CN110862067A - 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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CN110862067A
CN110862067A CN201911032712.0A CN201911032712A CN110862067A CN 110862067 A CN110862067 A CN 110862067A CN 201911032712 A CN201911032712 A CN 201911032712A CN 110862067 A CN110862067 A CN 110862067A
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hydrogen
carbon dioxide
gas
water
methanol
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CN110862067B (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 Institute Of Industrial Technology Dalian Institute Of Chemical Physics China Academy Of Sciences
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Zhangjiagang Institute Of Industrial Technology Dalian Institute Of Chemical Physics China Academy Of Sciences
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    • 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
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    • 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
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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 the methanol water into methanol steam; s2, feeding the mixed gas of hydrogen, carbon dioxide and carbon monoxide into a membrane separation and purification device at a controlled temperature, and S3, feeding the carbon dioxide mixed residual gas into a carbon dioxide liquefaction device; s4, conveying the hydrogen mixed residual gas to water gas reforming; and S5, mixing the reformed mixed gas with the mixed gas of hydrogen and carbon dioxide, and enabling the reformed mixed gas to enter the membrane separation and purification device again along with the mixed gas of hydrogen, carbon dioxide and carbon monoxide for hydrogen purification and separation. Realizes the circular purification of the gas and 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 the most ideal energy in the 21 st century, is used as automobile fuel, is easy to start at low temperature, has small corrosion effect on an engine, and can prolong the service life of the engine. Because the hydrogen and the air can be uniformly mixed, a carburetor used on a common automobile can be completely omitted, and the structure of the existing automobile can be simplified. It is more interesting to add only 4% hydrogen to the gasoline. When it is used as fuel of automobile engine, it can save oil by 40%, and has no need of making great improvement on gasoline engine. A hydrogen fuel cell serves as a power generation system.
No pollution, and no pollution to environment caused by fuel cell. It is through electrochemical reaction, rather than combustion (gasoline, diesel) or energy storage (battery) -the most typical traditional backup power scheme. Combustion releases pollutants like COx, NOx, SOx gases and dust. As described above, the fuel cell generates only water and heat. If the hydrogen is generated by renewable energy sources (photovoltaic panels, wind power generation, etc.), the whole cycle is a complete process without generating harmful emissions.
No noise, quiet fuel cell operation, about only 55dB noise, which corresponds to the level of normal human conversation. This makes the fuel cell suitable for a wide range of applications, including indoor installations, or where there is a limit to noise outdoors.
The efficiency is high, the generating efficiency of the fuel cell can reach more than 50%, which is determined by the conversion property of the fuel cell, chemical energy is directly converted into electric energy without intermediate conversion of heat energy and mechanical energy (a generator), and the efficiency is reduced once more because of once more energy conversion.
At present, the main source of hydrogen of a hydrogen energy source hydrogenation station is that an energy storage tank is transported back from outside, and the whole hydrogenation station needs to store a large amount of hydrogen; research finds that hydrogen in the hydrogen energy industry comprises four links, namely hydrogen preparation, hydrogen storage, hydrogen transportation and hydrogen addition (adding hydrogen into a hydrogen energy vehicle), wherein the two links of hydrogen preparation and hydrogen addition are safe at present, accidents easily occur in the hydrogen storage link, and the cost of the hydrogen transportation link is high and is related to the characteristics of hydrogen; the problems of explosion of the hydrogenation station and the reason of high hydrogenation cost frequently occur in the current news.
Therefore, in order to solve the problem of large hydrogen storage amount in the existing hydrogen station, shorten or reduce the high cost of hydrogen transportation link, reduce the investment of compressor equipment, reduce the operation energy consumption of equipment and reduce the maintenance cost of the equipment, a hydrogen station system needs to be redesigned.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: the defects of the prior art are overcome, the low-pressure hydrogen production system of the methanol-water hydrogenation station and the working method thereof are provided, and the problems of high potential safety hazard and long-distance high-cost hydrogen transportation caused by the fact that a large amount of hydrogen needs to be stored in the existing hydrogenation station are solved.
The technical scheme adopted by the invention for solving the technical problems is as follows:
a low-pressure hydrogen production system of a methanol-water hydrogenation station is characterized by comprising a first flow divider, a first-stage first diversion channel, a first-stage second diversion channel, a reformer, a second flow divider, 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 splitter outlet is connected with the first splitter passage and the second splitter passage; a conveying pump is arranged on the inlet pipeline of the first flow divider;
a first heat exchanger is arranged on the first-stage first diversion channel, a second heat exchanger is arranged on the first-stage second diversion channel, the working temperatures of the first heat exchanger and the second heat exchanger are 20-300 ℃, and the first heat exchanger and the second heat exchanger are suitable for preparing methanol water in the first-stage first diversion channel and the first-stage second diversion channel into methanol water vapor;
the outlets of the first-stage first diversion channel and the second-stage diversion channel are connected with a reformer and are suitable for sending methanol steam in the first-stage first diversion channel and the second-stage diversion channel into the reformer, and the methanol steam is used for preparing a mixed gas of hydrogen, carbon dioxide and carbon monoxide in the reformer;
the reaction equation is:
CH3OH→CO+2H2；
H2O+CO→CO2+H2；
CH3OH+H2O→CO2+3H2；
2CH3OH→CH3OCH3+H2O；
CO+3H2→CH4+H2O；
the gas phase component of the mixed gas of hydrogen, carbon dioxide and carbon monoxide is 65-75% of hydrogen, 20-26% of carbon dioxide and 0.3-3% of carbon monoxide;
the outlet of the reformer is connected with a second splitter, and the outlet of the second splitter is communicated with the inlet of the membrane separation and purification device through a second-stage first splitting channel and a second-stage second splitting channel;
the membrane separation and purification device is connected with the pure hydrogen output channel and the carbon dioxide mixed residual gas output channel, the membrane separation and purification device separates the mixed gas of hydrogen, carbon dioxide and carbon monoxide into the pure hydrogen and carbon dioxide mixed residual gas, the working temperature of the membrane separation and purification device 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 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 to 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 uses the converted heat energy to preheat the mixed gas of hydrogen, carbon dioxide and carbon monoxide in a secondary second diversion channel, and the second heat exchanger uses the converted heat energy to prepare methanol water vapor from the methanol water in the primary second diversion channel;
the separated carbon dioxide mixed residual gas is conveyed through 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 mixed gas of hydrogen, carbon dioxide and carbon monoxide in the second-stage first diversion channel, and the first heat exchanger is used for preparing methanol steam from methanol water in the first-stage first diversion channel.
Further, an outlet of the carbon dioxide mixed residual gas output channel is connected with a carbon dioxide liquefying device;
the carbon dioxide liquefaction 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 comprise 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 operating 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 is distributed according to the content of carbon monoxide, and the ratio of the water to the carbon monoxide to the water is 1: 1-20;
the water gas reforming reaction device reforms the fed hydrogen mixed residual gas into a reformed mixed gas by water distribution, and the gas phase components of the reformed mixed gas comprise 62-77% of hydrogen, 22-27% of carbon dioxide and 0.5-1.5% of carbon monoxide;
the water gas reforming reaction formula is as follows: CO + H2O→CO2+H2；
The water gas reforming reaction device is connected with a reforming gas channel, the outlet of the reforming gas channel is connected with the inlet of a second splitter, the reforming mixed gas is sent into the second splitter through the reforming gas channel, and the reforming mixed gas and the mixed gas of hydrogen, carbon dioxide and carbon monoxide prepared in the reformer are sent into a membrane separation and purification device together for circular purification.
Furthermore, a first temperature controller is arranged at an inlet of the reformer, and the methanol steam and the steam which are conveyed by the first-stage first diversion channel and the first-stage second diversion channel are input into the reformer after the temperature of the methanol steam and the steam is controlled 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 secondary first diversion channel and the secondary second diversion channel is subjected to temperature control by the second temperature controller and then is sent to the membrane separation and purification device.
Further, set up first air compressor machine, third thermostat, fourth thermostat on the carbon dioxide mixes the residual gas output channel, the third thermostat is located first air compressor machine upper reaches, the fourth thermostat is located first air compressor machine low reaches.
Furthermore, 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.
Furthermore, the hydrogen storage tank is connected with a hydrogenation machine and is suitable for outputting the hydrogen in the hydrogen storage tank.
In another aspect, a working method of a low-pressure hydrogen production system of a 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 through a conveying pump, heating and vaporizing the methanol water to form methanol steam, conveying the methanol steam to a reformer for reforming to form a mixed gas of hydrogen, carbon dioxide and carbon monoxide, wherein the ratio of methanol to 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 component of the mixed gas of hydrogen, carbon dioxide and carbon monoxide is 65-75% of hydrogen, 20-26% of carbon dioxide and 0.3-3% of carbon monoxide;
s2, feeding the mixed gas of hydrogen, carbon dioxide and carbon monoxide into a membrane separation and purification device at a controlled temperature, wherein the working temperature of the membrane separation and purification device is 380-420 ℃, and the membrane separation and purification device separates the fed mixed gas of hydrogen, carbon dioxide and carbon monoxide into pure hydrogen and carbon dioxide mixed residual gas;
the pure hydrogen is collected 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, sending 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 comprise 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 operating 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 is distributed according to the content of carbon monoxide, and the ratio of the water to the carbon monoxide to the water is 1: 1-20;
the water gas reforming reaction device reforms the fed hydrogen mixed residual gas into a reformed mixed gas by water distribution, and the gas phase components of the reformed mixed gas comprise 62-77% of hydrogen, 22-27% of carbon dioxide and 0.5-1.5% of carbon monoxide;
the water gas reforming reaction formula is as follows: CO + H2O→CO2+H2；
So that the proportion of hydrogen, carbon dioxide and carbon monoxide in the reforming mixed gas is close to the proportion of hydrogen, carbon dioxide and carbon monoxide in the mixed gas of hydrogen, carbon dioxide and carbon monoxide;
and S5, mixing the reformed mixed gas with the mixed gas of hydrogen, carbon dioxide and carbon monoxide, and enabling the reformed mixed gas to enter the membrane separation and purification device again along with the mixed gas of hydrogen, carbon dioxide and carbon monoxide for hydrogen purification and separation.
Further, in step S1, the methanol-water is sent to the reformer through the first stage of diversion channel and the second stage of diversion channel, respectively, and the first heat exchanger on the first stage of diversion channel and the second heat exchanger on the second stage of diversion channel process the methanol-water to heat and vaporize and form methanol steam, which is 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 secondary first diversion channel and a secondary second diversion channel respectively, and a third heat exchanger on the secondary first diversion channel and a fourth heat exchanger on the secondary 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 to 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 uses the converted heat energy to preheat the mixed gas of hydrogen, carbon dioxide and carbon monoxide in a secondary second diversion channel, and the second heat exchanger uses the converted heat energy to prepare methanol water vapor from methanol water in the primary second diversion channel;
the separated carbon dioxide mixed residual gas is conveyed through 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 mixed gas of hydrogen, carbon dioxide and carbon monoxide in the second-stage first diversion channel, and the first heat exchanger is used for preparing methanol steam from methanol water in the first-stage first diversion channel.
The invention has the beneficial effects that:
the low-pressure hydrogen production system of the methanol-water hydrogenation station is provided, methanol water is fed into a reformer for reforming through a first-stage first diversion channel and a second-stage diversion channel, the methanol water is vaporized in the two channels, and heat energy used for vaporization is heat energy of pure hydrogen and carbon dioxide mixed residual gas output by a membrane separation and purification device, so that the system layout is optimized, and energy sources for vaporizing the methanol water are saved.
In the hydrogen production system, the low pressure refers to that the conveying pump conveys methanol water under the working pressure of 2-5 MPa, and the methanol water is conveyed under the low-pressure environment, so that the whole hydrogen production system is safer and more stable;
secondly, when the mixed gas of hydrogen and carbon dioxide prepared by the reformer is sent into the membrane separation and purification device through the two-stage first diversion channel and the two-stage second diversion channel to be purified and separated, the preheating heat of the mixed gas of hydrogen and carbon dioxide in the two channels is also from the heat of the mixed residual gas of pure hydrogen and carbon dioxide output by the membrane separation and purification device, the heat of the mixed gas of pure hydrogen and carbon dioxide is fully utilized, and the energy source which is originally needed for heating the mixed gas of hydrogen and carbon dioxide is saved.
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 hydrogen mixed residual gas are collected, the pressure and temperature of the carbon dioxide liquefying device during working are controlled, the gas phase components of the hydrogen mixed residual gas are further controlled, the molar ratio of the carbon dioxide in the hydrogen mixed residual gas is controlled to be below 26% (the components of the hydrogen mixed residual gas comprise 65-75% of hydrogen, 20-26% of carbon dioxide and 3-9% of carbon monoxide), and the gas phase components of the hydrogen mixed residual gas meet the requirement of water gas reforming.
In this system, pass through water gas water distribution reforming with hydrogen mixed residual gas and become the reforming gas mixture, reduce the content of carbon monoxide in the hydrogen mixed residual gas, it is through water gas reforming reaction formula: CO + H20＝CO2+H2(ii) a Changing carbon monoxide and configured water to hydrogen and carbon dioxide, thereby readjusting the gas phase composition of the reformed gas mixture, the gas phase composition of the reformed gas mixture: 62-77% of hydrogen, 22-27% of carbon dioxide and 0.5-1.5% of carbon monoxide; comparing the components of the hydrogen mixed residual gas before: 65-75% of hydrogen, 20-26% of carbon dioxide and 3-9% of carbon monoxide; reducing the carbon monoxide content from 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, and the gas phase component and the mixed gas component can be mixed and then enter the membrane separation and purification device again for 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, exchanging heat between the methanol-water and mixed residual gas of pure hydrogen and carbon dioxide prepared by a membrane separation and purification device, sending the mixture to a reformer for reforming to prepare mixed gas of hydrogen, carbon dioxide and carbon monoxide, then exchanging heat between the mixed gas of hydrogen, carbon dioxide and carbon monoxide and mixed residual gas of pure hydrogen and carbon dioxide prepared by the membrane separation and purification device, sending the mixed gas of hydrogen, carbon dioxide and carbon monoxide to the membrane separation and purification device for hydrogen purification and separation, and storing the prepared hydrogen in a hydrogen storage tank of the hydrogenation station for hydrogen energy vehicles to use; meanwhile, the carbon dioxide mixed residual gas separated by the membrane separation and purification device is recycled again, the carbon dioxide mixed residual gas is separated into hydrogen mixed residual gas and liquid carbon dioxide by the carbon dioxide liquefaction device, the liquid carbon dioxide can be stored, and the carbon dioxide liquefaction device controls gas-phase components in the hydrogen mixed residual gas by controlling pressure and temperature during separation, so that the molar ratio of the carbon dioxide in the hydrogen mixed residual gas is lower than 26%, and the hydrogen mixed residual gas is prepared for a subsequent reforming mixed gas; and finally, reforming the hydrogen mixed residual gas through water gas water distribution, reducing carbon monoxide in the hydrogen mixed residual gas from 3-9% originally to 0.5-1.5%, and reforming the gas phase components of the mixed gas: 62-77% of hydrogen, 22-27% of carbon dioxide and 0.5-1.5% of carbon monoxide; the gas phase component of the reformed mixed gas is equivalent to the mixed gas component of the hydrogen, the carbon dioxide and the carbon monoxide prepared by the reformer, the reformed mixed gas and the mixed gas can be mixed and then enter the membrane separation and purification device for hydrogen purification and separation to prepare hydrogen, the gas in the system is circularly purified, the theoretical yield can reach 100 percent, and the hydrogen yield is more than or equal to 95 percent.
Meanwhile, the hydrogen station system for preparing hydrogen by using methanol directly consumes customers, saves freight compared with factory hydrogen in selling price, recovers the hydrogen in the carbon dioxide residual gas, can realize the yield of 100 percent theoretically, is actually more than 90 to 99 percent, and simultaneously recovers CO2The theoretical yield is 100 percent, and the actual yield is 90-99 percent. The process is combined with a hydrogenation station, so that high yield of hydrogen can be realized, and more CO can be recovered2And economic benefit is obtained, safety (high-pressure hydrogen storage is reduced), economy (methanol transportation cost is much lower than that of hydrogen) and CO recovery are really realized2Zero emission is realized, and ecological benefits are obtained.
On the one hand, hydrogen production is harmless and zero-state emission; on the other hand, the carbon dioxide emission reduction is made into methanol, greenhouse gas is changed into useful methanol liquid fuel, the methanol liquid fuel is taken as a hydrogenation station, the solar fuel has rich sources, light, wind, water and nuclear energy are all available, the carbon dioxide hydrogenation is used for preparing the methanol, and the methanol can be transported, stored and transported. The problems of manufacture, storage, transportation, installation and the like are solved in the whole view,
firstly, the liquid sunlight hydrogen station solves the safety problem of the high-pressure hydrogen station; secondly, the problems of storage, transportation and safety of hydrogen are solved; thirdly, hydrogen can be used as renewable energy to realize the aim of cleaning the whole process; fourthly, the liquid sunlight hydrogenation station can recover carbon dioxide, so that carbon dioxide emission reduction is realized, no further carbon dioxide is generated, and the carbon dioxide is always circulated therein; fifthly, the liquid sunlight hydrogenation station technology can be expanded to other chemical synthesis fields and can also be used for chemical hydrogenation; sixth, the system can be shared with a gas station and a methanol adding station. The system is particularly suitable for community distributed thermoelectric combined energy supply and the existing gas stations.
Drawings
The invention is further described below with reference to the accompanying drawings.
FIG. 1 is a schematic diagram of a hydroprocessing station system according to the present invention;
11. the system comprises a first-stage first diversion channel, a first-stage second diversion channel, a second-stage first diversion channel, a second-stage second diversion channel, a second-stage mixed residual gas output channel, a pure hydrogen output channel, a second-stage mixed residual gas output channel, a.
Detailed Description
The invention will now be further described with reference to specific examples. These drawings are simplified schematic diagrams only illustrating the basic structure of the present invention in a schematic manner, and thus show only the constitution related to the present invention.
Example one
As shown in fig. 1, a low-pressure hydrogen production system of a methanol-water hydrogenation station includes a first splitter 21, a first-stage first diversion channel 11, a first-stage second diversion channel 12, a reformer 4, a second splitter 22, a second-stage first diversion channel 13, a second-stage second diversion 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 a first diversion channel 11 and a second diversion channel 12; a conveying 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 first-stage second diversion channel 12, the working temperatures of the first heat exchanger 31 and the second heat exchanger 32 are 20-300 ℃, and the first heat exchanger and the second heat exchanger are suitable for preparing methanol steam from methanol water in the first-stage first diversion channel 11 and the first-stage second diversion channel 12.
Outlets of the first-stage first diversion channel 11 and the second-stage diversion channel 12 are connected with the reformer 4, and the methanol steam in the first-stage first diversion channel 11 and the second-stage diversion channel 12 is suitable for being sent into the reformer 4 and is used for preparing a mixed gas of hydrogen, carbon dioxide and carbon monoxide in the reformer 4; the gas phase component of the mixed gas of hydrogen, carbon dioxide and carbon monoxide is 65-75% of hydrogen, 20-26% of carbon dioxide and 0.3-3% of carbon monoxide.
Operation principle of the reformer 4: a catalyst is arranged in a reforming chamber of the reformer 4, when a methanol-water reforming hydrogen production system operates, the temperature of the reforming chamber is 220-320 ℃, methanol and steam pass through the catalyst under the pressure condition of 1-5M Pa in the reforming chamber, and a methanol cracking reaction and a carbon monoxide shift reaction are carried out under the action of the catalyst to generate a mixed gas of hydrogen, carbon dioxide and carbon monoxide, which is a multi-component and multi-reaction gas-solid catalytic reaction system;
the reaction equation is:
CH3OH→CO+2H2(ii) a (reversible reaction)
H2O+CO→CO2+H2(ii) a (reversible reaction)
CH3OH+H2O→CO2+3H2(ii) a (reversible reaction)
2CH3OH→CH3OCH3+H2O; (side reaction)
CO+3H2→CH4+H2O; (side reaction)
The reforming reaction generates a mixed gas of hydrogen, carbon dioxide and carbon monoxide.
The 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 secondary first flow dividing channel 13 and a secondary 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 hydrogen, carbon dioxide and carbon monoxide into pure hydrogen and 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 hydrogen 25-45%, and specifically comprises the following components: 29 percent; 55-75% of carbon dioxide, wherein the volume ratio of the carbon dioxide is as follows: 64.6 percent; 0-3% of water, and the volume ratio of water is specifically as follows: 3 percent; 0.3-3% of carbon monoxide, wherein the volume ratio of the carbon monoxide is as follows: 0.5 percent.
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 of palladium-silver alloy on the surface of porous ceramic, a plating film layer is the palladium-silver alloy, the mass percent of palladium-silver alloy is 75% -78%, the mass percent of silver is 22% -25%, the manufacturing process of the membrane separation device can refer to the invention patent 201210563913.5 applied by Shanghai Co-Ltd of the present applicant in 12/21 of 2012, 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 hydrogen filling 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 converted heat energy to preheat the mixed gas of hydrogen, carbon dioxide and carbon monoxide in the secondary second diversion channel 14, and the second heat exchanger 32 uses the converted heat energy to prepare methanol water vapor from the methanol water in the primary second diversion channel 12.
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 heat energy obtained by the conversion for preheating the mixed gas of hydrogen, carbon dioxide and carbon monoxide in the second-stage first diversion channel 13, and the first heat exchanger 31 uses the heat energy obtained by the conversion for preparing methanol water in the first-stage first diversion channel 11 into methanol water vapor.
In order to accurately control the temperature of the methanol steam entering the reformer 4, a first temperature controller 81 is arranged at an inlet of the reformer 4, and the methanol steam and the steam conveyed by the first-stage first diversion channel 11 and the first-stage second diversion channel 12 are input into the reformer 4 after the temperature of the methanol steam and the steam is controlled 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, the 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 secondary first diversion channel 13 and the secondary second diversion channel 14 is sent to the membrane separation and purification device 5 after the temperature of the mixed gas is controlled 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 arranged on the pure hydrogen output channel 16, and the fifth temperature controller 85 is located at the 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, the prepared hydrogen is directly stored in the hydrogen storage tank, and the prepared pure hydrogen is directly added into the hydrogen vehicle through the hydrogenation machine.
In this embodiment, the heat of the first heat exchanger 31 and the third heat exchanger 33 comes 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 diversion channel 11 can be evaporated and vaporized to form methanol water vapor when passing through the first heat exchanger 31; and the third heat exchanger 33 can preheat the mixed gas of hydrogen, carbon dioxide and carbon monoxide flowing through the second-stage first diversion channel 13 to about 400 ℃ and then enter the membrane separation and purification device 5 for reaction.
The heat of the second heat exchanger 32 and the fourth heat exchanger 34 comes from the temperature of the 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 diversion channel 12 can be evaporated and vaporized to form methanol water vapor when passing through the second heat exchanger 32; and the fourth heat exchanger 34 can preheat the mixed gas of hydrogen, carbon dioxide and carbon monoxide flowing from the second-stage flow dividing channel 14 to about 400 ℃ and then enter the membrane separation and purification device 5 for reaction.
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
On the basis of 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 comprise 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 the carbon dioxide is 5-30 Mpa, and the operating temperature is-35-30.8 ℃.
Specifically, set up first air compressor machine 91, third thermostat 83, fourth thermostat 84 on the mixed residual air outlet channel 15 of carbon dioxide, third thermostat 83 is located first air compressor machine 91 upstream, fourth thermostat 84 is located first air compressor machine 91 low reaches, sets up the steam trap between first air compressor machine 91 and the fourth thermostat 84, and the moisture in the mixed residual air of carbon dioxide can be got rid of to the steam trap. 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 simultaneously controlling the air pressure in the pipeline, so that the carbon dioxide is liquefied at low temperature and high pressure, and the workload of the subsequent carbon dioxide liquefying device 6 is reduced.
In order to control the molar ratio of carbon dioxide in the gaseous phase component of the hydrogen mixed residual gas to be 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(s) 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 the 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 during working are controlled, the gas phase components of the hydrogen mixed residual gas are further controlled, the molar ratio of the carbon dioxide in the hydrogen mixed residual gas is controlled to be below 26% (the components of the hydrogen mixed residual gas comprise 65-75% of hydrogen, 20-26% of carbon dioxide and 3-9% of carbon monoxide), and the gas phase components of the hydrogen mixed residual gas meet the requirement of water gas reforming.
EXAMPLE III
In this 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 is distributed according to the content of carbon monoxide, and the ratio of the water distribution (carbon monoxide: water) is 1: 1-20. The water gas reforming reaction device 7 reforms the fed hydrogen mixed residual gas into a reformed mixed gas by water distribution, and the gas phase components of the reformed mixed gas comprise 62-77% of hydrogen, 22-27% of carbon dioxide and 0.5-1.5% of carbon monoxide.
The water gas reforming reaction formula is as follows: CO + H2O→CO2+H2；
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 a 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 and purification device 5 together for circular purification.
Reforming the hydrogen mixed residual gas into reformed mixed gas by water gas water distribution, reducing the content of carbon monoxide in the hydrogen mixed residual gas, and performing water gas reforming reaction by a water gas reforming reaction formulaComprises the following steps: CO + H2O＝CO2+H2(ii) a Changing carbon monoxide and configured water to hydrogen and carbon dioxide, thereby readjusting the gas phase composition of the reformed gas mixture, the gas phase composition of the reformed gas mixture: 62-77% of hydrogen, 22-27% of carbon dioxide and 0.5-1.5% of carbon monoxide; comparing the components of the hydrogen mixed residual gas before: 65-75% of hydrogen, 20-26% of carbon dioxide and 3-9% of carbon monoxide; reducing the carbon monoxide content from 3-9% to 0.5-1.5%; the gas phase component of the reformed mixed gas is equivalent to the mixed gas component of the hydrogen, the carbon dioxide and the carbon monoxide prepared by the reformer 4, and the gas phase component and the mixed gas component can be mixed and then enter the membrane separation and purification device 5 again for hydrogen purification and separation to prepare the hydrogen.
Example four
This example is based on the hydrogen production systems of examples one, two and three;
a working method of a low-pressure hydrogen production system of a methanol-water hydrogenation station comprises the following steps:
s1, conveying methanol water through a conveying pump, heating and vaporizing the methanol water to form methanol steam, conveying the methanol steam into a reformer 4 to reform to form mixed gas of hydrogen, carbon dioxide and carbon monoxide, wherein the ratio of methanol to 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 hydrogen, carbon dioxide and carbon monoxide are 65-75% of hydrogen and 20-26% of carbon dioxide;
s2, feeding the mixed gas of hydrogen, carbon dioxide and carbon monoxide into a membrane separation and purification device 5 at a controlled temperature, wherein the membrane separation and purification device 5 separates the fed mixed gas of hydrogen, carbon dioxide and carbon monoxide into pure hydrogen and carbon dioxide mixed residual gas;
the pure hydrogen is collected into a hydrogen storage tank of a hydrogenation station;
the gas phase component of the carbon dioxide mixed residual gas is hydrogen volume ratio of 25-45%, and specifically comprises the following components: 29% and 55-75% of carbon dioxide by volume, specifically: 64.6 percent and the volume ratio of water is 0-3 percent, and specifically comprises the following components: 3 percent; 0.3-3% of carbon monoxide, wherein the volume ratio of the carbon monoxide is as follows: 0.5 percent.
S3, sending 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 operating 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 the water gas reforming reaction device 7;
the working temperature of the water gas reforming reaction device is 200-280 ℃, water is distributed according to the content of carbon monoxide, and the ratio of the water to the carbon monoxide to the water is 1: 1-20;
the water gas reforming reaction device 7 reforms the fed hydrogen mixed residual gas into a reformed mixed gas by water distribution, and the gas phase components of the reformed mixed gas comprise 62-77% of hydrogen, 22-27% of carbon dioxide and 0.5-1.5% of carbon monoxide;
the water gas reforming reaction formula is as follows: CO + H2O→CO2+H2；
So that the proportion of the hydrogen and the carbon dioxide in the reforming mixed gas is close to the proportion of the hydrogen and 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 65-75% of the hydrogen, 20-26% of the carbon dioxide and 0.3-3% of the carbon monoxide);
and S5, mixing the reformed mixed gas with the mixed gas of the hydrogen, the carbon dioxide and the carbon monoxide, and enabling the reformed 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 diversion channel 11 and the second stage diversion channel 12, respectively, the first heat exchanger 31 on the first stage diversion channel 11 and the second heat exchanger 32 on the second stage diversion channel 12 process the methanol water to heat and vaporize the methanol water to form methanol steam, and the methanol steam 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 secondary first diversion channel 13 and the secondary second diversion channel 14, respectively, and the third heat exchanger 33 on the secondary first diversion channel 13 and the fourth heat exchanger 34 on the secondary second diversion 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 to a hydrogen storage tank of the hydrogen filling 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 converted heat energy to preheat the mixed gas of hydrogen, carbon dioxide and carbon monoxide in the secondary second diversion channel 14, and the second heat exchanger 32 uses the converted heat energy to prepare methanol water in the primary second diversion 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 heat energy obtained by the conversion for preheating the mixed gas of hydrogen, carbon dioxide and carbon monoxide in the second-stage first diversion channel 13, and the first heat exchanger 31 uses the heat energy obtained by the conversion for preparing methanol water in the first-stage first diversion channel 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, exchanging heat between the methanol-water and the mixed residual gas of pure hydrogen and carbon dioxide prepared by the membrane separation and purification device 5, sending the mixed gas of hydrogen, carbon dioxide and carbon monoxide to the reformer 4 for reforming to prepare a mixed gas of hydrogen, carbon dioxide and carbon monoxide, exchanging heat between the mixed gas of hydrogen, carbon dioxide and carbon monoxide and the mixed residual gas of pure hydrogen and carbon dioxide prepared by the membrane separation and purification device 5, sending the mixed gas of hydrogen, carbon dioxide and carbon monoxide to the membrane separation and purification device 5 for hydrogen purification and separation, and storing the prepared hydrogen in a hydrogen storage tank of the hydrogenation station for a hydrogen energy; 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 liquefaction device 6, the liquid carbon dioxide can be stored, and the carbon dioxide liquefaction device 6 controls gas-phase components in the hydrogen mixed residual gas by controlling pressure and temperature during separation, so that the molar ratio of the carbon dioxide in the hydrogen mixed residual gas is lower than 26%, and the hydrogen mixed residual gas is prepared for a subsequent reforming mixed gas; and finally, reforming the hydrogen mixed residual gas through water gas water distribution, reducing carbon monoxide in the hydrogen mixed residual gas from 3-9% originally to 0.5-1.5%, and reforming the gas phase components of the mixed gas: 62-77% of hydrogen, 22-27% of carbon dioxide and 0.5-1.5% of carbon monoxide; the gas phase component of the reformed mixed gas is close to the 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% of hydrogen, 20-26% of carbon dioxide and 0.3-3% of carbon monoxide) prepared by the reformer 4, and the gas phase component can be mixed and then enter the membrane separation and purification device 5 for hydrogen purification and separation to prepare hydrogen.
In light of the foregoing description of the preferred embodiment of the present invention, many modifications and variations will be apparent to those skilled in the art without departing from the spirit and scope of the invention. The technical scope of the present invention is not limited to the content of the specification, and must be determined according to the scope of the claims.

Claims (10)

1. A low-pressure hydrogen production system of a methanol-water hydrogenation station is characterized by comprising a first flow divider, a first-stage first diversion channel, a first-stage second diversion channel, a reformer, a second flow divider, 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 splitter outlet is connected with the first splitter passage and the second splitter passage; a conveying pump is arranged on the inlet pipeline of the first flow divider;
a first heat exchanger is arranged on the first-stage first diversion channel, a second heat exchanger is arranged on the first-stage second diversion channel, the working temperatures of the first heat exchanger and the second heat exchanger are 20-300 ℃, and the first heat exchanger and the second heat exchanger are suitable for preparing methanol water in the first-stage first diversion channel and the first-stage second diversion channel into methanol water vapor;
the outlets of the first-stage first diversion channel and the second-stage diversion channel are connected with a reformer and are suitable for sending methanol steam in the first-stage first diversion channel and the second-stage diversion channel into the reformer, and the methanol steam is used for preparing a mixed gas of hydrogen, carbon dioxide and carbon monoxide in the reformer;
the reaction equation is:
CH3OH→CO+2H2；
H2O+CO→CO2+H2；
CH3OH+H2O→CO2+3H2；
2CH3OH→CH3OCH3+H2O；
CO+3H2→CH4+H2O；
the gas phase component of the mixed gas of hydrogen, carbon dioxide and carbon monoxide is 65-75% of hydrogen, 20-26% of carbon dioxide and 0.3-3% of carbon monoxide;
the outlet of the reformer is connected with a second splitter, and the outlet of the second splitter is communicated with the inlet of the membrane separation and purification device through a second-stage first splitting channel and a second-stage second splitting channel;
the membrane separation and purification device is connected with the pure hydrogen output channel and the carbon dioxide mixed residual gas output channel, the membrane separation and purification device separates the mixed gas of hydrogen, carbon dioxide and carbon monoxide into the pure hydrogen and carbon dioxide mixed residual gas, the working temperature of the membrane separation and purification device 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 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 to 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 uses the converted heat energy to preheat the mixed gas of hydrogen, carbon dioxide and carbon monoxide in a secondary second diversion channel, and the second heat exchanger uses the converted heat energy to prepare methanol water vapor from the methanol water in the primary second diversion channel;
the separated carbon dioxide mixed residual gas is conveyed through 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 mixed gas of hydrogen, carbon dioxide and carbon monoxide in the second-stage first diversion channel, and the first heat exchanger is used for preparing methanol steam from methanol water in the first-stage first diversion channel.
2. The low-pressure hydrogen production system of the methanol-water hydrogenation station as claimed in claim 1, wherein the outlet of the carbon dioxide mixed residual gas output channel is connected with a carbon dioxide liquefying device;
the carbon dioxide liquefaction 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 comprise 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 operating temperature is-35-30.8 ℃.
3. The low-pressure hydrogen production system of the methanol-water hydrogenation station as claimed in claim 2, wherein the carbon dioxide liquefaction device is connected with the water gas reforming reaction device, and the carbon dioxide liquefaction 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 is distributed according to the content of carbon monoxide, and the ratio of the water to the carbon monoxide to the water is 1: 1-20;
the water gas reforming reaction device reforms the fed hydrogen mixed residual gas into a reformed mixed gas by water distribution, and the gas phase components of the reformed mixed gas comprise 62-77% of hydrogen, 22-27% of carbon dioxide and 0.5-1.5% of carbon monoxide;
the water gas reforming reaction formula is as follows: CO + H2O→CO2+H2；
The water gas reforming reaction device is connected with a reforming gas channel, the outlet of the reforming gas channel is connected with the inlet of a second splitter, the reforming mixed gas is sent into the second splitter through the reforming gas channel, and the reforming mixed gas and the mixed gas of hydrogen, carbon dioxide and carbon monoxide prepared in the reformer are sent into a membrane separation and purification device together for circular purification.
4. The low-pressure hydrogen production system of the methanol-water hydrogenation station of claim 1, wherein a first temperature controller is arranged at an inlet of the reformer, and the methanol steam and the steam which are conveyed by the first-stage first diversion channel and the second-stage diversion channel are input into the reformer after the temperature of the methanol steam and the steam is controlled by the first temperature controller.
5. The low-pressure hydrogen production system of the methanol-water hydrogenation station of claim 1, wherein a second temperature controller is arranged at an inlet of the membrane separation and purification device, and the mixed gas of hydrogen, carbon dioxide and carbon monoxide conveyed by the secondary first diversion channel and the secondary second diversion channel is subjected to temperature control by the second temperature controller and then is conveyed to the membrane separation and purification device.
6. The low-pressure hydrogen production system of the methanol-water hydrogenation station according to claim 2, 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 positioned at the upstream of the first air compressor, and the fourth temperature controller is positioned at the downstream of the first air compressor.
7. The low-pressure hydrogen production system of the methanol-water hydrogenation station of claim 1, wherein a second air compressor and a fifth temperature controller are arranged on the pure hydrogen output channel, and the fifth temperature controller is positioned at the upstream of the second air compressor.
8. The low-pressure hydrogen production system of the methanol-water hydrogenation station as claimed in claim 1, wherein the hydrogen storage tank is connected with a hydrogenation machine and is suitable for outputting hydrogen in the hydrogen storage tank.
9. A working method of a low-pressure hydrogen production system of a methanol-water hydrogenation station is characterized in that the low-pressure hydrogen production system of the methanol-water hydrogenation station as claimed in any one of claims 1 to 8 is adopted, and comprises the following steps:
s1, conveying methanol water through a conveying pump, heating and vaporizing the methanol water to form methanol steam, conveying the methanol steam to a reformer for reforming to form a mixed gas of hydrogen, carbon dioxide and carbon monoxide, wherein the ratio of methanol to 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 component of the mixed gas of hydrogen, carbon dioxide and carbon monoxide is 65-75% of hydrogen, 20-26% of carbon dioxide and 0.3-3% of carbon monoxide;
s2, feeding the mixed gas of hydrogen, carbon dioxide and carbon monoxide into a membrane separation and purification device at a controlled temperature, wherein the working temperature of the membrane separation and purification device is 380-420 ℃, and the membrane separation and purification device separates the fed mixed gas of hydrogen, carbon dioxide and carbon monoxide into pure hydrogen and carbon dioxide mixed residual gas;
the pure hydrogen is collected 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, sending 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 comprise 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 operating 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 is distributed according to the content of carbon monoxide, and the ratio of the water to the carbon monoxide to the water is 1: 1-20;
the water gas reforming reaction device reforms the fed hydrogen mixed residual gas into a reformed mixed gas by water distribution, and the gas phase components of the reformed mixed gas comprise 62-77% of hydrogen, 22-27% of carbon dioxide and 0.5-1.5% of carbon monoxide;
the water gas reforming reaction formula is as follows: CO + H2O→CO2+H2；
So that the proportion of hydrogen, carbon dioxide and carbon monoxide in the reforming mixed gas is close to the proportion of hydrogen, carbon dioxide and carbon monoxide in the mixed gas of hydrogen, carbon dioxide and carbon monoxide;
and S5, mixing the reformed mixed gas with the mixed gas of hydrogen, carbon dioxide and carbon monoxide, and enabling the reformed mixed gas to enter the membrane separation and purification device again along with the mixed gas of hydrogen, carbon dioxide and carbon monoxide for hydrogen purification and separation.
10. The operating method of a low pressure hydrogen production system of a methanol-water hydrogenation station as claimed in claim 9, wherein in step S1, the methanol-water is fed into the reformer through the first and second splitter passages, and the first and second heat exchangers in the first and second splitter passages process the methanol-water to heat and vaporize the methanol-water to form methanol steam which 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 secondary first diversion channel and a secondary second diversion channel respectively, and a third heat exchanger on the secondary first diversion channel and a fourth heat exchanger on the secondary 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 to 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 uses the converted heat energy to preheat the mixed gas of hydrogen, carbon dioxide and carbon monoxide in a secondary second diversion channel, and the second heat exchanger uses the converted heat energy to prepare methanol water vapor from methanol water in the primary second diversion channel;
the separated carbon dioxide mixed residual gas is conveyed through 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 mixed gas of hydrogen, carbon dioxide and carbon monoxide in the second-stage first diversion channel, and the first heat exchanger is used for preparing methanol steam from methanol water in the first-stage first diversion channel.
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