CN110817798B - Medium pressure hydrogen production method - Google Patents
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- CN110817798B CN110817798B CN201911032764.8A CN201911032764A CN110817798B CN 110817798 B CN110817798 B CN 110817798B CN 201911032764 A CN201911032764 A CN 201911032764A CN 110817798 B CN110817798 B CN 110817798B
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- 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
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- 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
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- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
- C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
- C01B2203/0233—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a steam reforming step
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- 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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- 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
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- 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
Abstract
The invention relates to a methanol vapor and hydrogen mixed gas integrated medium-pressure hydrogen production system, which comprises a three-phase heat exchange device, a reforming device, a hydrogen separation device, a steam trap, a refrigerator and a carbon dioxide liquefying device, wherein the three-phase heat exchange device is connected with the reforming device; the temperature controlled by the refrigerator is-25-18 ℃; the medium pressure hydrogen producing process includes the first reforming reaction of methanol vapor in the upper reaction cavity to produce mixed gas of hydrogen, carbon dioxide and carbon monoxide, the subsequent hydrogen separation to separate the mixed carbon dioxide gas into liquefied carbon dioxide and mixed liquid carbon dioxide gas, and the subsequent carbon dioxide gas-liquid separator to produce mixed liquid carbon dioxide gas with the ratio of hydrogen, carbon dioxide and carbon monoxide approaching that of the mixed gas; enters the hydrogen separation cavity together for hydrogen separation operation. The hydrogen production efficiency of the hydrogen production system is improved, and the whole hydrogen production system structure is optimized and simplified, so that small-sized hydrogen production equipment can be manufactured by means of the hydrogen production system.
Description
Technical Field
The invention relates to a medium-pressure hydrogen production method.
Background
The hydrogen energy is used as the most ideal energy in the 21 st century, is used as automobile fuel, is easy to start at low temperature, has small corrosion effect on the engine, and can prolong the service life of the engine. Because the hydrogen and the air can be uniformly mixed, a carburetor used on a common automobile can be completely omitted, and the structure of the traditional automobile can be simplified. Of further interest is the addition of only 4% hydrogen to the gasoline. The fuel can save fuel by 40% when used as fuel of automobile engine, and does not need to improve the gasoline engine. The hydrogen fuel cell serves as a power generation system.
The fuel cell has no pollution to the environment. It is by electrochemical reaction, rather than by combustion (gasoline, diesel) or energy storage (battery) means-most typically conventional back-up power schemes. Combustion releases contaminants such as COx, NOx, SOx gas and dust. As described above, the fuel cell generates only water and heat. If hydrogen is generated by renewable energy sources (photovoltaic panels, wind power generation and the like), the whole cycle is a complete process without harmful substance emission.
The fuel cell operates quietly without noise, which is only about 55dB, corresponding to the level of normal human conversation. This makes the fuel cell suitable for a wider range including indoor installation or where noise is limited outdoors.
The high efficiency, the generating efficiency of the fuel cell can reach more than 50%, which is determined by the conversion property of the fuel cell, directly converts chemical energy into electric energy without intermediate conversion of heat energy and mechanical energy (generator), because the efficiency is reduced once more by one energy conversion.
At present, the main source of hydrogen in a hydrogen energy hydrogenation station is that an energy storage tank is used for transporting the hydrogen back from the outside, and the whole hydrogenation station needs to store a large amount of hydrogen; the research shows that the hydrogen in the hydrogen energy industry comprises four links, namely hydrogen preparation, hydrogen storage, hydrogen transportation and hydrogen addition (adding hydrogen into a hydrogen energy vehicle), wherein the two links, namely the hydrogen preparation and the hydrogen addition, are safer at present, the hydrogen storage link is easier to generate accidents, and the cost of the hydrogen transportation link is higher, so that the hydrogen transportation link is related to the characteristics of the hydrogen; at present, the problem of explosion of a hydrogenation station and the reason of high hydrogenation cost often occur in news.
Therefore, in order to reduce the problem of hydrogen storage in large quantities in the conventional hydrogen adding station, the high cost of hydrogen transportation links is shortened or reduced, and a hydrogen adding station system needs to be redesigned.
Disclosure of Invention
The invention aims to solve the technical problems that: the integrated reforming device for the mixed gas of the methanol and the water vapor solves the problem that the hydrogen production system is complicated because the prior reforming device for the methanol and the water vapor and the prior water gas reforming are two independent devices;
meanwhile, the medium-pressure hydrogen production method is provided, and the problems that the existing hydrogen production process is complex and the cyclic hydrogen production cannot be realized are solved.
The technical scheme adopted for solving the technical problems is as follows:
a methanol vapor and hydrogen mixed gas integrated medium-pressure hydrogen production system comprises a three-phase heat exchange device, a reforming device, a hydrogen separation device, a steam trap, a refrigerator and a carbon dioxide liquefying device;
the reforming device comprises a reaction cavity, and a heating cavity is arranged outside the reaction cavity; the reaction cavity comprises an upper reaction cavity suitable for reforming methanol vapor and a lower reaction cavity suitable for reforming hydrogen mixed residual gas, and the upper reaction cavity is communicated with the lower reaction cavity;
copper-based filler or zirconium-based filler is filled in the upper reaction cavity, and copper-based filler or zirconium-based filler is filled in the lower reaction cavity; the upper reaction cavity is provided with a first inlet and a first outlet, and the lower reaction cavity is provided with a second inlet;
the first inlet is connected with a methanol vapor inlet pipe, the first outlet is connected with an inlet of the hydrogen separation device, the hydrogen separation device is connected with a pure hydrogen outlet pipe and a carbon dioxide mixed residual gas outlet pipe, the carbon dioxide mixed residual gas outlet pipe is sequentially connected with a three-phase heat exchange device, a steam trap, a refrigerator and a carbon dioxide liquefying device, the carbon dioxide liquefying device is connected with the carbon dioxide outlet pipe and the hydrogen mixed residual gas outlet pipe, and the hydrogen mixed residual gas outlet pipe is connected with the second inlet; an air pump for raising the conveying pressure of the hydrogen mixed residual air in the pipe is arranged on the hydrogen mixed residual air outlet pipe; the methanol water vapor inlet pipe and the pure hydrogen outlet pipe are connected with a three-phase heat exchange device;
the methanol vapor inlet pipe is connected with a liquid pump, and the pumping pressure of the liquid pump is 7-18 MPa;
the temperature controlled by the refrigerator is-25-18 ℃.
Further, the pure hydrogen outlet pipe is connected with the hydrogen storage tank, a compressor is arranged on the hydrogen outlet pipe and is suitable for feeding pure hydrogen into the hydrogen storage tank, and the hydrogen storage tank is connected with the hydrogenation machine.
In yet another aspect, a medium pressure hydrogen production method, using the medium pressure hydrogen production system described above, includes the steps of:
s1, feeding methanol water into a methanol-water vapor pipe inlet pipe by a liquid pump, wherein the pumping pressure is 7-18 MPa, heating and vaporizing the methanol water into methanol water vapor, feeding the methanol water vapor into an upper reaction cavity of a reforming device, carrying out reforming reaction on the methanol water vapor in the upper reaction cavity to generate mixed gas of hydrogen, carbon dioxide and carbon monoxide, and feeding the mixed gas of the hydrogen, the carbon dioxide and the carbon monoxide into a hydrogen separation cavity of a hydrogen separation device;
the gas phase components of the mixed gas of the hydrogen, the carbon dioxide and the carbon monoxide are 65-75% of the hydrogen, 20-26% of the carbon dioxide and 0.3-3% of the carbon monoxide;
s2, a hydrogen absorption pipe in the hydrogen separation cavity separates mixed gas of hydrogen, carbon dioxide and carbon monoxide, and the separated pure hydrogen is output from a pure hydrogen outlet pipe and collected; outputting the residual carbon dioxide mixed residual gas from a carbon dioxide mixed residual gas outlet pipe, controlling the pressure of the carbon dioxide mixed residual gas by a liquid pump, controlling the temperature of the carbon dioxide mixed residual gas by a refrigerator, and then sending the carbon dioxide mixed residual gas into a carbon dioxide separation device for carbon dioxide liquefaction and separation;
the gas phase components of the carbon dioxide mixed residual gas comprise 25-45% of hydrogen, 55-75% of carbon dioxide, 0-3% of water and 0.3-3% of carbon monoxide;
the pressure controlled by the liquid pump is 7-18 MPa, and the temperature controlled by the refrigerator is-25-18 ℃;
s3, preparing liquid carbon dioxide and hydrogen mixed residual gas in a carbon dioxide separator from the carbon dioxide mixed residual gas, and outputting and collecting the liquid carbon dioxide;
the components of the hydrogen mixed residual gas are 65-75% of hydrogen, 20-26% of carbon dioxide and 3-9% of carbon monoxide;
s4, delivering the hydrogen mixed residual gas into a lower reaction cavity of the reforming device, preparing reformed mixed gas by water distribution, and carrying out water distribution according to the content of carbon monoxide, wherein the water distribution ratio is carbon monoxide: water is 1:1-20;
the fed hydrogen mixed residual gas is subjected to water distribution reforming in a lower reaction cavity to form reforming mixed gas, wherein the gas phase components of the reforming mixed gas are 62-77% of hydrogen, 22-27% of carbon dioxide and 0.5-1.5% of carbon monoxide;
the ratio of the hydrogen, the carbon dioxide and the carbon monoxide in the reforming mixed gas is close to the ratio of the hydrogen, the carbon dioxide and the carbon monoxide in the mixed gas of the hydrogen, the carbon dioxide and the carbon monoxide;
s5, the reforming mixed gas enters the upper reaction cavity to be mixed with the mixed gas of the hydrogen, the carbon dioxide and the carbon monoxide, and the reforming mixed gas and the mixed gas of the hydrogen, the carbon dioxide and the carbon monoxide are sent into the hydrogen separation device together after being mixed in the upper reaction cavity to carry out hydrogen separation operation again.
Furthermore, the output pure hydrogen and carbon dioxide mixed residual gas are output after being subjected to heat exchange and temperature reduction through the three-phase heat exchange device, and the methanol water is vaporized into methanol water vapor through the heat exchange of the three-phase heat exchange device.
Further, the methanol water is replaced by natural gas.
The beneficial effects of the invention are as follows:
the hydrogen production system of the invention makes the equipment for reforming the methanol vapor and the equipment for reforming the hydrogen mixed residual gas in the traditional hydrogen production system into one equipment, so that the reforming of the methanol vapor and the reforming of the hydrogen mixed residual gas can be concentrated in the reaction cavity with the same temperature, the hydrogen production efficiency of the hydrogen production system is improved, and the structure of the whole hydrogen production system is optimized and simplified, thereby being capable of being made into small-sized hydrogen production equipment by means of the hydrogen production system.
In the hydrogen production system, a liquid pump provides a medium-pressure (7-18 MPa) reaction environment, so that the whole hydrogen production system can run more safely and stably. And providing working pressure and temperature in the carbon dioxide liquefying device for the output carbon dioxide mixed residual gas through a liquid pump and a refrigerator, separating the carbon dioxide mixed residual gas into hydrogen mixed residual gas with a preset molar ratio, and then preparing the hydrogen mixed residual gas into reformed mixed gas through a water gas reforming device.
Secondly, recycling the carbon dioxide mixed residual gas generated in the hydrogen production system, controlling the pressure and the temperature for separating liquid carbon dioxide from the carbon dioxide mixed residual gas through a liquid pump and a refrigerator, separating the hydrogen mixed residual gas and the liquid carbon dioxide from the carbon dioxide mixed residual gas through a carbon dioxide liquefying device, and storing the liquid carbon dioxide; and finally, the hydrogen mixed residual gas is reformed by water gas distribution, so that the carbon monoxide in the hydrogen mixed residual gas is reduced to 0.5-1.5% from original 3-9%, and the gas phase components of the reformed mixed gas are as follows: 62-77% of hydrogen, 22-27% of carbon dioxide and 0.5-1.5% of carbon monoxide; the gas phase component of the reforming mixed gas is close to the mixed gas component of the hydrogen, the carbon dioxide and the carbon monoxide prepared by the reformer, so that the two components can be mixed and enter the hydrogen separation device again to perform hydrogen purification and separation hydrogen production operation, the gas in the system is circularly purified, the theoretical yield can reach 100%, and the hydrogen yield is more than or equal to 95%.
Meanwhile, the hydrogen station system for preparing hydrogen by utilizing methanol aims at direct consumption customers, and the selling price of hydrogen is saved compared with the factory hydrogen, so that the hydrogen in the carbon dioxide residual gas is recovered, the theoretical 100 percent yield can be realized, the actual yield is more than 90-99 percent, and the CO is recovered simultaneously 2 The theoretical yield is 100 percent and the actual yield is 90-99 percent. The process is combined with a hydrogenation station, so that high yield of hydrogen can be realized, and CO can be recovered more 2 And economic benefit is obtained, thus realizing safety (reducing high-pressure hydrogen storage), economy (because the transportation cost of methanol is much lower than that of hydrogen), and recovering CO 2 Zero emission is realized, and ecological benefits are obtained.
On the one hand, hydrogen production is harmless, and zero-state emission is realized; on the other hand, the emission of carbon dioxide is reduced to be made into methanol, the greenhouse gas is changed into useful methanol liquid fuel, the methanol liquid fuel is taken as a hydrogenation station, the source of solar fuel is very rich, light, wind, water and nuclear energy can be all used, the methanol can be prepared by hydrogenating the carbon dioxide, and the storage and transportation of the methanol are not problems. Solves the problems of manufacturing, storing, transporting, installing and the like in the whole,
firstly, the liquid sunlight hydrogenation station solves the safety problem of the high-pressure hydrogenation station; secondly, the problems of hydrogen storage, transportation and safety are solved; thirdly, hydrogen can be used as a renewable energy source to realize the aim of full-flow cleaning; fourthly, the liquid state sunlight hydrogenation station can recycle carbon dioxide, so that carbon dioxide emission reduction is realized, carbon dioxide is not further generated, and the carbon dioxide circulates at the position all the time; fifth, the liquid sunlight hydrogenation station technology can be extended to other chemical synthesis fields, and can also be used for chemical hydrogenation; sixth, the system can be multi-element co-station with a gas station or a methanol adding station. The system is particularly suitable for energy supply and current gas stations for community distributed combined heat and power.
Drawings
The invention is further described below with reference to the accompanying drawings.
FIG. 1 is a schematic diagram of a medium pressure hydrogen production system of the present invention;
FIG. 2 is a schematic diagram of a reforming unit integrated with a mixture of methanol vapor and hydrogen;
the device comprises a liquid pump 1, a three-phase heat exchange device 2, a reforming device 3, a reforming device 31, an upper reaction cavity 32, a lower reaction cavity 33, a heating cavity 4, a hydrogen separation device 5, a refrigerator 6, a carbon dioxide liquefying device 7 and a steam trap.
Detailed Description
The invention will now be further described with reference to specific examples. These drawings are simplified schematic views illustrating the basic structure of the present invention by way of illustration only, and thus show only the constitution related to the present invention.
Example 1
As shown in fig. 1 and 2, the integrated medium-pressure hydrogen production system with the mixture of methanol vapor and hydrogen comprises a three-phase heat exchange device 2, a reforming device 3, a hydrogen separation device 4, a steam trap 7, a refrigerator 5 and a carbon dioxide liquefying device.
The reforming device 3 comprises a reaction cavity, and a heating cavity 33 is arranged outside the reaction cavity; the reaction chamber comprises an upper reaction chamber 31 suitable for reforming methanol vapor and a lower reaction chamber 32 suitable for reforming hydrogen mixed residual gas, and the upper reaction chamber 31 is communicated with the lower reaction chamber 32;
the upper reaction cavity 31 is filled with copper-based filler or zirconium-based filler, and the lower reaction cavity 32 is filled with copper-based filler or zirconium-based filler; the upper reaction chamber 31 is provided with a first inlet and a first outlet, and the lower reaction chamber 32 is provided with a second inlet;
the first inlet is connected with a methanol vapor inlet pipe, the first outlet is connected with an inlet of the hydrogen separation device 4, the hydrogen separation device 4 is connected with a pure hydrogen outlet pipe and a carbon dioxide mixed residual gas outlet pipe, the carbon dioxide mixed residual gas outlet pipe is sequentially connected with the three-phase heat exchange device 2, the steam trap 7, the refrigerator 5 and the carbon dioxide liquefying device 6, the carbon dioxide liquefying device 6 is connected with the carbon dioxide outlet pipe and the hydrogen mixed residual gas outlet pipe, the hydrogen mixed residual gas outlet pipe is connected with the second inlet, and the methanol vapor inlet pipe and the pure hydrogen outlet pipe are both connected with the three-phase heat exchange device 2;
an air pump is arranged on the hydrogen mixed residual air outlet pipe and used for lifting the pressure of delivering the hydrogen mixed residual air in the pipe;
the steam trap 7 is arranged to reduce the moisture in the carbon dioxide mixed residual gas and prevent excessive moisture from entering the carbon dioxide liquefying device 6.
The methanol vapor inlet pipe is connected with a liquid pump 1, and the pumping pressure of the liquid pump 1 is 7-18 MPa; the temperature controlled by the refrigerator 5 is-25-18 ℃.
The pure hydrogen outlet pipe is connected with the hydrogen storage tank, the hydrogen outlet pipe is provided with a compressor, the pure hydrogen is suitable for being sent into the hydrogen storage tank, and the hydrogen storage tank is connected with the hydrogenation machine. The hydrogen production system realizes on-site hydrogen production, directly stores the prepared hydrogen into the hydrogen storage tank, and then directly adds the prepared pure hydrogen into the hydrogen vehicle through the hydrogenation machine.
During operation, methanol water is conveyed by the liquid pump 1 and is vaporized into methanol water vapor by the three-phase heat exchange device 2, the working pressure of the liquid pump 1 is 7-18 MPa, the methanol water vapor enters the upper reaction cavity 31 of the reforming device 3, and the methanol water vapor carries out catalytic reaction in the reformer, so that the methanol water vapor is a multi-component and multi-reaction gas-solid catalytic reaction system;
the reaction equation is: CH (CH) 3 OH→CO+2H 2 The method comprises the steps of carrying out a first treatment on the surface of the (reversible reaction)
H 2 O+CO→CO 2 +H 2 The method comprises the steps of carrying out a first treatment on the surface of the (reversible reaction)
CH 3 OH+H 2 O→CO 2 +3H 2 The method comprises the steps of carrying out a first treatment on the surface of the (reversible reaction)
2CH 3 OH→CH 3 OCH 3 +H 2 O; (side reaction)
CO+3H 2 →CH 4 +H 2 O; (side reactions);
the reforming reaction produces a mixed gas of hydrogen, carbon dioxide and carbon monoxide. The mixed gas of hydrogen, carbon dioxide and carbon monoxide enters a hydrogen separation device 4 to carry out hydrogen separation operation, a hydrogen absorption pipe in the hydrogen separation device 4 carries out hydrogen absorption separation on the mixed gas of hydrogen, carbon dioxide and carbon monoxide, and separated pure hydrogen is output from a pure hydrogen outlet pipe; the separated carbon dioxide mixed residual gas is output from a carbon dioxide mixed residual gas outlet pipe, the pressure and the temperature of the carbon dioxide mixed residual gas are controlled by an air compressor and a refrigerator 5 in sequence, the carbon dioxide mixed residual gas and carbon dioxide separation device performs liquefaction separation, separated liquid carbon dioxide is collected, the separated hydrogen mixed residual gas is sent into a lower reaction cavity 32 of a reforming device 3, the hydrogen mixed residual gas is changed into reformed mixed gas after being reformed by water gas, the gas phase component of the reformed mixed gas is close to the component proportion of the reformed mixed gas generated by reforming reaction, and the reformed mixed gas in the lower reaction cavity 32 directly enters an upper reaction cavity 31 and is mixed with the mixed gas of hydrogen, carbon dioxide and carbon monoxide, and the mixed gas enters a hydrogen separation device 4 again for cyclic hydrogen absorption separation, so that the hydrogen yield of the whole medium-pressure hydrogen production system is improved.
The medium-pressure hydrogen production system of the invention makes the equipment for reforming the methanol vapor and the equipment for reforming the hydrogen mixed residual gas in the traditional hydrogen production system into one equipment, so that the reforming of the methanol vapor and the reforming of the hydrogen mixed residual gas can be concentrated in the reaction cavity with the same temperature, the hydrogen production efficiency of the hydrogen production system is improved, and the structure of the whole hydrogen production system is optimized and simplified, thereby being capable of being made into small-sized hydrogen production equipment by means of the hydrogen production system.
In the medium-pressure hydrogen production system, a medium-pressure reforming reaction environment is provided by the liquid pump 1, the pressure provided by the liquid pump 1 is 7-18 MPa, so that when the whole hydrogen production system aims at treating the carbon dioxide mixed residual gas, only one refrigerator 5 is needed to control the temperature (-25-18 ℃) of the carbon dioxide mixed residual gas in the carbon dioxide liquefying device 6, the pressure of the carbon dioxide mixed residual gas in the carbon dioxide liquefying device 6 is directly controlled by the liquid pump 1 from the source, compared with the low-pressure hydrogen production system, an air compressor (the low-pressure hydrogen production system needs to be independently provided with an air compressor to provide the liquefying pressure for the carbon dioxide mixed residual gas) can be omitted, and the medium-pressure hydrogen production system is simplified and optimized.
The output carbon dioxide mixed residual gas is provided with working pressure and temperature in a carbon dioxide liquefying device 6 through a liquid pump 1 and a refrigerator 5, so that the carbon dioxide mixed residual gas is separated into hydrogen mixed residual gas with a preset molar ratio, and then the hydrogen mixed residual gas is prepared into reformed mixed gas through a water gas reforming device 3.
Example two
The medium pressure hydrogen production method adopts the medium pressure hydrogen production system and comprises the following steps:
s1, feeding methanol water into a methanol-water vapor pipe inlet pipe by a liquid pump 1, wherein the pumping pressure is 7-18 MPa, heating and vaporizing the methanol water into methanol water vapor, feeding the methanol water vapor into an upper reaction cavity 31 of a reforming device 3, carrying out reforming reaction on the methanol water vapor in the upper reaction cavity 31 to generate mixed gas of hydrogen, carbon dioxide and carbon monoxide, and feeding the mixed gas of the hydrogen, the carbon dioxide and the carbon monoxide into a hydrogen separation cavity of a hydrogen separation device 4;
the methanol vapor carries out catalytic reaction under the corresponding temperature and catalyst filler, which is a multi-component and multi-reaction gas-solid catalytic reaction system;
the reaction equation is: CH (CH) 3 OH→CO+2H 2 The method comprises the steps of carrying out a first treatment on the surface of the (reversible reaction)
H 2 O+CO→CO 2 +H 2 The method comprises the steps of carrying out a first treatment on the surface of the (reversible reaction)
CH 3 OH+H 2 O→CO 2 +3H 2 The method comprises the steps of carrying out a first treatment on the surface of the (reversible reaction)
2CH 3 OH→CH 3 OCH 3 +H 2 O; (side reaction)
CO+3H 2 →CH 4 +H 2 O; (side reactions);
the gas phase components of the mixed gas of the hydrogen, the carbon dioxide and the carbon monoxide are 65-75% of the hydrogen, 20-26% of the carbon dioxide and 0.3-3% of the carbon monoxide;
s2, a hydrogen absorption pipe in the hydrogen separation cavity separates mixed gas of hydrogen, carbon dioxide and carbon monoxide, and the separated pure hydrogen is output from a pure hydrogen outlet pipe and collected; outputting the residual carbon dioxide mixed residual gas from a carbon dioxide mixed residual gas outlet pipe, controlling the pressure of the carbon dioxide mixed residual gas by a liquid pump 1, controlling the temperature of the carbon dioxide mixed residual gas by a refrigerator 5, and then sending the carbon dioxide mixed residual gas into a carbon dioxide separation device for carbon dioxide liquefaction and separation;
the gas phase components of the carbon dioxide mixed residual gas comprise 25-45% of hydrogen, 55-75% of carbon dioxide, 0-3% of water and 0.3-3% of carbon monoxide;
the pressure controlled by the liquid pump 1 is 7-18 MPa, and the temperature controlled by the refrigerator 5 is-25-18 ℃;
s3, preparing liquid carbon dioxide and hydrogen mixed residual gas in a carbon dioxide separator from the carbon dioxide mixed residual gas, and outputting and collecting the liquid carbon dioxide;
the components of the hydrogen mixed residual gas are 65-75% of hydrogen, 20-26% of carbon dioxide and 3-9% of carbon monoxide;
the molar ratio of carbon dioxide in the gas phase component of the hydrogen mixed residual gas is controlled to be 20-26%, and the selection of the pressure and the temperature of the carbon dioxide liquefying device 6 during working is shown in the following table:
| scheme for the production of a semiconductor device | Pressure (MPa) | Temperature (. Degree. C.) |
| Scheme 1 | 7 | -25 |
| Scheme 2 | 10 | -10 |
| Scheme 3 | 15 | 0 |
| Scheme 4 | 18 | 18 |
S4, delivering the hydrogen mixed residual gas into a lower reaction cavity 32 of the reforming device 3, preparing reformed mixed gas by water distribution, and carrying out water distribution according to the content of carbon monoxide, wherein the ratio of water distribution to carbon monoxide is as follows: water is 1:1-20;
the water gas reforming reaction formula is: CO+H 2 O→CO 2 +H 2 ；
The fed hydrogen mixed residual gas is subjected to water distribution and reforming in the lower reaction cavity 32 to form reformed mixed gas, wherein the gas phase components of the reformed mixed gas comprise 62-77% of hydrogen, 22-27% of carbon dioxide and 0.5-1.5% of carbon monoxide;
the ratio of the hydrogen, the carbon dioxide and the carbon monoxide in the reforming mixed gas is close to the ratio of the hydrogen, the carbon dioxide and the carbon monoxide in the mixed gas of the hydrogen, the carbon dioxide and the carbon monoxide;
s5, the reforming mixed gas enters the upper reaction cavity 31 to be mixed with the mixed gas of the hydrogen, the carbon dioxide and the carbon monoxide, and the reforming mixed gas and the mixed gas of the hydrogen, the carbon dioxide and the carbon monoxide are sent into the hydrogen separation device 4 together after being mixed in the upper reaction cavity 31 to carry out hydrogen separation operation again.
Specifically, the output pure hydrogen and carbon dioxide mixed residual gas are output after heat exchange and temperature reduction through the three-phase heat exchange device 2, and the methanol water is vaporized into methanol water vapor through heat exchange of the three-phase heat exchange device 2.
In this embodiment, the methanol water may be replaced by natural gas, and the mixed gas of hydrogen, carbon dioxide and carbon monoxide is obtained by hydrogen production from natural gas.
According to the medium-pressure hydrogen production method, by means of the methanol vapor and hydrogen mixer integrated medium-pressure hydrogen production system in the first embodiment, methanol water is used as a hydrogen production raw material, a liquid pump 1 provides medium pressure (7-18 MPa) at a source to pump the methanol water into an upper reaction cavity 31 of a reforming device 3, mixed gas of hydrogen, carbon dioxide and carbon monoxide is generated through reaction, then the mixed gas of the hydrogen, the carbon dioxide and the carbon monoxide is sent into a hydrogen separation cavity of a hydrogen separation device 4, a hydrogen absorption pipe in the hydrogen separation cavity reacts and absorbs hydrogen, collected pure hydrogen can be directly output and collected, and the hydrogen production efficiency is greatly improved. Then, conveying the generated carbon dioxide mixed residual gas, controlling the pressure and the temperature of the carbon dioxide mixed residual gas in a carbon dioxide separation device through a liquid pump 1 and a refrigerator 5, liquefying and separating the carbon dioxide in the carbon dioxide mixed residual gas, controlling the components of the separated hydrogen mixed residual gas, and enabling the carbon dioxide molar ratio in the hydrogen mixed residual gas to be lower than 26 percent, so that the hydrogen mixed residual gas is ready for the subsequent reforming mixed gas; the hydrogen mixed residual gas is sent into the lower reaction cavity 32 of the reforming device 3, the operation temperature of the lower reaction cavity 32 and the upper reaction cavity 31 of the reforming device 3 is the same, the reforming mixed gas is generated by water gas water distribution reforming, the carbon monoxide in the hydrogen mixed residual gas is reduced to 0.5-1.5% from the original 3-9%, and the gas phase component of the reforming mixed gas is as follows: 62-77% of hydrogen, 22-27% of carbon dioxide and 0.5-1.5% of carbon monoxide; the gas phase component of the reforming mixed gas is close to the mixed gas component of the hydrogen, the carbon dioxide and the carbon monoxide prepared by the reformer, the reforming mixed gas enters the upper reaction cavity 31 and is mixed with the mixed gas of the hydrogen, the carbon dioxide and the carbon monoxide, and the mixed gas enters the hydrogen separation device 4 again for circulating hydrogen absorption separation, so that the gas in the system is circularly purified, the theoretical yield can reach 100%, and the hydrogen yield is more than or equal to 95%.
With the above-described preferred embodiments according to the present invention as an illustration, the above-described descriptions can be used by persons skilled in the relevant art to make various changes and modifications without departing from the scope of the technical idea of the present invention. The technical scope of the present invention is not limited to the description, but must be determined according to the scope of claims.
Claims (3)
1. A medium pressure hydrogen production method is characterized in that a medium pressure hydrogen production system is adopted, and the medium pressure hydrogen production system comprises
The device comprises a three-phase heat exchange device, a reforming device, a hydrogen separation device, a steam trap, a refrigerator and a carbon dioxide liquefying device;
the reforming device comprises a reaction cavity, and a heating cavity is arranged outside the reaction cavity; the reaction cavity comprises an upper reaction cavity suitable for reforming methanol vapor and a lower reaction cavity suitable for reforming hydrogen mixed residual gas, and the upper reaction cavity is communicated with the lower reaction cavity;
copper-based filler or zirconium-based filler is filled in the upper reaction cavity, and copper-based filler or zirconium-based filler is filled in the lower reaction cavity; the upper reaction cavity is provided with a first inlet and a first outlet, and the lower reaction cavity is provided with a second inlet;
the first inlet is connected with a methanol vapor inlet pipe, the first outlet is connected with an inlet of the hydrogen separation device, the hydrogen separation device is connected with a pure hydrogen outlet pipe and a carbon dioxide mixed residual gas outlet pipe, the carbon dioxide mixed residual gas outlet pipe is sequentially connected with a three-phase heat exchange device, a steam trap, a refrigerator and a carbon dioxide liquefying device, the carbon dioxide liquefying device is connected with the carbon dioxide outlet pipe and the hydrogen mixed residual gas outlet pipe, and the hydrogen mixed residual gas outlet pipe is connected with the second inlet; an air pump for raising the conveying pressure of the hydrogen mixed residual air in the pipe is arranged on the hydrogen mixed residual air outlet pipe; the methanol water vapor inlet pipe and the pure hydrogen outlet pipe are connected with a three-phase heat exchange device;
the methanol vapor inlet pipe is connected with a liquid pump, and the pumping pressure of the liquid pump is 7-18 MPa;
the temperature controlled by the refrigerator is-25-18 ℃;
the pure hydrogen outlet pipe is connected with the hydrogen storage tank, the compressor is arranged on the pure hydrogen outlet pipe and is suitable for conveying pure hydrogen into the hydrogen storage tank, and the hydrogen storage tank is connected with the hydrogenation machine;
the method comprises the following steps:
s1, feeding methanol water into a methanol vapor inlet pipe by a liquid pump, wherein the pumping pressure is 7-18 MPa, heating and vaporizing the methanol water into methanol vapor, feeding the methanol vapor into an upper reaction cavity of a reforming device, carrying out reforming reaction on the methanol vapor in the upper reaction cavity to generate mixed gas of hydrogen, carbon dioxide and carbon monoxide, and feeding the mixed gas of the hydrogen, the carbon dioxide and the carbon monoxide into a hydrogen separation cavity of a hydrogen separation device;
the gas phase components of the mixed gas of hydrogen, carbon dioxide and carbon monoxide are 65-75% of hydrogen, 20-26% of carbon dioxide and 0.3-3% of carbon monoxide, and the sum of the components is 100%;
s2, a hydrogen absorption pipe in the hydrogen separation cavity separates mixed gas of hydrogen, carbon dioxide and carbon monoxide, and the separated pure hydrogen is output from a pure hydrogen outlet pipe and collected; outputting the residual carbon dioxide mixed residual gas from a carbon dioxide mixed residual gas outlet pipe, controlling the pressure of the carbon dioxide mixed residual gas by a liquid pump, controlling the temperature of the carbon dioxide mixed residual gas by a refrigerator, and then sending the carbon dioxide mixed residual gas into a carbon dioxide separation device for carbon dioxide liquefaction and separation;
the gas phase components of the carbon dioxide mixed residual gas comprise 25-45% of hydrogen, 55-75% of carbon dioxide, 0-3% of water and 0.3-3% of carbon monoxide, and the sum of the components is 100%;
the pressure controlled by the liquid pump is 7-18 MPa, and the temperature controlled by the refrigerator is-25-18 ℃;
s3, preparing liquid carbon dioxide and hydrogen mixed residual gas in a carbon dioxide separator from the carbon dioxide mixed residual gas, and outputting and collecting the liquid carbon dioxide;
the components of the hydrogen mixed residual gas are 65-75% of hydrogen, 20-26% of carbon dioxide and 3-9% of carbon monoxide;
s4, delivering the hydrogen mixed residual gas into a lower reaction cavity of the reforming device, preparing reformed mixed gas by water distribution, and carrying out water distribution according to the content of carbon monoxide, wherein the water distribution ratio is carbon monoxide: water is 1:1-20;
the fed hydrogen mixed residual gas is subjected to water distribution reforming in a lower reaction cavity to form reforming mixed gas, wherein the gas phase components of the reforming mixed gas comprise 62-77% of hydrogen, 22-27% of carbon dioxide and 0.5-1.5% of carbon monoxide, and the sum of the components is 100%;
the ratio of the hydrogen, the carbon dioxide and the carbon monoxide in the reforming mixed gas is close to the ratio of the hydrogen, the carbon dioxide and the carbon monoxide in the mixed gas of the hydrogen, the carbon dioxide and the carbon monoxide;
s5, the reforming mixed gas enters the upper reaction cavity to be mixed with the mixed gas of the hydrogen, the carbon dioxide and the carbon monoxide, and the reforming mixed gas and the mixed gas of the hydrogen, the carbon dioxide and the carbon monoxide are sent into the hydrogen separation device together after being mixed in the upper reaction cavity to carry out hydrogen separation operation again.
2. The medium pressure hydrogen production method according to claim 1, wherein the outputted pure hydrogen and carbon dioxide mixed residual gas are outputted after being subjected to heat exchange and temperature reduction by a three-phase heat exchange device, and the methanol water is vaporized into methanol water vapor by heat exchange by the three-phase heat exchange device.
3. The medium pressure hydrogen production process of claim 1 wherein the methanol water is replaced with natural gas.
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