CN211998805U - Methanol steam reforming and hydrogen separation integrated ultrahigh pressure hydrogen production system - Google Patents
Methanol steam reforming and hydrogen separation integrated ultrahigh pressure hydrogen production system Download PDFInfo
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- CN211998805U CN211998805U CN201921826710.4U CN201921826710U CN211998805U CN 211998805 U CN211998805 U CN 211998805U CN 201921826710 U CN201921826710 U CN 201921826710U CN 211998805 U CN211998805 U CN 211998805U
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Abstract
The invention relates to a methanol steam reforming and hydrogen separation integrated ultrahigh pressure hydrogen production system, which comprises a reforming separation device, a three-phase heat exchange device, a steam trap, a water-cooled heat exchanger, a carbon dioxide separation device and a water gas reforming device, wherein the three-phase heat exchange device is connected with the steam trap; the operating temperature of the water-cooled heat exchanger is less than or equal to 30.8 ℃; the pumping pressure of the liquid pump is 40-100 MPa; pure hydrogen is pumped into a hydrogen storage tank under the pump pressure of a liquid pump. The gas in the system is circularly purified, the theoretical yield can reach 100 percent, and the yield of the hydrogen is more than or equal to 95 percent.
Description
Technical Field
The invention relates to a methanol steam reforming and hydrogen separation integrated ultrahigh pressure hydrogen production system.
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 reduce the problem of large amount of hydrogen storage in the existing hydrogen refueling station and shorten or reduce the high cost of the hydrogen transportation link, a hydrogen refueling 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 methanol steam reforming and hydrogen separation integrated ultrahigh pressure hydrogen production system is provided, and the problem that the hydrogen production system is numerous and complicated due to a split structure between a reformer and a hydrogen separation device in the conventional hydrogen production system is solved.
The technical scheme adopted by the invention for solving the technical problems is as follows:
a methanol steam reforming and hydrogen separation integrated ultrahigh pressure hydrogen production system comprises a reforming separation device, a three-phase heat exchange device, a steam trap, a water-cooling heat exchanger, a carbon dioxide separation device and a water gas reforming device;
the reforming separation device comprises a methanol steam inlet pipe, a hydrogen outlet pipe and a carbon dioxide mixed residual gas outlet pipe, wherein the carbon dioxide mixed residual gas outlet pipe is sequentially connected with a three-phase heat exchange device, a steam trap, a water-cooling heat exchanger, a carbon dioxide separation device and a water gas reforming device, the water-cooling heat exchanger is connected with a water-cooling tower, and the operating temperature of the water-cooling heat exchanger is less than or equal to 30.8 ℃; the outlet of the water gas reforming device is connected with a reformed mixed gas outlet pipe, and the reformed mixed gas outlet pipe is connected with the inlet of the reforming separation device; the reforming mixed gas outlet pipe is provided with an air pump for increasing the conveying pressure of the reforming mixed gas in the pipe;
the methanol steam inlet pipe and the hydrogen outlet pipe are both connected with the three-phase heat exchange device;
the methanol steam inlet pipe is connected with a liquid pump, and the pump pressure of the liquid pump is 40-100 MPa; and the pure hydrogen in the hydrogen outlet pipe is pumped into a hydrogen storage tank by a liquid pump.
Further, the reforming separation device comprises a reaction cavity, and the reaction cavity comprises a methanol steam inlet and a carbon dioxide mixed residual gas outlet;
catalyst filler is filled in the reaction cavity, methanol steam is input into the reaction cavity from the air inlet to perform catalytic reaction, and mixed gas of hydrogen, carbon dioxide and carbon monoxide is generated;
a hydrogen absorption pipe is inserted into the catalyst filler of the reaction cavity, and the hydrogen absorption pipe is suitable for separating the generated mixed gas of hydrogen, carbon dioxide and carbon monoxide into pure hydrogen and carbon dioxide mixed residual gas; pure hydrogen is output and collected from the outlet of the hydrogen absorption pipe, and carbon dioxide mixed residual gas is output from the outlet of the carbon dioxide mixed residual gas.
Further, the hydrogen absorption pipe is a niobium pipe, the catalyst filler comprises an inner layer catalytic filler and an outer layer catalytic filler, the niobium pipe is inserted into the inner layer catalytic filler, and the inner layer catalytic filler is wrapped by the outer layer catalytic filler;
the inner layer catalytic filler is a copper-based filler, and the outer layer catalytic filler is a zirconium-based filler;
the temperature of the methanol vapor for catalytic reaction is 200-500 ℃, and the temperature of the niobium tube for hydrogen separation is 200-500 ℃.
Further, the hydrogen absorption pipe is a palladium membrane pipe or a palladium alloy membrane pipe, the catalyst filler comprises an inner layer catalytic filler and an outer layer catalytic filler, the palladium membrane pipe or the palladium alloy membrane pipe is inserted into the inner layer catalytic filler, and the inner layer catalytic filler is wrapped by the outer layer catalytic filler;
the inner layer catalytic filler is a copper-based filler, and the outer layer catalytic filler is a zirconium-based filler;
the temperature of the methanol steam for catalytic reaction is 200-500 ℃, and the temperature of the palladium membrane tube or the palladium alloy membrane tube for hydrogen separation is 250-550 ℃.
Furthermore, a heating cavity used for providing working heat for the reaction cavity is arranged outside the reaction cavity, and the heat of the heating cavity is provided by the heat generated by the combustion of the carbon dioxide mixed residual gas.
Further, the pure hydrogen gas outlet pipe is connected with a hydrogen storage tank, the pure hydrogen gas is pumped into the hydrogen storage tank under the pressure of a liquid pump, and the hydrogen storage tank is connected with a hydrogenation machine.
In another aspect, a methanol-water ultrahigh pressure hydrogen production method adopts the ultrahigh pressure hydrogen production system, and comprises the following steps:
s1, feeding methanol water into a methanol steam pipe inlet pipe by a liquid pump, wherein the pump pressure is 40-100 MPa, heating and vaporizing the methanol water to form methanol steam, feeding the methanol steam into a reaction cavity of a reforming and separating device, and decomposing the methanol steam into a 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;
s2, separating the mixed gas of hydrogen, carbon dioxide and carbon monoxide by a hydrogen absorption pipe, outputting the separated pure hydrogen from the hydrogen absorption pipe, and sending the pure hydrogen into a hydrogen storage tank under the pumping pressure of a liquid pump; the residual carbon dioxide mixed residual gas is output from the reaction cavity, the water-cooled heat exchanger controls the temperature of the carbon dioxide mixed residual gas, and then the carbon dioxide mixed residual gas is sent 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 0.3-5% of carbon monoxide;
the pressure of the carbon dioxide mixed residual gas in the carbon dioxide separation device is indirectly controlled by a liquid pump, the pressure is 40-100 MPa, and the operating temperature of the water-cooling heat exchanger is less than or equal to 30.8 ℃;
s3, preparing the carbon dioxide mixed residual gas into liquid carbon dioxide and hydrogen mixed residual gas in a carbon dioxide separator, and outputting and collecting the liquid carbon dioxide;
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, feeding the hydrogen mixed residual gas into a water gas reforming device for reforming, preparing a reformed mixed gas by water distribution, and distributing water according to the content of carbon monoxide, wherein the water distribution ratio (carbon monoxide: water) is 1: 1-20;
the water gas reforming reaction device reforms the fed hydrogen mixed residual gas into 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;
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 feeding the reformed mixed gas together with the mixed gas of hydrogen, carbon dioxide and carbon monoxide into the reaction cavity again for hydrogen separation.
Further, the pure hydrogen of output and carbon dioxide mixed residual gas are all exported after three-phase heat transfer device heat transfer cooling, methanol-water is vaporized into methanol-water vapour through three-phase heat transfer device heat transfer.
Further, the methanol water is replaced by natural gas.
The invention has the beneficial effects that:
the ultrahigh pressure hydrogen production system adopts methanol water as a raw material, the operating pressure of the hydrogen production system is controlled by a liquid pump, hydrogen production is performed under the ultrahigh pressure (40-100 MPa) environment, the operating temperature of carbon dioxide mixed residual gas entering a carbon dioxide separator is controlled by a water-cooling heat exchanger and a water-cooling tower, the temperature is controlled to be less than or equal to 30.8 ℃, and the temperature control of the water-cooling heat exchanger and the water-cooling tower has the advantages of low cost and stable and reliable operation.
The invention has high hydrogen production efficiency, realizes the circular purification of the gas in the system, and can achieve the theoretical yield of 100 percent and the hydrogen yield of more than or equal to 95 percent.
The working method of the methanol-water ultrahigh-pressure hydrogen production system is characterized in that the pressure of methanol water pumped by the liquid pump is controlled at the source of the hydrogen production system to be controlled at ultrahigh pressure (40-100 MPa), the whole hydrogen production system can operate in the ultrahigh-pressure range, the whole hydrogen production system does not need to be provided with equipment such as an air compressor or a compressor for additionally increasing the working pressure of the system, the liquid pump at the inlet can control the working pressure of the whole hydrogen production system, and the pure hydrogen conveying pressure output from the separated pure hydrogen output pipe can be provided by the liquid pump under the ultrahigh-pressure (40-100 MPa) environment, so that the inconvenience of collecting pure hydrogen by arranging the compressor on a pure hydrogen output pipe in the prior art is avoided.
When the liquid carbon dioxide is separated from the carbon dioxide mixed residual gas generated in the hydrogen production system, the operation temperature of the carbon dioxide mixed residual gas entering the carbon dioxide separator is controlled only by the water-cooling heat exchanger and the water-cooling tower, the refrigeration temperature is controlled to be less than or equal to 30.8 ℃ (the temperature is selected to be 30.8 ℃ because of the critical temperature of CO 2), the carbon dioxide component in the separated hydrogen mixed residual gas can reach 20-26%, and the carbon dioxide component in the hydrogen mixed residual gas reaches 20-26% which means that the carbon dioxide component accounts for nearly the carbon dioxide component in the mixed gas of hydrogen, carbon dioxide and carbon monoxide coming out of the reformer, so that one step is met for recycling the mixed residual gas. And finally, reforming the hydrogen mixed residual gas through water gas water distribution, wherein carbon monoxide in the hydrogen mixed residual gas is reduced to 0.5-1.5% from 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 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, and recovers the hydrogen in the carbon dioxide residual gas, so that the theoretical yield of 100 percent can be realized, actually the yield is more than 90-99 percent, and simultaneously the theoretical yield of CO2 is recovered by 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, more CO2 can be recovered, economic benefit can be obtained, safety (high-pressure hydrogen storage is reduced) can be really realized, economy is realized (methanol transportation cost is much lower than that of hydrogen), CO2 is also recovered, zero emission is realized, and ecological benefit is 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.
According to the ultrahigh-pressure hydrogen production system, the reformer and the hydrogen separation device in the traditional hydrogen production system are combined into one device, so that the reforming reaction of methanol steam and the separation reaction of the mixed gas of hydrogen, carbon dioxide and carbon monoxide are carried out in one reaction cavity, the hydrogen production efficiency of the hydrogen production system is improved, the structure of the whole hydrogen production system is optimized and simplified, and the hydrogen production system can be made into small-sized hydrogen production equipment.
Drawings
The invention is further described below with reference to the accompanying drawings.
FIG. 1 is a diagram of an ultrahigh pressure hydrogen production system integrating methanol steam reforming and hydrogen separation according to the present invention;
FIG. 2 is a schematic diagram of a reforming separation apparatus;
the device comprises a liquid pump 1, a three-phase heat exchange device 2, a reforming separation device 3, an inner-layer catalytic filler 31A, an outer-layer catalytic filler 31B, a hydrogen absorption pipe 32, a heating cavity 33, a carbon dioxide separation device 4, a water gas reforming device 5, a water-cooling heat exchanger 6, a water trap 7, a steam trap 8 and an air pump.
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 methanol steam reforming and hydrogen separation integrated ultrahigh pressure hydrogen production system comprises a reforming and separating device 3, a three-phase heat exchange device 2, a steam trap 7, a water-cooled heat exchanger 6, a carbon dioxide separating device 4 and a water gas reforming device 5, wherein the reforming and separating device 3 comprises a methanol steam inlet pipe, a 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 water-cooled heat exchanger 6, the carbon dioxide separating device 4 and the water gas reforming device 5, the water-cooled heat exchanger 6 is connected with a water-cooled tower, and the operating temperature of the water-cooled heat exchanger 6 is 18-; the outlet of the water gas reforming device 5 is connected with a reformed mixed gas outlet pipe, the reformed mixed gas outlet pipe is connected with the inlet of the reforming separation device 3, and an air pump 8 for raising the conveying pressure of the reformed mixed gas in the pipe is arranged on the reformed mixed gas outlet pipe;
the methanol steam inlet pipe and the hydrogen outlet pipe are both connected with the three-phase heat exchange device 2; the methanol vapor advances union coupling liquid pump 1, the pumping pressure of liquid pump 1 is 40 ~ 100MPa, the pure hydrogen in the hydrogen outlet pipe sends into the hydrogen storage tank under the pumping pressure of liquid pump 1.
Specifically, as shown in fig. 2, the reforming separation device 3 includes a reaction chamber, and the reaction chamber includes a methanol steam inlet and a carbon dioxide mixed residual gas outlet;
catalyst filler is filled in the reaction cavity, methanol steam is input into the reaction cavity from a methanol steam inlet to perform catalytic reaction, and mixed gas of hydrogen, carbon dioxide and carbon monoxide is generated;
a hydrogen absorption pipe 32 is inserted into the catalyst packing of the reaction cavity, and the hydrogen absorption pipe 32 is suitable for separating the generated mixed gas of hydrogen, carbon dioxide and carbon monoxide into mixed residual gas of pure hydrogen and carbon dioxide; pure hydrogen is output and collected from the outlet of the hydrogen absorption pipe 32, and carbon dioxide mixed residual gas is output from the outlet of the carbon dioxide mixed residual gas.
Specifically, the hydrogen absorption pipe 32 is a niobium pipe, the catalyst filler includes an inner catalytic filler 31A and an outer catalytic filler 31B, the niobium pipe is inserted into the inner catalytic filler 31A, and the outer catalytic filler 31B wraps the inner catalytic filler 31A;
the inner layer catalytic filler is a copper-based filler, and the outer layer catalytic filler is a zirconium-based filler;
the temperature of the methanol vapor for catalytic reaction is 200-500 ℃, and the temperature of the niobium tube for hydrogen separation is 200-500 ℃.
Or, the hydrogen absorption pipe 32 is a palladium membrane pipe or a palladium alloy membrane pipe, the catalyst filler includes an inner layer catalytic filler 31A and an outer layer catalytic filler 31B, the palladium membrane pipe or the palladium alloy membrane pipe is inserted into the inner layer catalytic filler 31A, and the outer layer catalytic filler 31B wraps the inner layer catalytic filler 31A; the inner layer catalytic filler is a copper-based filler, and the outer layer catalytic filler is a zirconium-based filler; the temperature of the methanol steam for catalytic reaction is 200-500 ℃, and the temperature of the palladium membrane tube or the palladium alloy membrane tube for hydrogen separation is 250-550 ℃.
The function of the niobium tube, the palladium membrane tube or the palladium alloy membrane tube is the same, the mixed gas of hydrogen, carbon dioxide and carbon monoxide generated in the reaction cavity is subjected to hydrogen absorption and separation, pure hydrogen is output and collected, and the residual mixed gas of carbon dioxide is output for recovery operation.
Specifically, a heating cavity 33 for providing working heat to the reaction cavity is arranged outside the reaction cavity, and the heat of the heating cavity 33 is provided by the heat generated by the combustion of the carbon dioxide mixed residual gas. Therefore, the use of other equipment for supplying heat by using the reaction cavity can be reduced, and the cost is reduced.
The pure hydrogen gas outlet pipe is connected with a hydrogen storage tank, the pure hydrogen gas is pumped into the hydrogen storage tank under the pump pressure of a liquid pump, and the hydrogen storage tank is connected with a hydrogenation machine. 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.
During operation, methanol water is vaporized into methanol steam through the three-phase heat exchange device 2, the methanol steam enters the reaction cavity, the heating cavity 33 is heated to control the temperature in the reaction cavity, and the methanol steam carries out catalytic reaction under the corresponding temperature and the catalyst filler, so that the multi-component and multi-reaction gas-solid catalytic reaction system is formed;
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 mixed gas of hydrogen, carbon dioxide and carbon monoxide moves upwards to pass through a hydrogen absorption pipe 32, the hydrogen absorption pipe 32 separates hydrogen in the mixed gas, pure hydrogen is collected into a hydrogen storage tank after being output through the hydrogen absorption pipe 32, the residual carbon dioxide mixed residual gas is output from a carbon dioxide mixed residual gas outlet pipe of a reaction cavity, the carbon dioxide mixed residual gas is cooled through a three-phase heat exchange device 2, moisture in the mixed gas is removed through a steam trap 7, the pressure and the temperature of the mixed gas entering a carbon dioxide separation device 4 are controlled through a liquid pump 1 and a water-cooled heat exchanger 6, then the carbon dioxide mixed residual gas enters the carbon dioxide separation device 4 for liquefaction separation, the separated liquid carbon dioxide is collected, the separated hydrogen mixed residual gas is sent to a water gas reforming device 5, the hydrogen mixed residual gas is changed into reformed mixed gas after being reformed through water gas reforming, and the gas phase component of the reformed mixed gas reacts with the reformed, The component proportion of the mixed gas of carbon dioxide and carbon monoxide is close, therefore, the reformed mixed gas is sent into the reaction cavity to circularly absorb hydrogen, thereby improving the hydrogen yield of the whole ultrahigh pressure hydrogen production system. The delivery of the reformed mixed gas is realized by an air pump 8 provided on the reformed mixed gas outlet pipe.
According to the ultrahigh-pressure hydrogen production system, the reformer and the hydrogen separation device in the traditional hydrogen production system are combined into one device, so that the reforming reaction of methanol steam and the separation reaction of the mixed gas of hydrogen, carbon dioxide and carbon monoxide are carried out in one reaction cavity, the hydrogen production efficiency of the hydrogen production system is improved, the structure of the whole hydrogen production system is optimized and simplified, and the hydrogen production system can be made into small-sized hydrogen production equipment.
The working method of the methanol-water ultrahigh-pressure hydrogen production system is characterized in that the pressure of methanol water pumped by the liquid pump is controlled at the source of the hydrogen production system to be controlled at ultrahigh pressure (40-100 MPa), the whole hydrogen production system can operate in the ultrahigh-pressure range, the whole hydrogen production system does not need to be provided with equipment such as an air compressor or a compressor for additionally increasing the working pressure of the system, the liquid pump at the inlet can control the working pressure of the whole hydrogen production system, and the pure hydrogen conveying pressure output from the separated pure hydrogen output pipe can be provided by the liquid pump under the ultrahigh-pressure (40-100 MPa) environment, so that the inconvenience of collecting pure hydrogen by arranging the compressor on a pure hydrogen output pipe in the prior art is avoided.
In the hydrogen production system, a high-pressure reforming reaction environment is provided by the liquid pump 1, the pressure provided by the liquid pump 1 is 40-100 MPa, so that when the whole hydrogen production system is used for treating the carbon dioxide mixed residual gas, only the water-cooling heat exchanger 6 is needed to be configured to control the temperature of the carbon dioxide mixed residual gas in the carbon dioxide liquefying device to be less than or equal to 30.8 ℃, and the pressure of the carbon dioxide mixed residual gas in the carbon dioxide liquefying device is directly controlled by the liquid pump 1 from the source, so that an air compressor (an air compressor is needed to be separately configured for low-pressure hydrogen production to provide the pressure for liquefying work for the carbon dioxide mixed residual gas) can be omitted in the ultrahigh-pressure hydrogen production system compared with the low-pressure hydrogen production; compared with an ultrahigh pressure hydrogen production system, the traditional refrigerator can be changed into the existing water-cooled heat exchanger 6 for temperature control, the operation temperature of the carbon dioxide mixed residual gas entering the carbon dioxide separator is controlled by the water-cooled heat exchanger 6 and the water-cooled tower, the temperature is controlled to be 18-30.8 ℃, and the water-cooled heat exchanger 6 and the water-cooled tower control the temperature, so that the system has the advantages of low cost and stable and reliable operation, and is suitable for being installed in the region with the outdoor temperature of less than or equal to 30.8 ℃ throughout the year.
The output carbon dioxide mixed residual gas is provided with working pressure and temperature in a carbon dioxide liquefying device through a liquid pump 1 and a refrigerating machine, so that hydrogen mixed residual gas with a preset molar ratio is separated from the carbon dioxide mixed residual gas, and then the hydrogen mixed residual gas is prepared into reformed mixed gas through a water gas reforming device 5.
Example two
The ultrahigh-pressure hydrogen production system adopting the methanol-water ultrahigh-pressure hydrogen production system comprises the following steps:
s1, the liquid pump 1 sends the methanol water into a methanol steam pipe inlet pipe, the pump pressure is 40-100 MPa, the methanol water is heated and vaporized by a three-phase heat exchange device 2 to become methanol steam, the methanol steam enters a reaction cavity of a reforming separation device 3, and the methanol steam is decomposed into 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;
s2, separating the mixed gas of hydrogen, carbon dioxide and carbon monoxide by the hydrogen absorption pipe 32, collecting the separated pure hydrogen from the output of the hydrogen absorption pipe 32, and sending the pure hydrogen into a hydrogen storage tank under the pumping pressure of a liquid pump; outputting the residual carbon dioxide mixed residual gas from the reaction cavity, wherein 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;
controlling the pressure of the carbon dioxide mixed residual gas by a liquid pump 1 at the source, controlling the temperature of the carbon dioxide mixed residual gas by a water-cooling heat exchanger 6, wherein the pressure provided by the liquid pump 1 is 40-100 MPa, and the temperature controlled by the water-cooling heat exchanger 6 is less than or equal to 30.8 ℃; then sending the carbon dioxide mixed residual gas into a carbon dioxide separation device 4 for carbon dioxide liquefaction and separation;
s3, preparing the carbon dioxide mixed residual gas into liquid carbon dioxide and hydrogen mixed residual gas in a carbon dioxide separator, and outputting and collecting the liquid carbon dioxide; the components of the hydrogen mixed residual gas comprise 65-75% of hydrogen, 20-26% of carbon dioxide and 3-9% of carbon monoxide;
the molar ratio of carbon dioxide in the gaseous phase component of the hydrogen mixed residual gas is controlled to be 20-26%, the working pressure of the carbon dioxide liquefying device is 40-100 MPa, and the temperature is less than or equal to 30.8 ℃.
S4, feeding the hydrogen mixed residual gas into a water gas reforming device 5 for reforming, preparing a reformed mixed gas by water distribution, and distributing water according to the content of carbon monoxide, wherein the water distribution ratio (carbon monoxide: water) is 1: 1-20;
the water gas reforming reaction device reforms the fed hydrogen mixed residual gas into 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;
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, feeding the reformed mixed gas into the reaction cavity to be mixed with the mixed gas of hydrogen, carbon dioxide and carbon monoxide, and feeding the reformed mixed gas together with the mixed gas of hydrogen, carbon dioxide and carbon monoxide into the reaction cavity again to separate hydrogen.
Specifically, the mixed residual gas of pure hydrogen and carbon dioxide of output all exports after 2 heat transfer cooling of three-phase heat transfer device, the methanol-water vaporizes into methanol-water vapour through 2 heat transfer of three-phase heat transfer device.
In this embodiment, the methanol-water may be replaced by natural gas, and hydrogen is produced from natural gas to obtain a mixed gas of hydrogen, carbon dioxide and carbon monoxide.
The ultrahigh-pressure hydrogen production method is based on the methanol-water ultrahigh-pressure hydrogen production system in the first embodiment, methanol water is used as a hydrogen production raw material, ultrahigh pressure (40-100 MPa) is provided at the source of a liquid pump 1, the methanol water is pumped into a reaction cavity, methanol water vapor after the methanol water is vaporized reacts in the reaction cavity to generate a mixed gas of hydrogen, carbon dioxide and carbon monoxide, then the mixed gas of the hydrogen, the carbon dioxide and the carbon monoxide directly reacts with a hydrogen absorption pipe 32 in the reaction cavity to absorb hydrogen, pure hydrogen can be directly output and collected, and the pure hydrogen conveying pressure output from a separated pure hydrogen output pipe can be provided by the liquid pump under the ultrahigh-pressure (40-100 MPa) environment, so that the inconvenience that a compressor is required to be arranged on a pure hydrogen output pipe to collect the pure hydrogen in the past is eliminated.
For the transportation of the generated carbon dioxide mixed residual gas, the temperature is controlled by a water-cooled heat exchanger 6, the pressure of the carbon dioxide mixed residual gas is indirectly controlled by a liquid pump 1, the pressure (40-100 MPa) and the temperature (less than or equal to 30.8 ℃) of the carbon dioxide mixed residual gas in a carbon dioxide separation device 4 are controlled, the carbon dioxide in the carbon dioxide mixed residual gas is liquefied and separated, the components of the separated hydrogen mixed residual gas are controlled, 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 the 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 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 component 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%, and the hydrogen yield is more than 95-99%.
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 (6)
1. A methanol steam reforming and hydrogen separation integrated ultrahigh pressure hydrogen production system is characterized by comprising a reforming and separating device, a three-phase heat exchange device, a steam trap, a water-cooled heat exchanger, a carbon dioxide separating device and a water gas reforming device;
the reforming separation device comprises a methanol steam inlet pipe, a hydrogen outlet pipe and a carbon dioxide mixed residual gas outlet pipe, wherein the carbon dioxide mixed residual gas outlet pipe is sequentially connected with a three-phase heat exchange device, a steam trap, a water-cooling heat exchanger, a carbon dioxide separation device and a water gas reforming device, the water-cooling heat exchanger is connected with a water-cooling tower, and the operating temperature of the water-cooling heat exchanger is less than or equal to 30.8 ℃; the outlet of the water gas reforming device is connected with a reformed mixed gas outlet pipe, and the reformed mixed gas outlet pipe is connected with the inlet of the reforming separation device; the reforming mixed gas outlet pipe is provided with an air pump for increasing the conveying pressure of the reforming mixed gas in the pipe;
the methanol steam inlet pipe and the hydrogen outlet pipe are both connected with the three-phase heat exchange device;
the methanol steam inlet pipe is connected with a liquid pump, and the pump pressure of the liquid pump is 40-100 MPa; and the pure hydrogen in the hydrogen outlet pipe is pumped into a hydrogen storage tank by a liquid pump.
2. The methanol steam reforming and hydrogen separation integrated ultrahigh pressure hydrogen production system according to claim 1, wherein the reforming and separating device comprises a reaction chamber, and the reaction chamber comprises a methanol steam inlet and a carbon dioxide mixed residual gas outlet;
catalyst filler is filled in the reaction cavity, methanol steam is input into the reaction cavity from the air inlet to perform catalytic reaction, and mixed gas of hydrogen, carbon dioxide and carbon monoxide is generated;
a hydrogen absorption pipe is inserted into the catalyst filler of the reaction cavity, and the hydrogen absorption pipe is suitable for separating the generated mixed gas of hydrogen, carbon dioxide and carbon monoxide into pure hydrogen and carbon dioxide mixed residual gas; pure hydrogen is output and collected from the outlet of the hydrogen absorption pipe, and carbon dioxide mixed residual gas is output from the outlet of the carbon dioxide mixed residual gas.
3. The methanol steam reforming and hydrogen separation integrated ultrahigh-pressure hydrogen production system according to claim 2, wherein the hydrogen absorption pipe is a niobium pipe, the catalyst filler comprises an inner layer catalytic filler and an outer layer catalytic filler, the niobium pipe is inserted into the inner layer catalytic filler, and the outer layer catalytic filler wraps the inner layer catalytic filler;
the inner layer catalytic filler is a copper-based filler, and the outer layer catalytic filler is a zirconium-based filler;
the temperature of the methanol vapor for catalytic reaction is 200-500 ℃, and the temperature of the niobium tube for hydrogen separation is 200-500 ℃.
4. The methanol steam reforming and hydrogen separation integrated ultrahigh pressure hydrogen production system according to claim 2, wherein the hydrogen absorption pipe is a palladium membrane pipe or a palladium alloy membrane pipe, the catalyst filler comprises an inner layer catalytic filler and an outer layer catalytic filler, the palladium membrane pipe or the palladium alloy membrane pipe is inserted into the inner layer catalytic filler, and the outer layer catalytic filler wraps the inner layer catalytic filler;
the inner layer catalytic filler is a copper-based filler, and the outer layer catalytic filler is a zirconium-based filler;
the temperature of the methanol steam for catalytic reaction is 200-500 ℃, and the temperature of the palladium membrane tube or the palladium alloy membrane tube for hydrogen separation is 250-550 ℃.
5. The methanol steam reforming and hydrogen separation integrated ultrahigh pressure hydrogen production system according to claim 2, wherein a heating chamber for providing working heat to the reaction chamber is arranged outside the reaction chamber, and the heat of the heating chamber is provided by heat generated by combustion of carbon dioxide mixed residual gas.
6. The methanol steam reforming and hydrogen separation integrated ultrahigh pressure hydrogen production system according to claim 1, wherein the pure hydrogen gas outlet pipe is connected with a hydrogen storage tank, the pure hydrogen gas is fed into the hydrogen storage tank under the pump pressure of a liquid pump, and the hydrogen storage tank is connected with a hydrogenation machine.
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