioxide and the carbon monoxide in the mixed gas of the hydrogen, the carbon dioxide and the carbon monoxide;
s5, the reforming mixed gas enters an upper reaction cavity and is mixed with the mixed gas of hydrogen, carbon dioxide and carbon monoxide, and a hydrogen absorption pipe carries out hydrogen separation operation on the reforming mixed gas and the mixed gas of hydrogen, carbon dioxide and carbon monoxide.
6. The ultrahigh-pressure hydrogen production method according to claim 5, wherein the output pure hydrogen and carbon dioxide mixed residual gas are output after being subjected to heat exchange and temperature reduction by a three-phase heat exchange device, and the methanol water is vaporized into methanol water vapor by heat exchange by the three-phase heat exchange device.
7. The ultra-high pressure hydrogen process of claim 5, wherein said methanol water is replaced with natural gas.
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