CN110844883B - Hydrogen separation and water gas reforming integrated low-pressure hydrogen production system and method thereof - Google Patents
Hydrogen separation and water gas reforming integrated low-pressure hydrogen production system and method thereof Download PDFInfo
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- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 297
- 239000001257 hydrogen Substances 0.000 title claims abstract description 297
- 239000007789 gas Substances 0.000 title claims abstract description 237
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 186
- 150000002431 hydrogen Chemical class 0.000 title claims abstract description 111
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 79
- 238000002407 reforming Methods 0.000 title claims abstract description 75
- 238000000926 separation method Methods 0.000 title claims abstract description 70
- 238000004519 manufacturing process Methods 0.000 title abstract description 40
- 238000000034 method Methods 0.000 title description 11
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 268
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 134
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 134
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 57
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 50
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 50
- 238000006243 chemical reaction Methods 0.000 claims description 42
- 239000007788 liquid Substances 0.000 claims description 30
- 239000000945 filler Substances 0.000 claims description 28
- 238000010521 absorption reaction Methods 0.000 claims description 23
- 238000003860 storage Methods 0.000 claims description 16
- 238000005984 hydrogenation reaction Methods 0.000 claims description 15
- 239000003054 catalyst Substances 0.000 claims description 13
- 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 6
- 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
- 238000003825 pressing Methods 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 abstract description 9
- 238000009826 distribution Methods 0.000 abstract description 7
- 238000006057 reforming reaction Methods 0.000 abstract description 6
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 description 30
- 239000000446 fuel Substances 0.000 description 14
- 238000006555 catalytic reaction Methods 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 230000002441 reversible effect Effects 0.000 description 6
- 238000007086 side reaction Methods 0.000 description 4
- 239000003345 natural gas Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 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
- 238000010248 power generation Methods 0.000 description 2
- 238000005086 pumping Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 230000008016 vaporization Effects 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
- 238000001816 cooling Methods 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
- 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
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000009834 vaporization 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
- C01B3/326—Catalytic reaction of gaseous or liquid organic compounds other than hydrocarbons with gasifying agents characterised by the catalyst
-
- 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
- C01B3/508—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by selective and reversible uptake by an appropriate medium, i.e. the uptake being based on physical or chemical sorption phenomena or on reversible chemical reactions
-
- 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
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/042—Purification by adsorption on solids
-
- 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
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/0465—Composition of the impurity
- C01B2203/047—Composition of the impurity the impurity being carbon monoxide
-
- 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
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/0465—Composition of the impurity
- C01B2203/0475—Composition of the impurity the impurity being 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
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
-
- 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
Abstract
The invention relates to a hydrogen separation and water gas reforming integrated low-pressure hydrogen production system, which comprises a reformer, a three-phase heat exchange device, a steam trap, an air compressor, a refrigerator, a carbon dioxide liquefying device and a hydrogen separation and water gas reforming integrated device; the pressure controlled by the air compressor is 5-30 MPa, and the temperature controlled by the refrigerator is-35-30.8 ℃. The low-pressure hydrogen preparation method includes that methanol steam is subjected to reforming reaction in a reformer to generate mixed gas of hydrogen, carbon dioxide and carbon monoxide, and the mixed gas of the hydrogen is sent into a water gas reforming cavity of a water gas reforming integrated device to be prepared into reformed mixed gas by water distribution; the reformed mixed gas enters a hydrogen separation cavity to be mixed with mixed gas of hydrogen, carbon dioxide and carbon monoxide, and the mixed gas performs hydrogen separation operation in the hydrogen separation cavity; 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 hydrogen separation and water gas reforming integrated low-pressure hydrogen production system and a 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, accidents easily occur in the hydrogen storage link, the cost of the hydrogen transportation link is higher, and the characteristics of the hydrogen are related; 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 defect of the prior art is overcome, a hydrogen separation and water gas reforming integrated low-pressure hydrogen production system is provided, and the problem that the hydrogen production system is complicated due to a split structure between a water gas reforming and hydrogen separation device in the existing hydrogen production system is solved;
meanwhile, the low-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 hydrogen separation and water gas reforming integrated low-pressure hydrogen system comprises a reformer, a three-phase heat exchange device, a steam trap, an air compressor, a refrigerator, a carbon dioxide liquefying 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 methanol water vapor inlet pipe is connected with the three-phase heat exchange device, and the reformer is suitable for preparing the methanol water vapor into 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 out 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 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 air compressor, the steam trap, the refrigerator 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 methanol vapor inlet is connected with a liquid pump, and the working pressure of the liquid pump is 2-5 MPa;
the pressure controlled by the air compressor is 5-30 MPa, and the temperature controlled by the refrigerator is-35-30.8 ℃.
Furthermore, the carbon dioxide mixed residual gas outlet pipe and the pure hydrogen outlet pipe are connected with a three-phase heat exchange device.
Further, the hydrogen absorption tube is a niobium tube, the catalyst filler is copper-based filler, and the operation temperature of the reaction cavity is 200-350 ℃;
or the catalyst filler is zirconium-based filler, and the operation temperature of the reaction cavity 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 operation temperature of the reaction cavity is 250-550 ℃.
Further, the pure hydrogen outlet pipe is connected with a hydrogen storage tank, a compressor is arranged on the hydrogen outlet pipe and is suitable for pressing pure hydrogen into the hydrogen storage tank, and the hydrogen storage tank is connected with a hydrogenation machine.
In yet another aspect, a low pressure hydrogen production method, using the low pressure hydrogen production system described above, comprises the steps of:
s1, feeding methanol water into a methanol-water vapor pipe inlet pipe by a liquid pump, wherein the pumping pressure is 2-5 MPa, heating and vaporizing the methanol water into methanol water vapor, feeding the methanol water vapor into a reformer, carrying out reforming reaction on the methanol water vapor in the reformer to generate mixed gas of hydrogen, carbon dioxide and carbon monoxide, and feeding the mixed gas of the hydrogen, the carbon dioxide and the carbon monoxide into a hydrogen separation cavity of a water gas reforming integrated device;
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, a hydrogen absorption pipe in the hydrogen separation cavity separates mixed gas of hydrogen, carbon dioxide and carbon monoxide, and the separated pure hydrogen is output from the hydrogen absorption pipe and collected; outputting the residual carbon dioxide mixed residual gas from the hydrogen separation cavity, controlling the pressure of the carbon dioxide mixed residual gas through an air compressor, controlling the temperature of the carbon dioxide mixed residual gas through a refrigerator, 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 air compressor is 5-30 MPa, and the temperature controlled by the refrigerator is-35-30.8 ℃;
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, feeding the hydrogen mixed residual gas into a water gas reforming cavity of the water gas reforming integrated device, and distributing water to prepare reformed mixed gas, 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 water gas reforming cavity to form reforming mixed gas, wherein the gas phase components of the reforming 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 is close 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;
s5, the reformed mixed gas enters a hydrogen separation cavity to be mixed with the mixed gas of the hydrogen, the carbon dioxide and the carbon monoxide, and the reformed 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.
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 hydrogen production system combines the water gas reforming and hydrogen separation device in the traditional hydrogen production system into one device, so that the hydrogen mixed residual gas 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 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 small hydrogen production device can be manufactured by means of the hydrogen production system.
In the hydrogen production system, the liquid pump provides a low-pressure reaction environment, so that the whole hydrogen production system can be operated more safely and stably. And providing working pressure and temperature in the carbon dioxide liquefying device for the output carbon dioxide mixed residual gas through an air compressor and a refrigerator, separating the carbon dioxide mixed residual gas into hydrogen mixed residual gas with a preset molar ratio, and then preparing the hydrogen mixed residual gas into reformed mixed gas through a water gas reforming device.
Secondly, recycling the carbon dioxide mixed residual gas generated in the hydrogen production system, controlling the pressure and temperature of separating liquid carbon dioxide from the carbon dioxide mixed residual gas through an air compressor and a refrigerator, separating the hydrogen mixed residual gas and the liquid carbon dioxide from the carbon dioxide mixed residual gas through a carbon dioxide liquefying device, and storing the liquid carbon dioxide; and finally, the hydrogen mixed residual gas is reformed by water gas distribution, 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 components of the reformed mixed gas are 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 membrane separation and purification device again to carry out hydrogen purification and separation hydrogen production operation, 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 schematic diagram of a hydrogen separation and water gas reforming integrated low pressure hydrogen system of the present invention;
FIG. 2 is a schematic diagram of a water gas reforming integrated plant;
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 cavity 31, a hydrogen separation cavity 32, a hydrogen absorption pipe 33, a heating cavity 34, a reformer 4, an air compressor 5, an air compressor 6, a refrigerator 7 and a carbon dioxide liquefying device.
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, the integrated hydrogen separation and water gas reforming low-pressure hydrogen production system comprises a reformer 4, a three-phase heat exchange device 2, a steam trap, an air compressor 5, a refrigerator 6, a carbon dioxide liquefying device 7 and an integrated hydrogen separation and water gas reforming device 3;
the reformer 4 is connected with a methanol steam inlet pipe and a mixed gas outlet pipe; the reformer 4 is adapted to produce methanol vapor as a 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 out 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 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 air compressor 5, the steam trap, the refrigerator 6 and the carbon dioxide liquefying device 7, the carbon dioxide liquefying device 7 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 methanol vapor inlet is connected with a liquid pump 1, the methanol vapor inlet pipe is connected with a three-phase heat exchange device 2, and the working pressure of the liquid pump 1 is 2-5 MPa;
the pressure controlled by the air compressor 5 is 5-30 MPa, and the temperature controlled by the refrigerator 6 is-35-30.8 ℃.
Specifically, the carbon dioxide mixed residual gas outlet pipe and the pure hydrogen outlet pipe are both connected with the three-phase heat exchange device 2, the pure hydrogen and the carbon dioxide mixed residual gas are both subjected to heat exchange and temperature reduction with the three-phase heat exchange device 2 and then output, and the exchanged heat is provided for the methanol water vapor inlet pipe for carrying out vaporization operation on the methanol water.
The steam trap is arranged on the carbon dioxide mixed residual gas outlet pipe, so that the moisture in the carbon dioxide mixed residual gas can be reduced through the steam trap.
Specifically, in this embodiment, the hydrogen absorption tube 33 is a niobium tube, the catalyst filler is a copper-based filler, and the operation temperature of the reaction chamber is 200-350 ℃; or the catalyst filler is zirconium-based filler, and the operation temperature of the reaction cavity is 350-550 ℃.
Or, the hydrogen absorption tube 33 is a palladium membrane tube or a palladium alloy membrane tube, the catalyst filler is a zirconium-based filler, and the operation temperature of the reaction cavity 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 200-350 ℃, and the catalytic reaction temperature of the zirconium-based filler is 350-550 ℃.
The pure hydrogen outlet pipe is connected with the hydrogen storage tank, the hydrogen outlet pipe is provided with a compressor, the pure hydrogen is suitable for being pressed into the hydrogen storage tank, 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.
The hydrogen production system combines the water gas reforming and hydrogen separation device in the traditional hydrogen production system into one device, so that the hydrogen mixed residual gas water gas reforming operation and the mixed gas separation reaction of hydrogen, carbon dioxide and carbon monoxide are operated in the same 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 is vaporized into methanol water vapor by the three-phase heat exchange device 2, the working pressure of the liquid pump 1 is 2-5 MPa, the methanol water vapor enters the reformer 4, and the methanol water vapor carries out catalytic reaction in the reformer 4, so that the methanol water vapor is a multi-component and multi-reaction gas-solid catalytic reaction system;
the reaction equation is:
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 reaction)
The reforming reaction produces 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 carries out hydrogen absorption separation on the mixed gas of hydrogen, carbon dioxide and carbon monoxide, and separated pure hydrogen is output from a pure hydrogen outlet pipe; the separated carbon dioxide mixed residual gas is output from a carbon dioxide mixed residual gas outlet pipe, the pressure and the temperature of the carbon dioxide mixed residual gas are controlled by an air compressor 5 and a refrigerator 6 in sequence, the carbon dioxide mixed residual gas and carbon dioxide separation device performs liquefaction separation, 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 hydrogen mixed residual gas is changed into reformed mixed gas after being subjected to water gas reforming, the proportion of gas phase components of the reformed mixed gas and the mixed gas components of hydrogen, carbon dioxide and carbon monoxide generated by reforming reaction are close, the reformed mixed gas in the water gas reforming cavity 31 directly enters a hydrogen separation cavity 32 and is mixed with the mixed gas of the hydrogen, the carbon dioxide and the carbon monoxide, and the hydrogen is circularly absorbed and separated again by a hydrogen absorption pipe 33, so that the hydrogen yield of the whole low-pressure hydrogen production system is improved.
The air compressor 5 provides pressure for conveying the hydrogen mixed residual gas discharged by the carbon dioxide separation device, and if the air pressure is insufficient, an air pump can be arranged on a conveying pipeline of the hydrogen mixed residual gas to ensure the conveying pressure.
According to the low-pressure hydrogen production system, the pressure provided by the liquid pump 1 is 2-5 MPa, the whole hydrogen production system operates in a low-pressure state, and the hydrogen production operation is safer; the water gas reforming and hydrogen separation device is combined into one device, so that the whole hydrogen production system structure is optimized and simplified, and the small hydrogen production device can be manufactured by means of the hydrogen production system.
Example two
The low-pressure hydrogen preparation method adopts the low-pressure hydrogen preparation system and comprises the following steps:
s1, feeding methanol water into a methanol-water vapor pipe inlet pipe by a liquid pump 1, wherein the pumping pressure is 2-5 MPa, the methanol water is heated and gasified into methanol water vapor, the methanol water vapor enters a reformer 4, the methanol water vapor undergoes a reforming reaction in the reformer 4 to generate mixed gas of hydrogen, carbon dioxide and carbon monoxide, and the methanol water vapor undergoes a catalytic reaction at a corresponding temperature and under a catalyst filler, so that the system 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);
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; then the mixed gas of hydrogen, carbon dioxide and carbon monoxide is sent into the hydrogen separation cavity 32 of the water gas reforming integrated device 3;
s2, the temperature of the heating cavity 34 directly controls the operation temperatures of the hydrogen separation cavity 32 and the water gas reforming cavity 31, a hydrogen absorption pipe 33 in the hydrogen separation cavity 32 separates the mixed gas of hydrogen, carbon dioxide and carbon monoxide, and the separated pure hydrogen is output from the hydrogen absorption pipe 33 and collected; outputting the rest carbon dioxide mixed residual gas from the hydrogen separation cavity 32, controlling the pressure of the carbon dioxide mixed residual gas through the air compressor 5, controlling the temperature of the carbon dioxide mixed residual gas through the refrigerator 6, and then sending the carbon dioxide mixed residual gas into the 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 air compressor 5 is 5-30 MPa, and the temperature controlled by the refrigerator 6 is-35-30.8 ℃;
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%, and the selection of the pressure and the temperature of the carbon dioxide liquefying device 7 during working is shown in the following table:
| scheme for the production of a semiconductor device | Pressure (Mpa) | Temperature (. Degree. C.) |
| Scheme 1 | 5 | -35 |
| Scheme 2 | 7 | -25 |
| Scheme 3 | 10 | -10 |
| Scheme 4 | 15 | 0 |
| Scheme 5 | 20 | 20 |
| Scheme 6 | 25 | 25 |
| Scheme 7 | 30 | 30.8 |
S4, feeding the hydrogen mixed residual gas into a water gas reforming cavity 31 of the water gas reforming integrated device 3, and distributing water to prepare reformed mixed gas, 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 water gas reforming cavity 31 to form reforming mixed gas, wherein the gas phase components of the reforming mixed gas comprise 62-77% of hydrogen, 22-27% of carbon dioxide and 0.5-1.5% of carbon monoxide;
the water gas reforming reaction formula is: CO+H 2 O→CO 2 +H 2 ；
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;
and S5, the reformed 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 reformed 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 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 low-pressure hydrogen preparation method, by means of the hydrogen separation and water gas reforming integrated low-pressure hydrogen preparation system in the first embodiment, methanol water is used as a hydrogen preparation raw material, a liquid pump 1 provides low pressure (2-5 MPa) at a source to pump the methanol water into a reformer 4 to react to generate mixed gas of hydrogen, carbon dioxide and carbon monoxide, then the mixed gas of the hydrogen, the carbon dioxide and the carbon monoxide is sent into a hydrogen separation cavity 32 of a water gas reforming integrated device 3 to directly react with a hydrogen absorption pipe 33 in the hydrogen separation cavity 32 to absorb hydrogen, pure hydrogen can be directly output and collected, and the hydrogen preparation efficiency is greatly improved. Then, conveying the generated carbon dioxide mixed residual gas, controlling the pressure and the temperature of the carbon dioxide mixed residual gas in a carbon dioxide separation device through a air compressor 5 and a cooling machine, liquefying and separating the carbon dioxide in the carbon dioxide mixed residual gas, controlling the components of the separated hydrogen mixed residual gas, and enabling the carbon dioxide molar ratio in the hydrogen mixed residual gas to be lower than 26 percent, so that the hydrogen mixed residual gas is ready for the subsequent reforming mixed gas; the hydrogen mixed residual gas is sent into the water gas reforming cavity 31 of the water gas reforming integrated device 3, the operation temperature of the water gas reforming of the hydrogen mixed residual gas is the same as the hydrogen separation operation temperature of the hydrogen absorption pipe 33, and the carbon monoxide in the hydrogen mixed residual gas is reduced to 0.5-1.5% from the original 3-9% by water gas water distribution reforming, so that the gas phase components of the reformed mixed gas are 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 4, the reforming mixed gas directly enters the hydrogen separation cavity 32 from the water gas reforming cavity 31, is mixed with the mixed gas of the hydrogen, the carbon dioxide and the carbon monoxide, and is circularly absorbed and separated 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%.
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 (3)
1. The integrated low-pressure hydrogen-producing system is characterized by comprising a reformer, a three-phase heat exchange device, a steam trap, an air compressor, a refrigerator, a carbon dioxide liquefying device and an integrated hydrogen separation and water gas reforming device;
the reformer is connected with a methanol steam inlet pipe and a mixed gas outlet pipe; the methanol vapor inlet pipe is connected with the three-phase heat exchange device, and the reformer is suitable for preparing the methanol vapor into the 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 out 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 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 air compressor, the steam trap, the refrigerator 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 methanol vapor inlet is connected with a liquid pump, and the working pressure of the liquid pump is 2-5 MPa;
the pressure controlled by the air compressor is 5-30 MPa, and the temperature controlled by the refrigerator is-35-30.8 ℃;
the pure hydrogen outlet pipe is connected with a hydrogen storage tank, a compressor is arranged on the hydrogen outlet pipe and is suitable for pressing pure hydrogen into the hydrogen storage tank, and the hydrogen storage tank is connected with a hydrogenation machine;
and the carbon dioxide mixed residual gas outlet pipe and the pure hydrogen outlet pipe are connected with the three-phase heat exchange device.
2. The hydrogen separation and water gas reforming integrated low-pressure hydrogen system according to claim 1, wherein the hydrogen absorption tube is a niobium tube, the catalyst filler is a copper-based filler, and the operating temperature of the reaction chamber is 200-350 ℃;
or the catalyst filler is zirconium-based filler, and the operation temperature of the reaction cavity is 350-550 ℃.
3. The hydrogen separation and water gas reforming integrated low-pressure hydrogen system according to 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 operation temperature of the reaction chamber is 250-550 ℃.
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| CA1291319C (en) * | 1985-06-10 | 1991-10-29 | Bahjat S. Beshty | Method of steam reforming methanol to hydrogen |
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| US20170183226A1 (en) * | 2015-06-05 | 2017-06-29 | Guangdong Hydrogen Energy Science And Te | Residual gas heat exchange combustion-supporting system based on methanol-water mixture reforming hydrogen production system, and method thereof |
| CN211847143U (en) * | 2019-10-28 | 2020-11-03 | 中科院大连化学物理研究所张家港产业技术研究院有限公司 | Hydrogen separation and water gas reforming integrated low-pressure hydrogen production system |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CA1291319C (en) * | 1985-06-10 | 1991-10-29 | Bahjat S. Beshty | Method of steam reforming methanol to hydrogen |
| WO2005033003A1 (en) * | 2003-10-06 | 2005-04-14 | Statoil Asa | Hydrogen production from methanol |
| CN101616865A (en) * | 2006-11-30 | 2009-12-30 | 国际壳牌研究有限公司 | Produce the system and method for hydrogen and carbonic acid gas |
| US20170183226A1 (en) * | 2015-06-05 | 2017-06-29 | Guangdong Hydrogen Energy Science And Te | Residual gas heat exchange combustion-supporting system based on methanol-water mixture reforming hydrogen production system, and method thereof |
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| CN211847143U (en) * | 2019-10-28 | 2020-11-03 | 中科院大连化学物理研究所张家港产业技术研究院有限公司 | Hydrogen separation and water gas reforming integrated low-pressure hydrogen production system |
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