CN110937572B - Reforming and separating integrated low-pressure hydrogen production system and hydrogen production method thereof - Google Patents
Reforming and separating integrated low-pressure hydrogen production system and hydrogen production method thereof Download PDFInfo
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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
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- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
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- C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
- C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
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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
- C01B2203/12—Feeding the process for making hydrogen or synthesis gas
- C01B2203/1205—Composition of the feed
- C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
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- C01B2203/1205—Composition of the feed
- C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
- C01B2203/1235—Hydrocarbons
- C01B2203/1241—Natural gas or methane
Abstract
The invention relates to a reforming and separating integrated low-pressure hydrogen-producing system, which comprises a reforming and separating device, a three-phase heat exchange device, an air compressor, a steam trap, a refrigerator and a carbon dioxide liquefying device, wherein the reforming and separating device is connected with the three-phase heat exchange device; the pumping pressure of the liquid pump is 2-5 MPa; the pressure controlled by the air compressor is 5-30 MPa, and the temperature controlled by the refrigerator is-35-30.8 ℃. The low pressure hydrogen producing process includes reforming methanol vapor in the upper reaction cavity and separating mixed gas with hydrogen in the hydrogen absorbing pipe; preparing liquid carbon dioxide and hydrogen mixed residual gas from the carbon dioxide mixed residual gas in a carbon dioxide separator, wherein the proportion of the reforming mixed gas is close to that of the mixed gas of hydrogen, carbon dioxide and carbon monoxide; the hydrogen absorption pipe performs hydrogen separation operation on the reformed mixed gas and the mixed gas of hydrogen, carbon dioxide and carbon monoxide. The gas in the system is circularly purified, the theoretical yield can reach 100%, and the hydrogen yield is more than or equal to 95%.
Description
Technical Field
The invention relates to a reforming and separating integrated low-pressure hydrogen production system and a hydrogen production method thereof.
Background
The hydrogen energy is used as the most ideal energy in the 21 st century, is used as automobile fuel, is easy to start at low temperature, has small corrosion effect on the engine, and can prolong the service life of the engine. Because the hydrogen and the air can be uniformly mixed, a carburetor used on a common automobile can be completely omitted, and the structure of the traditional automobile can be simplified. Of further interest is the addition of only 4% hydrogen to the gasoline. The fuel can save fuel by 40% when used as fuel of automobile engine, and does not need to improve the gasoline engine. The hydrogen fuel cell serves as a power generation system.
The fuel cell has no pollution to the environment. It is by electrochemical reaction, rather than by combustion (gasoline, diesel) or energy storage (battery) means-most typically conventional back-up power schemes. Combustion releases contaminants such as COx, NOx, SOx gas and dust. As described above, the fuel cell generates only water and heat. If hydrogen is generated by renewable energy sources (photovoltaic panels, wind power generation and the like), the whole cycle is a complete process without harmful substance emission.
The fuel cell operates quietly without noise, which is only about 55dB, corresponding to the level of normal human conversation. This makes the fuel cell suitable for a wider range including indoor installation or where noise is limited outdoors.
The high efficiency, the generating efficiency of the fuel cell can reach more than 50%, which is determined by the conversion property of the fuel cell, directly converts chemical energy into electric energy without intermediate conversion of heat energy and mechanical energy (generator), because the efficiency is reduced once more by one energy conversion.
At present, the main source of hydrogen in a hydrogen energy hydrogenation station is that an energy storage tank is used for transporting the hydrogen back from the outside, and the whole hydrogenation station needs to store a large amount of hydrogen; the research shows that the hydrogen in the hydrogen energy industry comprises four links, namely hydrogen preparation, hydrogen storage, hydrogen transportation and hydrogen addition (adding hydrogen into a hydrogen energy vehicle), wherein the two links, namely the hydrogen preparation and the hydrogen addition, are safer at present, the hydrogen storage link is easier to generate accidents, and the cost of the hydrogen transportation link is higher, so that the hydrogen transportation link is related to the characteristics of the hydrogen; at present, the problem of explosion of a hydrogenation station and the reason of high hydrogenation cost often occur in news.
Therefore, in order to reduce the problem of hydrogen storage in large quantities in the conventional hydrogen adding station, the high cost of hydrogen transportation links is shortened or reduced, and a hydrogen adding station system needs to be redesigned.
Disclosure of Invention
The invention aims to solve the technical problems that: the device overcomes the defects of the prior art, provides a reforming and separation integrated reaction device, and solves the problem that the existing reformer for methanol vapor, hydrogen separation and water gas reforming are three independent devices, so that a hydrogen production system is complicated.
Meanwhile, the low-pressure hydrogen production method solves the problems that the existing hydrogen production process is complex and the cyclic hydrogen production cannot be realized.
The technical scheme adopted for solving the technical problems is as follows:
a reforming and separating integrated low-pressure hydrogen-making system comprises a reforming and separating device, a three-phase heat exchange device, an air compressor, a steam trap, a refrigerator and a carbon dioxide liquefying device;
the reforming separation device comprises an upper reaction cavity and a lower reaction cavity, wherein the upper reaction cavity is communicated with the lower reaction cavity, the upper reaction cavity is filled with a first catalytic filler, and the lower reaction cavity is filled with a second catalytic filler;
the upper reaction cavity is provided with a first inlet for inputting methanol vapor and a first outlet for outputting carbon dioxide mixed residual gas, a hydrogen absorption pipe is inserted into the upper reaction cavity, the hydrogen absorption pipe carries out hydrogen absorption separation on the mixed gas in the upper reaction cavity, and the absorbed hydrogen is output from the hydrogen absorption pipe; the lower reaction cavity is provided with a second inlet for inputting hydrogen mixed residual gas;
the first inlet is connected with a methanol vapor inlet pipe, the outlet of the hydrogen absorption pipe is connected with a pure hydrogen outlet pipe, the first outlet is connected with a carbon dioxide mixed residual gas outlet pipe, the methanol vapor inlet pipe, the pure hydrogen outlet pipe and the carbon dioxide mixed residual gas outlet pipe are all connected with a three-phase heat exchange device, the carbon dioxide mixed residual gas outlet pipe is sequentially connected with an air compressor, a steam trap, a refrigerator and a carbon dioxide liquefying device, the carbon dioxide liquefying device is connected with a hydrogen mixed residual gas outlet pipe, and the hydrogen mixed residual gas outlet pipe is connected with a second inlet of the reforming and separating device;
the methanol vapor inlet pipe is connected with a liquid pump, and the pumping pressure of the liquid pump is 2-5 MPa;
the pressure controlled by the air compressor is 5-30 MPa, and the temperature controlled by the refrigerator is-35-30.8 ℃.
Further, the hydrogen absorption tube is a niobium tube, the first catalytic filler is copper-based filler or zirconium-based filler, the second catalytic filler is copper-based filler or zirconium-based filler, and the operation temperature of the upper reaction cavity and the lower reaction cavity is 200-500 ℃.
Further, the hydrogen absorption tube is a palladium membrane tube or a palladium alloy membrane tube, the first catalytic filler is copper-based filler or zirconium-based filler, the second catalytic filler is copper-based filler or zirconium-based filler, and the operation temperature of the upper reaction cavity and the lower reaction cavity is 250-550 ℃.
Further, the pure hydrogen outlet pipe is connected with the hydrogen storage tank, a compressor is arranged on the pure 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 low pressure hydrogen production method, which adopts the reforming and separation integrated low pressure hydrogen production system, comprises the following steps:
s1, feeding methanol water into a methanol-water vapor pipe inlet pipe by a liquid pump, wherein the pumping pressure is 2-5 MPa, heating and vaporizing the methanol water into methanol water vapor, entering an upper reaction cavity of a reforming and separating device, performing a reforming reaction on the methanol water vapor in the upper reaction cavity to generate a mixed gas of hydrogen, carbon dioxide and carbon monoxide, and then performing hydrogen separation on the generated mixed gas of hydrogen, carbon dioxide and carbon monoxide by a hydrogen absorption pipe;
the gas phase components of the mixed gas of the hydrogen, the carbon dioxide and the carbon monoxide are 65-75% of the hydrogen, 20-26% of the carbon dioxide and 0.3-3% of the carbon monoxide;
s2, separating the mixed gas of the hydrogen, the carbon dioxide and the carbon monoxide by the hydrogen absorption tube, and collecting the separated pure hydrogen from the output of the hydrogen absorption tube; 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 through an air compressor, controlling the temperature of the carbon dioxide mixed residual gas through a refrigerator, and then sending the carbon dioxide mixed residual gas into a carbon dioxide separation device for carbon dioxide liquefaction and separation;
the gas phase components of the carbon dioxide mixed residual gas comprise 25-45% of hydrogen, 55-75% of carbon dioxide, 0-3% of water and 0.3-3% of carbon monoxide;
the pressure controlled by the air compressor is 5-30 MPa, and the temperature controlled by the refrigerator is-35-30.8 ℃;
s3, preparing liquid carbon dioxide and hydrogen mixed residual gas in a carbon dioxide separator from the carbon dioxide mixed residual gas, and outputting and collecting the liquid carbon dioxide;
the components of the hydrogen mixed residual gas are 65-75% of hydrogen, 20-26% of carbon dioxide and 3-9% of carbon monoxide;
s4, delivering the hydrogen mixed residual gas into a lower reaction cavity of the reforming separation device, 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 fed hydrogen mixed residual gas is subjected to water distribution reforming in a lower reaction cavity to form reforming mixed gas, wherein the gas phase components of the reforming mixed gas are 62-77% of hydrogen, 22-27% of carbon dioxide and 0.5-1.5% of carbon monoxide;
the ratio of the hydrogen, the carbon dioxide and the carbon monoxide in the reforming mixed gas is close to the ratio of the hydrogen, the carbon dioxide and the carbon monoxide in the mixed gas of the hydrogen, the carbon dioxide and the carbon monoxide;
s5, the reforming mixed gas enters an upper reaction cavity and is mixed with the mixed gas of hydrogen, carbon dioxide and carbon monoxide, and a hydrogen absorption pipe carries out hydrogen separation operation on the reforming mixed gas and the mixed gas of hydrogen, carbon dioxide and carbon monoxide.
Furthermore, the output pure hydrogen and carbon dioxide mixed residual gas are output after being subjected to heat exchange and temperature reduction through the three-phase heat exchange device, and the methanol water is vaporized into methanol water vapor through the heat exchange of the three-phase heat exchange device.
Further, the methanol water is replaced by natural gas.
The beneficial effects of the invention are as follows:
the low-pressure hydrogen production system integrates the methanol steam reforming, the hydrogen absorption separation of mixed gas and the hydrogen mixed residual gas reforming into one reaction cavity at the same operation temperature, so that the integration of a methanol water reforming device, a hydrogen separation device and a water gas reformer is realized, the layout structure of the whole hydrogen production system is optimized, and small hydrogen production equipment can be manufactured by means of the hydrogen production system.
According to the low-pressure hydrogen preparation method, the reforming separation of methanol and steam and the hydrogen absorption separation of a hydrogen absorption pipe are carried out in an upper reaction cavity, separated hydrogen is collected, separated carbon dioxide mixed residual gas is recycled, the pressure and temperature of separating liquid carbon dioxide from the carbon dioxide mixed residual gas are controlled by an air compressor and a refrigerator, the carbon dioxide mixed residual gas is separated into hydrogen mixed residual gas and liquid carbon dioxide by a carbon dioxide liquefying device, the liquid carbon dioxide can be stored, and when the carbon dioxide liquefying device is separated, the pressure and temperature are controlled, so that the gas phase components in the hydrogen mixed residual gas are controlled, the carbon dioxide mole ratio in the hydrogen mixed residual gas is lower than 26%, and the hydrogen mixed residual gas is prepared for the subsequent reforming mixed gas; the hydrogen mixed residual gas is reformed by water gas distribution in the reaction chamber, so that the carbon monoxide in the hydrogen mixed residual gas is reduced to 0.5-1.5% from original 3-9%, and the gas phase 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 upper reaction cavity again, and are mixed with the mixed gas of the hydrogen, the carbon dioxide and the carbon monoxide, and the hydrogen absorption pipe performs hydrogen purification and separation hydrogen production operation again, so that the gas in the system is circularly purified, the theoretical yield can reach 100%, and the hydrogen yield is more than or equal to 95%.
Meanwhile, the hydrogen station system for preparing hydrogen by utilizing methanol aims at direct consumption customers, and the selling price of hydrogen is saved compared with the factory hydrogen, so that the hydrogen in the carbon dioxide residual gas is recovered, the theoretical 100 percent yield can be realized, the actual yield is more than 90-99 percent, and the CO is recovered simultaneously 2 The theoretical yield is 100 percent and the actual yield is 90-99 percent. The process is combined with a hydrogenation station, so that the high yield of hydrogen can be realized,at the same time recycle CO 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.
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 state sunlight hydrogenation station technology can be extended to other chemical synthesis fields, and can also be used for chemical hydrogenation; sixth, the system can be multi-element co-station with a gas station or a methanol adding station. The system is particularly suitable for energy supply and current gas stations for community distributed combined heat and power.
Drawings
The invention is further described below with reference to the accompanying drawings.
FIG. 1 is a reforming, separation integrated low pressure hydrogen system;
FIG. 2 is a schematic diagram of a reforming separation device;
the device comprises a liquid pump 1, a three-phase heat exchange device 2, a reforming separation device 3, a reforming separation device 31, an upper reaction cavity 32, a lower reaction cavity 33, a heating cavity 34, a hydrogen absorption pipe 4, a carbon dioxide liquefying device 5, a refrigerator 6, an air compressor 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 reforming and separation integrated low-pressure hydrogen production system comprises a reforming and separation device 3, a three-phase heat exchange device 2, an air compressor, a steam trap, a refrigerator 5 and a carbon dioxide liquefying device 4.
The reforming separation device 3 comprises an upper reaction cavity 31 and a lower reaction cavity 32, wherein the upper reaction cavity 31 is communicated with the lower reaction cavity 32, the upper reaction cavity 31 is filled with a first catalytic filler, and the lower reaction cavity 32 is filled with a second catalytic filler;
the upper reaction chamber 31 is provided with a first inlet for inputting methanol vapor and a first outlet for outputting carbon dioxide mixed residual gas, a hydrogen absorption pipe 34 is inserted into the upper reaction chamber 31, the hydrogen absorption pipe 34 performs hydrogen absorption separation on the mixed gas in the upper reaction chamber 31, and the absorbed hydrogen is output from the hydrogen absorption pipe 34; the lower reaction chamber 32 is provided with a second inlet for inputting hydrogen mixed residual gas;
the first inlet is connected with a methanol vapor inlet pipe, the outlet of the hydrogen absorption pipe 34 is connected with a pure hydrogen outlet pipe, the first outlet is connected with a carbon dioxide mixed residual gas outlet pipe, the methanol vapor inlet pipe, the pure hydrogen outlet pipe and the carbon dioxide mixed residual gas outlet pipe are all connected with the three-phase heat exchange device 2, the carbon dioxide mixed residual gas outlet pipe is sequentially connected with the air compressor 6, the steam trap 7, the refrigerator 5 and the carbon dioxide liquefying device 4, the carbon dioxide liquefying device 4 is connected with a hydrogen mixed residual gas outlet pipe, and the hydrogen mixed residual gas outlet pipe is connected with the second inlet of the reforming and separating device 3;
the steam trap 7 is used for removing moisture in the carbon dioxide mixed residual gas, and the carbon dioxide mixed residual gas is liquefied by carbon dioxide after controlling the moisture.
The methanol vapor inlet pipe is connected with a liquid pump 1, and the pumping pressure of the liquid pump 1 is 2-5 MPa;
the pressure controlled by the air compressor 6 is 5-30 MPa, and the temperature controlled by the refrigerator 5 is-35-30.8 ℃.
Specifically, the hydrogen absorption tube 34 is a niobium tube, the first catalytic filler is a copper-based filler or a zirconium-based filler, the second catalytic filler is a copper-based filler or a zirconium-based filler, and the operating temperature of the upper reaction chamber 31 and the lower reaction chamber 32 is 200-500 ℃.
The hydrogen absorption tube 34 may also be a palladium membrane tube or a palladium alloy membrane tube, the first catalytic filler is copper-based filler or zirconium-based filler, the second catalytic filler is copper-based filler or zirconium-based filler, and the operating temperature of the upper reaction chamber 31 and the lower reaction chamber 32 is 250-550 ℃.
The method is characterized in that a niobium pipe, a palladium membrane pipe or a palladium alloy membrane pipe is adopted, the actions are the same, the mixed gas of hydrogen, carbon dioxide and carbon monoxide generated in a reaction cavity is subjected to hydrogen absorption and separation, pure hydrogen output is collected, and the rest carbon dioxide mixed residual gas is output in addition for recycling operation.
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 hydrogen production system realizes on-site hydrogen production, directly stores the prepared hydrogen into the hydrogen storage tank, and then directly adds the prepared pure hydrogen into the hydrogen vehicle through the hydrogenation machine.
During operation, methanol water is vaporized into methanol water vapor through the three-phase heat exchange device 2, the methanol water vapor enters the upper reaction cavity 31 of the reforming separation device 3, the heating cavity 33 heats and controls the temperature in the upper reaction cavity 31, and the methanol water vapor carries out catalytic reaction under the corresponding temperature and catalyst filler, so that the gas-solid catalytic reaction system with multiple components and multiple reactions is provided;
the reaction equation is: CH (CH) 3 OH→CO+2H 2 The method comprises the steps of carrying out a first treatment on the surface of the (reversible reaction)
H 2 O+CO→CO 2 +H 2 The method comprises the steps of carrying out a first treatment on the surface of the (reversible reaction)
CH 3 OH+H 2 O→CO 2 +3H 2 The method comprises the steps of carrying out a first treatment on the surface of the (reversible reaction)
2CH 3 OH→CH 3 OCH 3 +H 2 O; (side reaction)
CO+3H 2 →CH 4 +H 2 O; (side reactions);
the reforming reaction produces a mixed gas of hydrogen, carbon dioxide and carbon monoxide.
The hydrogen absorption pipe 34 in the upper reaction cavity 31 carries out hydrogen absorption operation on the mixed gas of hydrogen, carbon dioxide and carbon monoxide, the hydrogen absorption pipe 34 separates the hydrogen in the mixed gas, pure hydrogen is collected into a hydrogen storage tank after being output by the hydrogen absorption pipe 34, the rest carbon dioxide mixed residual gas is output from a carbon dioxide mixed residual gas outlet pipe of the upper reaction cavity 31, the carbon dioxide mixed residual gas is cooled by the three-phase heat exchange device 2, the pressure and the temperature of the carbon dioxide mixed residual gas entering the carbon dioxide separation device are controlled by the air compressor 6 and the refrigerator 5, then the carbon dioxide mixed residual gas and the carbon dioxide separation device carry out liquefaction separation, the separated liquid carbon dioxide is collected, the separated hydrogen mixed residual gas is sent into the lower reaction cavity 32 of the reforming separation device 3 for water gas water distribution reforming, the hydrogen mixed residual gas is changed into reformed mixed gas after being reformed, the gas component proportion of the reformed mixed gas and the mixed gas generated by the reaction is close, the reformed mixed gas enters the upper reaction cavity 31 from the lower reaction cavity 32 and is mixed with the mixed gas of the hydrogen, the carbon dioxide and the carbon monoxide, the liquefied carbon dioxide is continuously carried out liquefaction separation on the mixed gas after the mixed gas by the air pipe 34, and the separated liquid carbon dioxide is sent into the separated liquid carbon dioxide, and the mixed residual gas after the water gas is subjected to the hydrogen absorption separation, and the mixed gas, the carbon dioxide and the carbon dioxide is subjected to the carbon dioxide separation, and the carbon dioxide and carbon dioxide.
According to the low-pressure hydrogen production system, the reforming separation device 3 integrates the functions of methanol steam reforming, hydrogen separation and water gas reforming, so that the hydrogen production system is optimized, and small-sized hydrogen production equipment can be manufactured by means of the hydrogen production system. The pressure provided by the liquid pump 1 is 2-5 MPa, the whole hydrogen production system operates in a low-pressure state, and the hydrogen production operation is safer.
Example two
The method for low-pressure hydrogen production adopts the reforming and separating integrated low-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 2-5 MPa, heating and vaporizing the methanol water into methanol water vapor, and then feeding the methanol water vapor into an upper reaction cavity 31 of a reforming separation device 3, wherein the methanol water vapor carries out reforming reaction in the upper reaction cavity 31 to generate mixed gas of hydrogen, carbon dioxide and carbon monoxide, thus the system is a multi-component and multi-reaction gas-solid catalytic reaction system;
the reaction equation is: CH (CH) 3 OH→CO+2H 2 The method comprises the steps of carrying out a first treatment on the surface of the (reversible reaction)
H 2 O+CO→CO 2 +H 2 The method comprises the steps of carrying out a first treatment on the surface of the (reversible reaction)
CH 3 OH+H 2 O→CO 2 +3H 2 The method comprises the steps of carrying out a first treatment on the surface of the (reversible reaction)
2CH 3 OH→CH 3 OCH 3 +H 2 O; (side reaction)
CO+3H 2 →CH 4 +H 2 O; (side reactions);
the gas phase components of the mixed gas of the hydrogen, the carbon dioxide and the carbon monoxide are 65-75% of the hydrogen, 20-26% of the carbon dioxide and 0.3-3% of the carbon monoxide;
then the hydrogen absorption pipe 34 separates the generated mixed gas of hydrogen, carbon dioxide and carbon monoxide;
s2, a hydrogen absorption tube 34 inserted into the upper reaction cavity 31 separates the mixed gas of hydrogen, carbon dioxide and carbon monoxide, and the separated pure hydrogen is output from the hydrogen absorption tube 34 and collected; outputting the rest carbon dioxide mixed residual gas from a carbon dioxide mixed residual gas outlet pipe, controlling the pressure of the carbon dioxide mixed residual gas through an air compressor 6, controlling the temperature of the carbon dioxide mixed residual gas through 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 air compressor 6 is 5-30 MPa, and the temperature controlled by the refrigerator 5 is-35-30.8 ℃;
s3, preparing liquid carbon dioxide and hydrogen mixed residual gas in a carbon dioxide separator from the carbon dioxide mixed residual gas, and outputting and collecting the liquid carbon dioxide;
the components of the hydrogen mixed residual gas are 65-75% of hydrogen, 20-26% of carbon dioxide and 3-9% of carbon monoxide;
the molar ratio of carbon dioxide in the gas phase component of the hydrogen mixed residual gas is controlled to be 20-26%, and the selection of the pressure and the temperature of the carbon dioxide liquefying device 4 during working is shown in the following table:
| scheme for the production of a semiconductor device | Pressure (Mpa) | Temperature (. Degree. C.) |
| Scheme 1 | 5 | -35 |
| Scheme 2 | 7 | -25 |
| Scheme 3 | 10 | -10 |
| Scheme 4 | 15 | 0 |
| Scheme 5 | 20 | 20 |
| Scheme 6 | 25 | 25 |
| Scheme 7 | 30 | 30.8 |
S4, delivering the hydrogen mixed residual gas into a lower reaction cavity 32 of the reforming separation device 3, uniformly controlling the working temperatures of the lower reaction cavity 32 and an upper reaction cavity 31 by a heating cavity 33, preparing the hydrogen mixed residual gas into a reforming 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 water gas reforming reaction formula is: CO+H 2 O→CO 2 +H 2 ；
The fed hydrogen mixed residual gas is subjected to water distribution and reforming in the lower reaction cavity 32 to form reformed mixed gas, wherein the gas phase components of the reformed mixed gas comprise 62-77% of hydrogen, 22-27% of carbon dioxide and 0.5-1.5% of carbon monoxide;
the ratio of the hydrogen, the carbon dioxide and the carbon monoxide in the reforming mixed gas is close to the ratio of the hydrogen, the carbon dioxide and the carbon monoxide in the mixed gas of the hydrogen, the carbon dioxide and the carbon monoxide;
s5, the reformed mixed gas enters the upper reaction cavity 31 and is mixed with the mixed gas of hydrogen, carbon dioxide and carbon monoxide, and the hydrogen absorption pipe 34 carries out hydrogen separation operation on the reformed mixed gas and the mixed gas of hydrogen, carbon dioxide and carbon monoxide.
Specifically, the output pure hydrogen and carbon dioxide mixed residual gas are output after heat exchange and temperature reduction through the three-phase heat exchange device 2, and the methanol water is vaporized into methanol water vapor through heat exchange of the three-phase heat exchange device 2.
In this embodiment, the methanol water may be replaced by natural gas, and the mixed gas of hydrogen, carbon dioxide and carbon monoxide is obtained by hydrogen production from natural gas.
According to the low-pressure hydrogen preparation method, by means of the reforming and separating integrated low-pressure hydrogen preparation system in the first embodiment, methanol water is used as hydrogen preparation raw material, the liquid pump 1 provides low pressure (2-5 MPa) at the source to pump the methanol water into the upper reaction cavity 31 of the reforming and separating device 3, mixed gas of hydrogen, carbon dioxide and carbon monoxide is generated through reaction, then the hydrogen absorption pipe 34 reacts and absorbs hydrogen to the mixed gas of hydrogen, carbon dioxide and carbon monoxide, pure hydrogen can be directly output and collected, and the hydrogen preparation efficiency is greatly improved. Then, conveying the generated carbon dioxide mixed residual gas, controlling the pressure and the temperature of the carbon dioxide mixed residual gas in a carbon dioxide separation device through a air compressor 6 and a cooling machine, liquefying and separating the carbon dioxide in the carbon dioxide mixed residual gas, controlling the components of the separated hydrogen mixed residual gas, and enabling the carbon dioxide molar ratio in the hydrogen mixed residual gas to be lower than 26 percent, so that the hydrogen mixed residual gas is ready for the subsequent reforming mixed gas; the mixed residual hydrogen is sent into the lower reaction cavity 32 of the reforming separation device 3, the working temperature of the lower reaction cavity 32 and the upper reaction cavity 31 and the working temperature of the hydrogen absorption pipe 34 are uniformly controlled by the heating cavity 33, the mixed residual hydrogen is reformed by water gas distribution, the carbon monoxide in the mixed residual hydrogen is reduced to 0.5-1.5% from original 3-9%, and the gas phase component of the reformed mixed gas is as follows: 62-77% of hydrogen, 22-27% of carbon dioxide and 0.5-1.5% of carbon monoxide; the gas phase component of the reforming mixed gas is close to the mixed gas component of the hydrogen, the carbon dioxide and the carbon monoxide prepared by the reformer, the reforming mixed gas directly enters the upper reaction chamber 31 from the lower reaction chamber 32, is mixed with the mixed gas of the hydrogen, the carbon dioxide and the carbon monoxide, and is subjected to circulating hydrogen absorption separation again through the hydrogen absorption pipe 34, so that the gas in the system is circularly purified, the theoretical yield can reach 100%, and the hydrogen yield is more than or equal to 95%.
With the above-described preferred embodiments according to the present invention as an illustration, the above-described descriptions can be used by persons skilled in the relevant art to make various changes and modifications without departing from the scope of the technical idea of the present invention. The technical scope of the present invention is not limited to the description, but must be determined according to the scope of claims.
Claims (5)
1. The reforming and separating integrated low-pressure hydrogen-producing system is characterized by comprising a reforming and separating device, a three-phase heat exchange device, an air compressor, a steam trap, a refrigerator and a carbon dioxide liquefying device;
the reforming separation device comprises an upper reaction cavity and a lower reaction cavity, wherein the upper reaction cavity is communicated with the lower reaction cavity, the upper reaction cavity is filled with a first catalytic filler, and the lower reaction cavity is filled with a second catalytic filler;
the upper reaction cavity is provided with a first inlet for inputting methanol vapor and a first outlet for outputting carbon dioxide mixed residual gas, a hydrogen absorption pipe is inserted into the upper reaction cavity, the hydrogen absorption pipe carries out hydrogen absorption separation on the mixed gas in the upper reaction cavity, and the absorbed hydrogen is output from the hydrogen absorption pipe; the lower reaction cavity is provided with a second inlet for inputting hydrogen mixed residual gas;
the first inlet is connected with a methanol vapor inlet pipe, the outlet of the hydrogen absorption pipe is connected with a pure hydrogen outlet pipe, the first outlet is connected with a carbon dioxide mixed residual gas outlet pipe, the methanol vapor inlet pipe, the pure hydrogen outlet pipe and the carbon dioxide mixed residual gas outlet pipe are all connected with a three-phase heat exchange device, the carbon dioxide mixed residual gas outlet pipe is sequentially connected with an air compressor, a steam trap, a refrigerator and a carbon dioxide liquefying device, the carbon dioxide liquefying device is connected with a hydrogen mixed residual gas outlet pipe, and the hydrogen mixed residual gas outlet pipe is connected with a second inlet of the reforming and separating device;
the methanol vapor inlet pipe is connected with a liquid pump, and the pumping pressure of the liquid pump is 2-5 MPa;
the pressure controlled by the air compressor is 5-30 MPa, and the temperature controlled by the refrigerator is-35-30.8 ℃;
the hydrogen absorption pipe is a niobium pipe, the first catalytic filler is copper-based filler or zirconium-based filler, the second catalytic filler is copper-based filler or zirconium-based filler, and the operation temperature of the upper reaction cavity and the lower reaction cavity is 200-500 ℃;
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.
2. The reforming and separation integrated low-pressure hydrogen production system according to claim 1, wherein the hydrogen absorption tube is replaced by a palladium membrane tube or a palladium alloy membrane tube, and the temperature of the operation of the upper reaction chamber and the lower reaction chamber is replaced by 250-550 ℃.
3. A method for low-pressure hydrogen production, characterized in that the reforming and separation integrated low-pressure hydrogen production system according to any one of claims 1 to 2 is used, comprising the steps of:
s1, feeding methanol water into a methanol vapor inlet pipe by a liquid pump, wherein the pumping pressure is 2-5 MPa, heating and vaporizing the methanol water into methanol vapor, entering an upper reaction cavity of a reforming and separating device, performing a reforming reaction on the methanol vapor in the upper reaction cavity to generate a mixed gas of hydrogen, carbon dioxide and carbon monoxide, and then performing hydrogen separation on the generated mixed gas of hydrogen, carbon dioxide and carbon monoxide by a hydrogen absorption pipe;
the gas phase components of the mixed gas of the hydrogen, the carbon dioxide and the carbon monoxide are 65-75% of the hydrogen, 20-26% of the carbon dioxide and 0.3-3% of the carbon monoxide;
s2, separating the mixed gas of the hydrogen, the carbon dioxide and the carbon monoxide by the hydrogen absorption tube, and collecting the separated pure hydrogen from the output of the hydrogen absorption tube; 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 through an air compressor, controlling the temperature of the carbon dioxide mixed residual gas through a refrigerator, and then sending the carbon dioxide mixed residual gas into a carbon dioxide separation device for carbon dioxide liquefaction and separation;
the gas phase components of the carbon dioxide mixed residual gas comprise 25-45% of hydrogen, 55-75% of carbon dioxide, 0-3% of water and 0.3-3% of carbon monoxide;
the pressure controlled by the air compressor is 5-30 MPa, and the temperature controlled by the refrigerator is-35-30.8 ℃;
s3, preparing liquid carbon dioxide and hydrogen mixed residual gas in a carbon dioxide separator from the carbon dioxide mixed residual gas, and outputting and collecting the liquid carbon dioxide;
the components of the hydrogen mixed residual gas are 65-75% of hydrogen, 20-26% of carbon dioxide and 3-9% of carbon monoxide;
s4, delivering the hydrogen mixed residual gas into a lower reaction cavity of the reforming separation device, 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 fed hydrogen mixed residual gas is subjected to water distribution reforming in a lower reaction cavity to form reforming mixed gas, wherein the gas phase components of the reforming mixed gas are 62-77% of hydrogen, 22-27% of carbon dioxide and 0.5-1.5% of carbon monoxide;
the ratio of the hydrogen, the carbon dioxide and the carbon monoxide in the reforming mixed gas is close to the ratio of the hydrogen, the carbon dioxide and the carbon monoxide in the mixed gas of the hydrogen, the carbon dioxide and the carbon monoxide;
s5, the reforming mixed gas enters an upper reaction cavity and is mixed with the mixed gas of hydrogen, carbon dioxide and carbon monoxide, and a hydrogen absorption pipe carries out hydrogen separation operation on the reforming mixed gas and the mixed gas of hydrogen, carbon dioxide and carbon monoxide.
4. The method for low-pressure hydrogen production according to claim 3, wherein the outputted pure hydrogen and carbon dioxide mixed residual gas are outputted after being subjected to heat exchange and temperature reduction by the 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.
5. A low pressure hydrogen production process according to claim 3 wherein the methanol water is replaced by natural gas.
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