CN110862067B - Low-pressure hydrogen production system of methanol water hydrogenation station and working method thereof - Google Patents

Low-pressure hydrogen production system of methanol water hydrogenation station and working method thereof Download PDF

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CN110862067B
CN110862067B CN201911032712.0A CN201911032712A CN110862067B CN 110862067 B CN110862067 B CN 110862067B CN 201911032712 A CN201911032712 A CN 201911032712A CN 110862067 B CN110862067 B CN 110862067B
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hydrogen
carbon dioxide
gas
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CN110862067A (en
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岳锌
韩涤非
李军
李佳毅
岳野
姚婷婷
赵纪军
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Zhangjiagang Industry Technology Research Institute Co ltd Dalian Institute Of Chemical Physics Chinese Academy Of Sciences
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Zhangjiagang Industry Technology Research Institute Co ltd Dalian Institute Of Chemical Physics Chinese Academy Of Sciences
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/323—Catalytic reaction of gaseous or liquid organic compounds other than hydrocarbons with gasifying agents
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
    • C01B3/12—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of water vapour with carbon monoxide
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/50—Carbon dioxide
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    • 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
    • C01B2203/0283—Processes for making hydrogen or synthesis gas containing a CO-shift step, i.e. a water gas shift step
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    • 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
    • C01B2203/0405—Purification by membrane separation
    • 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
    • C01B2203/046—Purification by cryogenic separation
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    • 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
    • C01B2203/12—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 low-pressure hydrogen production system of a methanol water hydrogenation station and a working method thereof. The working method comprises the following steps: s1, heating methanol water into methanol water vapor; s2, sending the mixed gas of hydrogen, carbon dioxide and carbon monoxide into a membrane separation and purification device at a controlled temperature, and S3, sending the mixed gas of carbon dioxide into a carbon dioxide liquefying device; s4, conveying the hydrogen mixed residual gas to water gas reforming; s5, mixing the reforming mixed gas with the mixed gas of the hydrogen and the carbon dioxide, and enabling the reforming mixed gas to enter the membrane separation and purification device again along with the mixed gas of the hydrogen, the carbon dioxide and the carbon monoxide for hydrogen purification and separation. Realize the circular purification of the gas and realize the hydrogen yield of more than or equal to 95 percent.

Description

Low-pressure hydrogen production system of methanol water hydrogenation station and working method thereof
Technical Field
The invention relates to a low-pressure hydrogen production system of a methanol water hydrogenation station and a working 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 the conventional hydrogen adding station, the high cost of hydrogen transportation link is shortened or reduced, the investment of compressor equipment is reduced, the energy consumption for equipment operation is reduced, and the maintenance cost of the equipment is reduced, so that 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 low-pressure hydrogen production system of a methanol-water hydrogenation station and a working method thereof, and solves the problems of high potential safety hazard and long-distance high-cost hydrogen transportation caused by the need of storing a large amount of hydrogen in the conventional hydrogenation station.
The technical scheme adopted for solving the technical problems is as follows:
the low-pressure hydrogen production system of the methanol water hydrogenation station is characterized by comprising a first diverter, a first-stage first diversion channel, a first-stage second diversion channel, a reformer, a second diverter, a second-stage first diversion channel, a second-stage second diversion channel, a membrane separation and purification device, a pure hydrogen output channel and a carbon dioxide mixed residual gas output channel;
the first diverter outlet is connected with a first-stage first diversion channel and a second-stage second diversion channel; a delivery pump is arranged on the inlet pipeline of the first flow divider;
the first heat exchanger is arranged on the first-stage first diversion channel, the second heat exchanger is arranged on the second-stage second diversion channel, the working temperature of the first heat exchanger and the second heat exchanger is 20-300 ℃, and the first-stage first diversion channel and the second-stage first diversion channel are suitable for preparing methanol water in the first-stage first diversion channel and the second-stage first diversion channel into methanol water vapor;
The outlets of the first-stage first diversion channel and the second-stage diversion channel are connected with the reformer, and are suitable for sending the methanol vapor in the first-stage first diversion channel and the second-stage diversion channel into the reformer, and the methanol vapor is used for preparing mixed gas of hydrogen, carbon dioxide and carbon monoxide in the reformer;
the reaction equation is:
CH 3 OH→CO+2H 2 ；
H 2 O+CO→CO 2 +H 2 ；
CH 3 OH+H 2 O→CO 2 +3H 2 ；
2CH 3 OH→CH 3 OCH 3 +H 2 O；
CO+3H 2 →CH 4 +H 2 O；
the gas phase components of the mixed gas of the hydrogen, the carbon dioxide and the carbon monoxide are 65-75% of hydrogen, 20-26% of carbon dioxide and 0.3-3% of carbon monoxide;
the outlet of the reformer is connected with a second shunt, and the outlet of the second shunt is communicated with the inlet of the membrane separation and purification device through a second-stage first shunt channel and a second-stage second shunt channel;
the membrane separation and purification device is connected with a pure hydrogen output channel and a carbon dioxide mixed residual gas output channel, separates the mixed gas of the fed hydrogen, carbon dioxide and carbon monoxide into the pure hydrogen and carbon dioxide mixed residual gas, and has the working temperature of 380-420 ℃, the temperature of the separated pure hydrogen is 380-420 ℃, and the temperature of the separated carbon dioxide mixed residual gas is 380-420 ℃;
the gas phase components of the carbon dioxide mixed residual gas comprise 25-45% of hydrogen, 55-75% of carbon dioxide, 0.3-3% of carbon monoxide and 0-3% of water;
The separated pure hydrogen is conveyed into a hydrogen storage tank of a hydrogenation station through a pure hydrogen output channel, the pure hydrogen output channel sequentially passes through a fourth heat exchanger and a second heat exchanger, the fourth heat exchanger is used for preheating mixed gas of hydrogen, carbon dioxide and carbon monoxide in a second-stage second split-flow channel, and the second heat exchanger is used for preparing methanol water in the first-stage second split-flow channel into methanol water vapor;
the separated carbon dioxide mixed residual gas is conveyed by a carbon dioxide mixed residual gas output channel, the carbon dioxide mixed residual gas output channel sequentially passes through a third heat exchanger and a first heat exchanger, the third heat exchanger is used for preheating the mixed gas of hydrogen, carbon dioxide and carbon monoxide in the second-stage first split-flow channel, and the first heat exchanger is used for preparing methanol water in the first-stage first split-flow channel into methanol water vapor.
Further, the outlet of the carbon dioxide mixed residual gas output channel is connected with a carbon dioxide liquefying device;
the carbon dioxide liquefying device separates the carbon dioxide mixed residual gas into liquid carbon dioxide and hydrogen mixed residual gas, and the liquid carbon dioxide is collected; the components of the hydrogen mixed residual gas are 65-75% of hydrogen, 20-26% of carbon dioxide and 3-9% of carbon monoxide;
When the carbon dioxide liquefying device works, the pressure applied to the carbon dioxide mixed residual gas is 5-30 Mpa, and the working temperature is-35-30.8 ℃.
Further, the carbon dioxide liquefying device is connected with the water gas reforming reaction device, and the carbon dioxide liquefying device sends the separated hydrogen mixed residual gas into the water gas reforming reaction device for reforming;
the working temperature of the water gas reforming reaction device is 200-280 ℃, water distribution is carried out according to the content of carbon monoxide, and the water distribution ratio (carbon monoxide: water) is 1:1-20;
the water gas reforming reaction device reforms the fed hydrogen mixed residual gas into reforming mixed gas by distributing water, and 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 water gas reforming reaction device is connected with a reformed gas channel, the outlet of the reformer channel is connected with the inlet of the second flow divider, the reformed mixed gas is sent into the second flow divider through the reformed gas channel, and the reformed mixed gas and the mixed gas of hydrogen, carbon dioxide and carbon monoxide prepared in the reformer are sent into the membrane separation purification device together for circulation purification.
Furthermore, the inlet of the reformer is provided with a first temperature controller, and the methanol steam and the water steam conveyed by the first-stage first diversion channel and the first-stage second diversion channel are input into the reformer after being subjected to temperature control by the first temperature controller.
Furthermore, a second temperature controller is arranged at the inlet of the membrane separation and purification device, and the mixed gas of hydrogen, carbon dioxide and carbon monoxide conveyed by the second-stage first diversion channel and the second-stage second diversion channel is sent to the membrane separation and purification device after being subjected to temperature control by the second temperature controller.
Further, a first air compressor, a third temperature controller and a fourth temperature controller are arranged on the carbon dioxide mixed residual gas output channel, the third temperature controller is located at the upstream of the first air compressor, and the fourth temperature controller is located at the downstream of the first air compressor.
Further, a second air compressor and a fifth temperature controller are arranged on the pure hydrogen output channel, and the fifth temperature controller is located at the upstream of the second air compressor.
Further, the hydrogen storage tank is connected with the hydrogenation machine and is suitable for outputting hydrogen in the hydrogen storage tank.
In another aspect, a working method of the low-pressure hydrogen production system of the methanol water hydrogenation station adopts the low-pressure hydrogen production system of the methanol water hydrogenation station, and comprises the following steps:
S1, conveying methanol water by a conveying pump, heating and vaporizing the methanol water to form methanol water vapor, and conveying the methanol water vapor into a reformer to reform to form mixed gas of hydrogen, carbon dioxide and carbon monoxide, wherein the ratio of the methanol to the water in the methanol water is 1:1; the working pressure of the conveying pump is 2-5 MPa;
the working pressure of the reformer is 2-5 MPa, and the working temperature of the reformer is 220-320 ℃; 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, sending the mixed gas of hydrogen, carbon dioxide and carbon monoxide into a membrane separation and purification device at the working temperature of 380-420 ℃, and separating the mixed gas of the sent hydrogen, carbon dioxide and carbon monoxide into pure hydrogen and carbon dioxide mixed residual gas by the membrane separation and purification device;
collecting the pure hydrogen into a hydrogen storage tank of a hydrogenation station;
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;
s3, delivering the carbon dioxide mixed residual gas into a carbon dioxide liquefying device;
The carbon dioxide liquefying device separates the carbon dioxide mixed residual gas into liquid carbon dioxide and hydrogen mixed residual gas;
the liquid carbon dioxide is collected;
the components of the hydrogen mixed residual gas are 65-75% of hydrogen, 20-26% of carbon dioxide and 3-9% of carbon monoxide;
when the carbon dioxide liquefying device works, the pressure applied to the carbon dioxide mixed residual gas is 5-30 Mpa, and the working temperature is-35-30.8 ℃;
s4, conveying the hydrogen mixed residual gas to a water gas reforming reaction device;
the working temperature of the water gas reforming reaction device is 200-280 ℃, water distribution is carried out according to the content of carbon monoxide, and the water distribution ratio (carbon monoxide: water) is 1:1-20;
the water gas reforming reaction device reforms the fed hydrogen mixed residual gas into reforming mixed gas by distributing water, and 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;
S5, mixing the reforming mixed gas with the mixed gas of the hydrogen, the carbon dioxide and the carbon monoxide, and enabling the reforming mixed gas to enter the membrane separation and purification device again along with the mixed gas of the hydrogen, the carbon dioxide and the carbon monoxide for hydrogen purification and separation.
Further, in step S1, the methanol water is sent to the reformer through a first stage first diversion channel and a second stage second diversion channel, respectively, and the processed methanol water on the first heat exchanger on the first stage first diversion channel and the second heat exchanger on the second stage diversion channel are heated and vaporized to form methanol steam, and then sent to the reformer;
in step S2, the mixed gas of hydrogen, carbon dioxide and carbon monoxide generated from the reformer is sent to a membrane separation and purification device through a second-stage first diversion channel and a second-stage second diversion channel respectively, wherein a third heat exchanger on the second-stage first diversion channel and a fourth heat exchanger on the second-stage second diversion channel are used for preheating the mixed gas of hydrogen, carbon dioxide and carbon monoxide, and then sent to the membrane separation and purification device;
in the step 3, the separated pure hydrogen is conveyed into a hydrogen storage tank of a hydrogenation station through a pure hydrogen output channel, the pure hydrogen output channel sequentially passes through a fourth heat exchanger and a second heat exchanger, the fourth heat exchanger is used for preheating mixed gas of hydrogen, carbon dioxide and carbon monoxide in a second-stage second split-flow channel, and the second heat exchanger is used for preparing methanol water in the first-stage second split-flow channel into methanol water vapor;
The separated carbon dioxide mixed residual gas is conveyed by a carbon dioxide mixed residual gas output channel, the carbon dioxide mixed residual gas output channel sequentially passes through a third heat exchanger and a first heat exchanger, the third heat exchanger is used for preheating the mixed gas of hydrogen, carbon dioxide and carbon monoxide in the second-stage first split-flow channel, and the first heat exchanger is used for preparing methanol water in the first-stage first split-flow channel into methanol water vapor.
The beneficial effects of the invention are as follows:
the low-pressure hydrogen production system of the methanol water hydrogenation station is characterized in that the methanol water is fed into the reformer through the first-stage first diversion channel and the second-stage diversion channel for reforming, the methanol water is vaporized in the first-stage first diversion channel and the second-stage diversion channel, and the heat energy used for vaporization is derived from the heat energy of the mixed residual gas of pure hydrogen and carbon dioxide output by the membrane separation and purification device, so that the system layout is more optimized, and the energy source for vaporizing the methanol water is saved.
In the hydrogen production system, the related low pressure means that the methanol water is conveyed by a conveying pump under the working pressure of 2-5 MPa, and the methanol water is conveyed in a low-pressure environment, so that the whole hydrogen production system is safer and more stable;
and secondly, when the mixed gas of the hydrogen and the carbon dioxide prepared by the reformer is sent into the membrane separation and purification device through the second-stage first diversion channel and the second-stage second diversion channel for purification and separation operation, the preheating heat of the mixed gas of the hydrogen and the carbon dioxide in the two channels is also from the heat of the mixed residual gas of the pure hydrogen and the carbon dioxide output by the membrane separation and purification device, the heat of the mixed gas of the pure hydrogen and the carbon dioxide is fully utilized, and the energy source which is originally needed for heating the mixed gas of the hydrogen and the carbon dioxide is omitted.
According to the hydrogen production system of the hydrogen station, the carbon dioxide in the carbon dioxide mixed residual gas separated after hydrogen production is liquefied and separated, the separated pure carbon dioxide and the hydrogen mixed residual gas are collected, the pressure and the temperature of a carbon dioxide liquefying device during operation are controlled, the gas phase components of the hydrogen mixed residual gas are further controlled, the mole ratio of the carbon dioxide in the hydrogen mixed residual gas is controlled to be less than 26 percent (the components of the hydrogen mixed residual gas are 65-75 percent of hydrogen, 20-26 percent of carbon dioxide and 3-9 percent of carbon monoxide), and the gas phase components of the hydrogen mixed residual gas meet the requirement of water gas reforming.
In the system, the hydrogen mixed residual gas is reformed into the reformed mixed gas through water gas distribution, so that the content of carbon monoxide in the hydrogen mixed residual gas is reduced, and the water gas reforming reaction formula is as follows: CO+H 2 0＝CO 2 +H 2 The method comprises the steps of carrying out a first treatment on the surface of the Changing the carbon monoxide and the configured water into hydrogen and carbon dioxide, thereby readjusting the gas phase composition of the reforming mixture gas: 62-77% of hydrogen, 22-27% of carbon dioxide and 0.5-1.5% of carbon monoxide; the components of the hydrogen mixed residual gas before comparison: 65-75% of hydrogen, 20-26% of carbon dioxide and 3-9% of carbon monoxide; reducing the carbon monoxide from original 3-9% to 0.5-1.5%; the gas phase component of the reforming mixed gas is equivalent 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 working method of the low-pressure hydrogen production system of the methanol water hydrogenation station comprises the steps of taking methanol water as a hydrogen production raw material, transferring the methanol water to a reformer for reforming after heat exchange with pure hydrogen and carbon dioxide mixed residual gas prepared by a membrane separation and purification device to prepare mixed gas of hydrogen, carbon dioxide and carbon monoxide, transferring the mixed gas of the hydrogen, the carbon dioxide and the carbon monoxide to the membrane separation and purification device for hydrogen purification and separation after heat exchange with the pure hydrogen and the carbon dioxide mixed residual gas prepared by the membrane separation and purification device, and storing the prepared hydrogen in a hydrogen storage tank of the hydrogenation station for a hydrogen energy automobile; meanwhile, recycling the carbon dioxide mixed residual gas separated by the membrane separation and purification device again, separating the hydrogen mixed residual gas and liquid carbon dioxide from the carbon dioxide mixed residual gas by a carbon dioxide liquefying device, and controlling the gas phase component in the hydrogen mixed residual gas by controlling the pressure and the temperature when the carbon dioxide liquefying device separates, so that the carbon dioxide molar ratio in the hydrogen mixed residual gas is lower than 26%, and the hydrogen mixed residual gas is prepared as a reforming mixed gas in the subsequent step; 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 equivalent 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 diagram of a hydrogen station system of the present invention;
11. the device comprises a primary first diversion channel, 12, a primary second diversion channel, 13, a secondary first diversion channel, 14, a secondary second diversion channel, 15, a carbon dioxide mixed residual gas output channel, 16, a pure hydrogen output channel, 18, a reformed gas channel, 21, a first diverter, 22, a second diverter, 31, a first heat exchanger, 32, a second heat exchanger, 33, a third heat exchanger, 34, a fourth heat exchanger, 4, a reformer, 5, a membrane separation purification device, 6, a carbon dioxide liquefying device, 7, a water gas reforming reaction device, 81, a first temperature controller, 82, a second temperature controller, 83, a third temperature controller, 84, a fourth temperature controller, 85, a fifth temperature controller, 91, a first air compressor, 92 and a second air compressor.
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, the low-pressure hydrogen production system of the methanol water hydrogenation station comprises a first splitter 21, a first-stage first split-flow channel 11, a first-stage second split-flow channel 12, a reformer 4, a second splitter 22, a second-stage first split-flow channel 13, a second-stage second split-flow channel 14, a membrane separation and purification device 5, a pure hydrogen output channel 16 and a carbon dioxide mixed residual gas output channel 15.
The outlet of the first flow divider 21 is connected with the primary first flow dividing channel 11 and the primary second flow dividing channel 12; a delivery pump is arranged on the inlet pipeline of the first flow divider;
the first heat exchanger 31 is arranged on the first-stage first diversion channel 11, the second heat exchanger 32 is arranged on the second-stage diversion channel 12, the working temperature of the first heat exchanger 31 and the second heat exchanger 32 is 20-300 ℃, and the first-stage first diversion channel 11 and the second-stage diversion channel 12 are suitable for preparing methanol water into methanol water vapor.
The outlets of the first-stage first diversion channel 11 and the second-stage diversion channel 12 are connected with the reformer 4, and are suitable for feeding the methanol vapor in the first-stage first diversion channel 11 and the second-stage diversion channel 12 into the reformer 4, and the methanol vapor is used for preparing mixed gas of hydrogen, carbon dioxide and carbon monoxide in the reformer 4; the gas phase components of the mixed gas of the hydrogen, the carbon dioxide and the carbon monoxide are 65-75% of hydrogen, 20-26% of carbon dioxide and 0.3-3% of carbon monoxide.
The working principle of the reformer 4: the reforming chamber of the reformer 4 is internally provided with a catalyst, when the methanol-water reforming hydrogen production system is in operation, the temperature of the reforming chamber is 220-320 ℃, methanol and steam pass through the catalyst under the pressure condition of 1-5 Mpa in the reforming chamber, under the action of the catalyst, methanol cracking reaction and carbon monoxide conversion reaction are carried out, and mixed gas of hydrogen, carbon dioxide and carbon monoxide is generated, which 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 outlet of the reformer 4 is connected with a second flow divider 22, and the outlet of the second flow divider 22 is communicated with the inlet of the membrane separation and purification device 5 through a second-stage first flow dividing channel 13 and a second-stage second flow dividing channel 14; the membrane separation and purification device 5 is connected with a pure hydrogen output channel 16 and a carbon dioxide mixed residual gas output channel 15, the membrane separation and purification device 5 separates the mixed gas of the fed hydrogen, carbon dioxide and carbon monoxide into the pure hydrogen and the carbon dioxide mixed residual gas, the working temperature of the membrane separation and purification device 5 is 380-420 ℃, the temperature of the separated pure hydrogen is 380-420 ℃, and the temperature of the separated carbon dioxide mixed residual gas is 380-420 ℃; the gas phase component of the carbon dioxide mixed residual gas is 25-45% of hydrogen, and specifically comprises the following components: 29%; 55-75% of carbon dioxide, which is specifically: 64.6%; 0-3% of water, wherein the water volume ratio is specifically as follows: 3%;0.3 to 3 percent of carbon monoxide, wherein the volume ratio of the carbon monoxide is as follows: 0.5%.
The working principle of the membrane separation and purification device 5 is as follows: the hydrogen purification device adopts a membrane separation device, the membrane separation device is a membrane separation device for vacuum plating palladium-silver alloy on the surface of porous ceramic, a coating layer is made of the palladium-silver alloy, the palladium-silver alloy accounts for 75-78% by mass, the silver accounts for 22-25% by mass, and the manufacturing process of the membrane separation device can refer to an application patent 201210563913.5 applied by Shanghai-obtained dynamic hydrogen machine Co., ltd.2012, 12 months and 21 days of the inventor, and a membrane separator of methanol-water hydrogen production equipment and a preparation method thereof.
The separated pure hydrogen is conveyed to a hydrogen storage tank of the hydrogenation station by the pure hydrogen output channel 16, the pure hydrogen output channel 16 sequentially passes through a fourth heat exchanger 34 and a second heat exchanger 32, the fourth heat exchanger 34 uses the exchanged heat energy to preheat the mixed gas of hydrogen, carbon dioxide and carbon monoxide in the second split-flow channel 14, and the second heat exchanger 32 uses the exchanged heat energy to prepare methanol water in the first-stage second split-flow channel 12 into methanol water vapor.
The separated carbon dioxide mixed residual gas is conveyed by a carbon dioxide mixed residual gas output channel 15, the carbon dioxide mixed residual gas output channel 15 sequentially passes through a third heat exchanger 33 and a first heat exchanger 31, the third heat exchanger 33 uses the exchanged heat energy for preheating the mixed gas of hydrogen, carbon dioxide and carbon monoxide in the second-stage first split flow path 13, and the first heat exchanger 31 uses the exchanged heat energy for preparing methanol water in the first-stage first split flow path 11 into methanol water vapor.
In order to accurately control the temperature of the methanol vapor entering the reformer 4, a first temperature controller 81 is arranged at the inlet of the reformer 4, and the methanol vapor and the water vapor conveyed by the first-stage first diversion channel 11 and the first-stage second diversion channel 12 are input into the reformer 4 after being subjected to temperature control by the first temperature controller 81.
In order to accurately control the temperature of the mixed gas of hydrogen, carbon dioxide and carbon monoxide entering the membrane separation and purification device 5, a second temperature controller 82 is arranged at the inlet of the membrane separation and purification device 5, and the mixed gas of hydrogen, carbon dioxide and carbon monoxide conveyed by the second-stage first diversion channel 13 and the second-stage second diversion channel 14 is conveyed into the membrane separation and purification device 5 after being subjected to temperature control by the second temperature controller 82.
In order to collect the stable output of the pure hydrogen, a second air compressor 92 and a fifth temperature controller 85 are disposed on the pure hydrogen output channel 16, and the fifth temperature controller 85 is located upstream of the second air compressor 92.
The hydrogen storage tank is connected with the hydrogenation machine and is suitable for outputting the hydrogen in the hydrogen storage tank. 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.
In this embodiment, the heat of the first heat exchanger 31 and the third heat exchanger 33 is derived from the temperature of the carbon dioxide mixed residual gas, the heat exchange temperature of the third heat exchanger 33 is about 300 ℃, and the heat exchange temperature of the first heat exchanger 31 is about 200 ℃, so that the methanol water in the first-stage first split-flow channel 11 can be vaporized to form methanol water vapor when passing through the first heat exchanger 31; the third heat exchanger 33 may preheat the mixed gas of hydrogen, carbon dioxide and carbon monoxide flowing from the second-stage first split flow path 13 to about 400 c and react in the membrane separation and purification device 5.
The heat of the second heat exchanger 32 and the fourth heat exchanger 34 is derived from the temperature of pure hydrogen, the heat exchange temperature of the fourth heat exchanger 34 is about 300 ℃, and the heat exchange temperature of the second heat exchanger 32 is about 200 ℃, so that the methanol water in the first-stage second shunt channel 12 can be vaporized to form methanol water vapor when passing through the second heat exchanger 32; the fourth heat exchanger 34 may preheat the mixed gas of hydrogen, carbon dioxide and carbon monoxide flowing from the second split flow path 14 to about 400 ℃ and react in the membrane separation and purification device 5.
According to the hydrogen production system, methanol water is conveyed in a low-pressure environment, and the whole hydrogen production system is safer and more stable.
Example two
Based on the first embodiment, the low-pressure hydrogen production system of the methanol-water hydrogenation station of the present embodiment further processes the carbon dioxide mixed residual gas separated by the membrane separation and purification device 5 in the first embodiment.
The outlet of the carbon dioxide mixed residual gas output channel 15 is connected with the carbon dioxide liquefying device 6; the carbon dioxide liquefying device 6 separates the carbon dioxide mixed residual gas into liquid carbon dioxide and hydrogen mixed residual gas, and the liquid carbon dioxide is collected; the components of the hydrogen mixed residual gas are 65-75% of hydrogen, 20-26% of carbon dioxide and 3-9% of carbon monoxide; when the carbon dioxide liquefying device 6 works, the pressure applied to the mixed gas of carbon dioxide is 5-30 Mpa, and the working temperature is-35-30.8 ℃.
Specifically, the first air compressor 91, the third temperature controller 83 and the fourth temperature controller 84 are disposed on the carbon dioxide mixed residual gas output channel 15, the third temperature controller 83 is located at the upstream of the first air compressor 91, the fourth temperature controller 84 is located at the downstream of the first air compressor 91, a steam trap is disposed between the first air compressor 91 and the fourth temperature controller 84, and the steam trap can remove moisture in the carbon dioxide mixed residual gas. The third temperature controller 83 and the fourth temperature controller 84 are used for reducing the temperature of the carbon dioxide mixed residual gas, and controlling the air pressure in the pipeline at the same time, so that the air pressure liquefies the carbon dioxide at low temperature and high pressure, and the workload of the subsequent carbon dioxide liquefying device 6 is reduced.
In order to control the mole ratio of carbon dioxide in the gas phase component of the hydrogen mixed residual gas to 20-26%, the selection of the pressure and the temperature of the carbon dioxide liquefying device 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
In this embodiment, the carbon dioxide in the carbon dioxide mixed residual gas separated after hydrogen production is liquefied and separated, the separated pure carbon dioxide and the hydrogen mixed residual gas are collected, the pressure and the temperature of the carbon dioxide liquefying device 6 are controlled during operation, the gas phase component of the hydrogen mixed residual gas is further controlled, the molar ratio of the carbon dioxide in the hydrogen mixed residual gas is controlled below 26% (the components of the hydrogen mixed residual gas are 65-75% of hydrogen, 20-26% of carbon dioxide and 3-9% of carbon monoxide), and the gas phase component of the hydrogen mixed residual gas meets the requirement of water gas reforming.
Example III
In the second embodiment, on the basis of the second embodiment, the prepared hydrogen mixed residual gas is subjected to water gas water distribution reforming;
specifically, the carbon dioxide liquefying device 6 is connected with the water gas reforming reaction device 7, and the carbon dioxide liquefying device 6 sends the separated hydrogen mixed residual gas into the water gas reforming reaction device 7 for reforming;
the working temperature of the water gas reforming reaction device 7 is 200-280 ℃, water distribution is carried out according to the content of carbon monoxide, and the water distribution ratio (carbon monoxide: water) is 1:1-20. The water gas reforming reaction device 7 reforms the fed hydrogen mixed residual gas into reforming mixed gas by distributing water, and 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 water gas reforming reaction device 7 is connected with a reformed gas channel 18, the channel outlet of the reformer 4 is connected with the inlet of the second flow divider 22, the reformed mixed gas is sent into the second flow divider 22 through the reformed gas channel 18, and the reformed mixed gas and the mixed gas of hydrogen, carbon dioxide and carbon monoxide prepared in the reformer 4 are sent into the membrane separation purification device 5 together for circulation purification.
The hydrogen mixed residual gas is reformed into reforming mixed gas through water gas distribution, the content of carbon monoxide in the hydrogen mixed residual gas is reduced, and the water gas reforming reaction formula is as follows: CO+H 2 O＝CO 2 +H 2 The method comprises the steps of carrying out a first treatment on the surface of the Changing the carbon monoxide and the configured water into hydrogen and carbon dioxide, thereby readjusting the gas phase composition of the reforming mixture gas: 62-77% of hydrogen, 22-27% of carbon dioxide and 0.5-1.5% of carbon monoxide; the components of the hydrogen mixed residual gas before comparison: 65-75% of hydrogen, 20-26% of carbon dioxide and 3-9% of carbon monoxide; reducing the carbon monoxide from original 3-9% to 0.5-1.5%; the gas phase component of the reforming mixed gas is equivalent to the mixed gas component of the hydrogen, the carbon dioxide and the carbon monoxide prepared by the reformer 4, so that the two components can be mixed and then enter the membrane separation and purification device 5 to perform hydrogen purification and separation hydrogen production operation.
Example IV
The present embodiment is based on the hydrogen production system of the first, second and third embodiments;
the working method of the low-pressure hydrogen production system of the methanol-water hydrogenation station comprises the following steps:
s1, conveying methanol water by a conveying pump, heating and vaporizing the methanol water to form methanol water vapor, and conveying the methanol water vapor into a reformer 4 for reforming to form mixed gas of hydrogen, carbon dioxide and carbon monoxide, wherein the ratio of the methanol to the water in the methanol water is 1:1, and the working pressure of the conveying pump is 2-5 MPa;
The working pressure of the reformer 4 is 2-5 MPa, preferably 2.5MPa, and the working temperature of the reformer 4 is 220-320 ℃; the gas phase components of the mixed gas of the hydrogen, the carbon dioxide and the carbon monoxide are 65-75% of the hydrogen and 20-26% of the carbon dioxide;
s2, sending the mixed gas of hydrogen, carbon dioxide and carbon monoxide into a membrane separation and purification device 5 in a temperature-controlled manner, wherein the membrane separation and purification device 5 separates the sent mixed gas of hydrogen, carbon dioxide and carbon monoxide into pure hydrogen and carbon dioxide mixed residual gas;
collecting the pure hydrogen into a hydrogen storage tank of a hydrogenation station;
the gas phase component of the carbon dioxide mixed residual gas is 25-45% of hydrogen by volume, and specifically comprises the following components: 29 percent and 55 to 75 percent of carbon dioxide volume ratio, and specifically comprises the following steps: 64.6% and a water volume ratio of 0-3%, specifically: 3%;0.3 to 3 percent of carbon monoxide, wherein the volume ratio of the carbon monoxide is as follows: 0.5%.
S3, delivering the carbon dioxide mixed residual gas into a carbon dioxide liquefying device 6;
the carbon dioxide liquefying device 6 separates the carbon dioxide mixed residual gas into liquid carbon dioxide and hydrogen mixed residual gas;
when the carbon dioxide liquefying device works, the pressure applied to the carbon dioxide mixed residual gas is 5-30 Mpa, and the working temperature is-35-30.8 ℃;
The liquid carbon dioxide is collected;
the components of the hydrogen mixed residual gas comprise 65-75% of hydrogen, 20-26% of carbon dioxide and 3-9% of carbon monoxide;
s4, conveying the hydrogen mixed residual gas to a water gas reforming reaction device 7;
the working temperature of the water gas reforming reaction device is 200-280 ℃, water distribution is carried out according to the content of carbon monoxide, and the water distribution ratio (carbon monoxide: water) is 1:1-20;
the water gas reforming reaction device 7 reforms the fed hydrogen mixed residual gas into reforming mixed gas by distributing water, 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 to the carbon dioxide in the reforming mixed gas is close to the ratio of the hydrogen to the carbon dioxide in the mixed gas of the hydrogen, the carbon dioxide and the carbon monoxide (the gas phase component of the mixed gas of the hydrogen, the carbon dioxide and the carbon monoxide is 65 to 75 percent of hydrogen, 20 to 26 percent of carbon dioxide and 0.3 to 3 percent of carbon monoxide);
s5, mixing the reforming mixed gas with the mixed gas of the hydrogen, the carbon dioxide and the carbon monoxide, and enabling the reforming mixed gas to enter the membrane separation and purification device 5 again along with the mixed gas of the hydrogen, the carbon dioxide and the carbon monoxide for hydrogen purification and separation.
In step S1, the methanol water is sent to the reformer 4 through the first-stage first diversion channel 11 and the second-stage second diversion channel 12, and the first heat exchanger 31 on the first-stage first diversion channel 11 and the second heat exchanger 32 on the second-stage diversion channel 12 process the methanol water to heat and evaporate to form methanol steam, which is sent to the reformer 4;
in step S2, the mixed gas of hydrogen, carbon dioxide and carbon monoxide generated from the reformer 4 is sent to the membrane separation and purification device 5 through the second-stage first split flow channel 13 and the second-stage second split flow channel 14, respectively, and the third heat exchanger 33 on the second-stage first split flow channel 13 and the fourth heat exchanger 34 on the second-stage second split flow channel 14 are used for preheating the mixed gas of hydrogen, carbon dioxide and carbon monoxide, and then sent to the membrane separation and purification device 5;
in step 3, the separated pure hydrogen is conveyed into a hydrogen storage tank of the hydrogenation station through a pure hydrogen output channel 16, the pure hydrogen output channel 16 sequentially passes through a fourth heat exchanger 34 and a second heat exchanger 32, the fourth heat exchanger 34 uses the exchanged heat energy to preheat the mixed gas of hydrogen, carbon dioxide and carbon monoxide in the second-stage second split-flow channel 14, and the second heat exchanger 32 uses the exchanged heat energy to prepare methanol water in the first-stage second split-flow channel 12 into methanol water vapor;
The separated carbon dioxide mixed residual gas is conveyed by a carbon dioxide mixed residual gas output channel 15, the carbon dioxide mixed residual gas output channel 15 sequentially passes through a third heat exchanger 33 and a first heat exchanger 31, the third heat exchanger 33 uses the exchanged heat energy for preheating the mixed gas of hydrogen, carbon dioxide and carbon monoxide in the second-stage first split flow path 13, and the first heat exchanger 31 uses the exchanged heat energy for preparing methanol water in the first-stage first split flow path 11 into methanol water vapor.
The working method of the low-pressure hydrogen production system of the methanol water hydrogenation station comprises the steps of taking methanol water as a hydrogen production raw material, transferring the methanol water to a reformer 4 for reforming after heat exchange with pure hydrogen and carbon dioxide mixed residual gas prepared by a membrane separation and purification device 5 to prepare mixed gas of hydrogen, carbon dioxide and carbon monoxide, transferring the mixed gas of the hydrogen, the carbon dioxide and the carbon monoxide to the membrane separation and purification device 5 for hydrogen purification and separation after heat exchange with the pure hydrogen and the carbon dioxide mixed residual gas prepared by the membrane separation and purification device 5, and storing the prepared hydrogen in a hydrogen storage tank of the hydrogenation station for a hydrogen energy automobile; meanwhile, the carbon dioxide mixed residual gas separated by the membrane separation and purification device 5 is recycled again, the carbon dioxide mixed residual gas is separated into hydrogen mixed residual gas and liquid carbon dioxide by the carbon dioxide liquefying device 6, the liquid carbon dioxide can be stored, and when the carbon dioxide liquefying device 6 is separated, the pressure and the temperature are controlled, so that the gas phase component in the hydrogen mixed residual gas is 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 the subsequent process; 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 made to approach to the gas phase component of the mixed gas of hydrogen, carbon dioxide and carbon monoxide (the gas phase component of the mixed gas of hydrogen, carbon dioxide and carbon monoxide is 65-75% hydrogen, 20-26% carbon dioxide and 0.3-3% carbon monoxide) prepared by the reformer 4, so that the two components can be mixed and then enter the membrane separation and purification device 5 again to carry out hydrogen purification and separation hydrogen production operation.
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 low-pressure hydrogen production system of the methanol water hydrogenation station is characterized by comprising a first diverter, a first-stage first diversion channel, a first-stage second diversion channel, a reformer, a second diverter, a second-stage first diversion channel, a second-stage second diversion channel, a membrane separation and purification device, a pure hydrogen output channel and a carbon dioxide mixed residual gas output channel;
the first diverter outlet is connected with a first-stage first diversion channel and a second-stage second diversion channel; a delivery pump is arranged on the inlet pipeline of the first flow divider;
the first heat exchanger is arranged on the first-stage first diversion channel, the second heat exchanger is arranged on the second-stage second diversion channel, the working temperature of the first heat exchanger and the second heat exchanger is 20-300 ℃, and the first-stage first diversion channel and the second-stage first diversion channel are suitable for preparing methanol water in the first-stage first diversion channel and the second-stage first diversion channel into methanol water vapor;
The outlets of the first-stage first diversion channel and the second-stage diversion channel are connected with the reformer, and are suitable for sending the methanol vapor in the first-stage first diversion channel and the second-stage diversion channel into the reformer, and the methanol vapor is used for preparing mixed gas of hydrogen, carbon dioxide and carbon monoxide in the reformer;
the reaction equation is:
CH 3 OH→CO+2H 2 ；
H 2 O+CO→CO 2 +H 2 ；
CH 3 OH+H 2 O→CO 2 +3H 2 ；
2CH 3 OH→CH 3 OCH 3 +H 2 O；
CO+3H 2 →CH 4 +H 2 O；
the gas phase components of the mixed gas of the hydrogen, the carbon dioxide and the carbon monoxide are 65-75% of hydrogen, 20-26% of carbon dioxide and 0.3-3% of carbon monoxide;
the outlet of the reformer is connected with a second shunt, and the outlet of the second shunt is communicated with the inlet of the membrane separation and purification device through a second-stage first shunt channel and a second-stage second shunt channel;
the membrane separation and purification device is connected with a pure hydrogen output channel and a carbon dioxide mixed residual gas output channel, separates the mixed gas of the fed hydrogen, carbon dioxide and carbon monoxide into the pure hydrogen and carbon dioxide mixed residual gas, and has the working temperature of 380-420 ℃, the temperature of the separated pure hydrogen is 380-420 ℃, and the temperature of the separated carbon dioxide mixed residual gas is 380-420 ℃;
the gas phase components of the carbon dioxide mixed residual gas comprise 25-45% of hydrogen, 55-75% of carbon dioxide, 0.3-3% of carbon monoxide and 0-3% of water;
The separated pure hydrogen is conveyed into a hydrogen storage tank of a hydrogenation station through a pure hydrogen output channel, the pure hydrogen output channel sequentially passes through a fourth heat exchanger and a second heat exchanger, the fourth heat exchanger is used for preheating mixed gas of hydrogen, carbon dioxide and carbon monoxide in a second-stage second split-flow channel, and the second heat exchanger is used for preparing methanol water in the first-stage second split-flow channel into methanol water vapor;
the separated carbon dioxide mixed residual gas is conveyed by a carbon dioxide mixed residual gas output channel, the carbon dioxide mixed residual gas output channel sequentially passes through a third heat exchanger and a first heat exchanger, the third heat exchanger uses the heat energy obtained by the heat exchange to preheat the mixed gas of hydrogen, carbon dioxide and carbon monoxide in the second-stage first split-flow channel, and the first heat exchanger uses the heat energy obtained by the heat exchange to prepare methanol water in the first-stage first split-flow channel into methanol water vapor;
the outlet of the carbon dioxide mixed residual gas output channel is connected with a carbon dioxide liquefying device;
the carbon dioxide liquefying device separates the carbon dioxide mixed residual gas into liquid carbon dioxide and hydrogen mixed residual gas, and the liquid carbon dioxide is collected; the components of the hydrogen mixed residual gas are 65-75% of hydrogen, 20-26% of carbon dioxide and 3-9% of carbon monoxide;
When the carbon dioxide liquefying device works, the pressure applied to the carbon dioxide mixed residual gas is 5-30 Mpa, and the working temperature is-35-30.8 ℃;
the carbon dioxide liquefying device is connected with the water gas reforming reaction device, and the carbon dioxide liquefying device sends the separated hydrogen mixed residual gas into the water gas reforming reaction device for reforming;
the working temperature of the water gas reforming reaction device is 200-280 ℃, water distribution is carried out according to the content of carbon monoxide, and the water distribution ratio is carbon monoxide: water is 1:1-20;
the water gas reforming reaction device reforms the fed hydrogen mixed residual gas into reforming mixed gas by distributing water, and 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 water gas reforming reaction device is connected with a reformed gas channel, the outlet of the reformer channel is connected with the inlet of the second flow divider, the reformed mixed gas is sent into the second flow divider through the reformed gas channel, and the reformed mixed gas and the mixed gas of hydrogen, carbon dioxide and carbon monoxide prepared in the reformer are sent into the membrane separation purification device together for circulation purification;
The inlet of the reformer is provided with a first temperature controller, and the methanol steam and the water steam conveyed by the first-stage first diversion channel and the first-stage second diversion channel are input into the reformer after being subjected to temperature control by the first temperature controller.
2. The low-pressure hydrogen production system of the methanol-water hydrogenation station according to claim 1, wherein a second temperature controller is arranged at the inlet of the membrane separation and purification device, and the mixed gas of hydrogen, carbon dioxide and carbon monoxide conveyed by the second-stage first diversion channel and the second-stage second diversion channel is sent to the membrane separation and purification device after being subjected to temperature control by the second temperature controller.
3. The low-pressure hydrogen production system of a methanol-water hydrogenation station according to claim 1, wherein a first air compressor, a third temperature controller and a fourth temperature controller are arranged on the carbon dioxide mixed residual gas output channel, the third temperature controller is located at the upstream of the first air compressor, and the fourth temperature controller is located at the downstream of the first air compressor.
4. The low pressure hydrogen production system of a methanol to water hydrogen station of claim 1 wherein a second air compressor and a fifth temperature controller are disposed on the pure hydrogen output channel, the fifth temperature controller being located upstream of the second air compressor.
5. The low pressure hydrogen suppression system of a methanol to water hydrogenation station of claim 1 wherein said hydrogen storage tank is connected to a hydrogenation machine adapted to output hydrogen from the hydrogen storage tank.
6. A working method of a low-pressure hydrogen production system of a methanol water hydrogenation station, which is characterized by adopting the low-pressure hydrogen production system of the methanol water hydrogenation station as claimed in any one of claims 1 to 5, comprising the following steps:
s1, conveying methanol water by a conveying pump, heating and vaporizing the methanol water to form methanol water vapor, and conveying the methanol water vapor into a reformer to reform to form mixed gas of hydrogen, carbon dioxide and carbon monoxide, wherein the ratio of the methanol to the water in the methanol water is 1:1; the working pressure of the conveying pump is 2-5 MPa;
the working pressure of the reformer is 2-5 MPa, and the working temperature of the reformer is 220-320 ℃; 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, sending the mixed gas of hydrogen, carbon dioxide and carbon monoxide into a membrane separation and purification device at the working temperature of 380-420 ℃, and separating the mixed gas of the sent hydrogen, carbon dioxide and carbon monoxide into pure hydrogen and carbon dioxide mixed residual gas by the membrane separation and purification device;
collecting the pure hydrogen into a hydrogen storage tank of a hydrogenation station;
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;
s3, delivering the carbon dioxide mixed residual gas into a carbon dioxide liquefying device;
the carbon dioxide liquefying device separates the carbon dioxide mixed residual gas into liquid carbon dioxide and hydrogen mixed residual gas;
the liquid carbon dioxide is collected;
the components of the hydrogen mixed residual gas are 65-75% of hydrogen, 20-26% of carbon dioxide and 3-9% of carbon monoxide;
when the carbon dioxide liquefying device works, the pressure applied to the carbon dioxide mixed residual gas is 5-30 Mpa, and the working temperature is-35-30.8 ℃;
s4, conveying the hydrogen mixed residual gas to a water gas reforming reaction device;
the working temperature of the water gas reforming reaction device is 200-280 ℃, water distribution is carried out according to the content of carbon monoxide, and the water distribution ratio is carbon monoxide: water is 1:1-20;
the water gas reforming reaction device reforms the fed hydrogen mixed residual gas into reforming mixed gas by distributing water, and 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;
s5, mixing the reforming mixed gas with the mixed gas of the hydrogen, the carbon dioxide and the carbon monoxide, and enabling the reforming mixed gas to enter the membrane separation and purification device again along with the mixed gas of the hydrogen, the carbon dioxide and the carbon monoxide for hydrogen purification and separation.
7. The method according to claim 6, wherein in step S1, the methanol water is fed into the reformer through a first stage first split flow channel and a second stage split flow channel, respectively, and the methanol water processed by the first heat exchanger on the first stage split flow channel and the second heat exchanger on the second stage split flow channel is heated and vaporized to form methanol steam, and is fed into the reformer;
in step S2, the mixed gas of hydrogen, carbon dioxide and carbon monoxide generated from the reformer is sent to a membrane separation and purification device through a second-stage first diversion channel and a second-stage second diversion channel respectively, wherein a third heat exchanger on the second-stage first diversion channel and a fourth heat exchanger on the second-stage second diversion channel are used for preheating the mixed gas of hydrogen, carbon dioxide and carbon monoxide, and then sent to the membrane separation and purification device;
In the step 3, the separated pure hydrogen is conveyed into a hydrogen storage tank of a hydrogenation station through a pure hydrogen output channel, the pure hydrogen output channel sequentially passes through a fourth heat exchanger and a second heat exchanger, the fourth heat exchanger is used for preheating mixed gas of hydrogen, carbon dioxide and carbon monoxide in a second-stage second split-flow channel, and the second heat exchanger is used for preparing methanol water in the first-stage second split-flow channel into methanol water vapor;
the separated carbon dioxide mixed residual gas is conveyed by a carbon dioxide mixed residual gas output channel, the carbon dioxide mixed residual gas output channel sequentially passes through a third heat exchanger and a first heat exchanger, the third heat exchanger is used for preheating the mixed gas of hydrogen, carbon dioxide and carbon monoxide in the second-stage first split-flow channel, and the first heat exchanger is used for preparing methanol water in the first-stage first split-flow channel into methanol water vapor.
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