CN110817800B - Methanol steam reforming and hydrogen separation integrated ultrahigh pressure hydrogen production system and method thereof - Google Patents
Methanol steam reforming and hydrogen separation integrated ultrahigh pressure hydrogen production system and method thereof Download PDFInfo
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Abstract
The invention relates to a methanol steam reforming and hydrogen separation integrated ultrahigh pressure hydrogen system, which comprises a reforming and separating device, a three-phase heat exchange device, a steam trap, a water-cooling heat exchanger, a carbon dioxide separating device and a water gas reforming device; the operation 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 fed into the hydrogen storage tank under the pumping pressure of the liquid pump. A method for preparing hydrogen from methanol water by ultrahigh pressure includes feeding methanol water into inlet pipe of methanol water vapor pipe by liquid pump under 40-100 MPa, separating into pure hydrogen and mixed gas in reaction chamber of reforming separator, feeding pure hydrogen into hydrogen storage tank under pump pressure of liquid pump, reforming residual gas to obtain reformed mixed gas, and feeding reformed mixed gas into reaction chamber again for separating hydrogen. 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 an integrated ultrahigh pressure hydrogen production system and method by methanol steam reforming and hydrogen separation.
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 defect of the prior art is overcome, an integrated ultrahigh pressure hydrogen production system integrating methanol steam reforming and hydrogen separation is provided, and the problem that the hydrogen production system is complicated due to a split structure between a reformer and a hydrogen separation device in the existing hydrogen production system is solved;
meanwhile, the ultrahigh-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 methanol steam reforming and hydrogen separation integrated ultrahigh pressure hydrogen system comprises a reforming and separating device, a three-phase heat exchange device, a steam trap, a water-cooling 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 operation 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 reforming mixed gas outlet pipe, and the reforming mixed gas outlet pipe is connected with the inlet of the reforming separation device; an air pump for raising the conveying pressure of the reformed mixed gas in the pipe is arranged on the reformed mixed gas outlet pipe;
the methanol water vapor inlet pipe and the hydrogen outlet pipe are connected with the 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 40-100 MPa; pure hydrogen in the hydrogen outlet pipe is sent into a hydrogen storage tank under the pumping pressure of a liquid pump.
Further, the reforming separation device comprises a reaction cavity, and the reactor comprises a methanol vapor inlet and a carbon dioxide mixed residual gas outlet;
the reaction cavity is filled with catalyst filler, and methanol vapor is input into the reaction cavity from the air inlet to perform catalytic reaction to generate mixed gas of hydrogen, carbon dioxide and carbon monoxide;
a hydrogen absorption pipe is inserted into the catalyst filler of the reaction cavity, and is suitable for separating 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, and carbon dioxide mixed residual gas is output from the outlet of the carbon dioxide mixed residual gas.
Further, the hydrogen absorption tube is a niobium tube, the catalyst filler comprises an inner catalytic filler and an outer catalytic filler, the niobium tube is inserted into the inner catalytic filler, and the outer catalytic filler wraps the inner catalytic filler;
the inner layer filler is copper-based filler, and the outer layer filler is zirconium-based filler;
the temperature of the catalytic reaction of the methanol vapor is 200-500 ℃, and the temperature of the niobium pipe for separating hydrogen is 200-500 ℃.
Further, the hydrogen absorption tube is a palladium membrane tube or a palladium alloy membrane tube, the catalyst filler comprises an inner catalytic filler and an outer catalytic filler, the niobium tube is inserted into the inner catalytic filler, and the outer catalytic filler wraps the inner catalytic filler;
the inner layer filler is copper-based filler, and the outer layer filler is zirconium-based filler;
the temperature of the catalytic reaction of the methanol vapor is 200-500 ℃, and the temperature of the palladium membrane tube or the palladium alloy membrane tube for separating hydrogen is 250-550 ℃.
Further, a heating cavity 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 burning the carbon dioxide mixed residual gas.
Furthermore, the pure hydrogen outlet pipe is connected with the hydrogen storage tank, pure hydrogen is sent into the hydrogen storage tank under the pumping pressure of the liquid pump, and the hydrogen storage tank is connected with the hydrogenation machine.
In yet another aspect, a method for ultrahigh pressure hydrogen production from methanol water, which adopts the ultrahigh 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 40-100 MPa, heating and vaporizing the methanol water into methanol water vapor, and then feeding the methanol water vapor into a reaction cavity of a reforming and separating device, and decomposing the methanol water vapor into mixed gas of hydrogen, carbon dioxide and carbon monoxide;
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 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; outputting the residual carbon dioxide mixed residual gas from the reaction cavity, controlling the temperature of the carbon dioxide mixed residual gas by a water-cooling heat exchanger, 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 0.3-5% 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 operation temperature of the water-cooling heat exchanger is less than or equal to 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, feeding the hydrogen mixed residual gas into a water gas reforming device for reforming, and preparing reformed mixed gas by 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 reforming mixed gas by distributing water, and the gas phase components of the reforming mixed gas comprise 62-77% of hydrogen, 22-27% of carbon dioxide and 0.5-1.5% of carbon monoxide;
the ratio of the hydrogen, the carbon dioxide and the carbon monoxide in the reforming mixed gas is close to the ratio of the hydrogen, the carbon dioxide and the carbon monoxide in the mixed gas of the hydrogen, the carbon dioxide and the carbon monoxide;
s5, mixing the reforming mixed gas with the mixed gas of the hydrogen, the carbon dioxide and the carbon monoxide, and sending the reforming mixed gas into the reaction cavity again along with the mixed gas of the hydrogen, the carbon dioxide and the carbon monoxide to separate the hydrogen.
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 ultrahigh pressure hydrogen production system adopts methanol water as raw material, the operation pressure of the hydrogen production system is controlled by the liquid pump, hydrogen production is controlled under the ultrahigh pressure (40-100 MPa) environment, and the operation temperature of carbon dioxide mixed residual gas entering the carbon dioxide separator is controlled by the water cooling heat exchanger and the water cooling tower, and the temperature is controlled to be less than or equal to 30.8 ℃, so that the water cooling heat exchanger and the water cooling tower have 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, has the theoretical yield reaching 100 percent and realizes the hydrogen yield 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 the methanol water pumped by the liquid pump is controlled to be in an ultrahigh pressure (40-100 MPa) at the source of the hydrogen production system, the whole hydrogen production can be operated 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 working pressure of the whole hydrogen production system can be controlled by the liquid pump at the inlet, and the pure hydrogen conveying pressure output in the separated pure hydrogen output pipe can be provided by the liquid pump in the ultrahigh pressure (40-100 MPa) environment, so that the inconvenience that the pure hydrogen is required to be collected by the compressor on the pure hydrogen output pipe in the past 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 by a water-cooling heat exchanger and a 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 ratio of the carbon dioxide component in the mixed gas of hydrogen, carbon dioxide and carbon monoxide coming out of the reformer is close, and one step is satisfied for recycling the mixed residual gas. 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 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 equivalent to the mixed gas component of the hydrogen, the carbon dioxide and the carbon monoxide prepared by the reformer, so that the two components can be mixed and enter the membrane separation and purification device again to carry out hydrogen purification and separation hydrogen production operation, the gas in the system is circularly purified, the theoretical yield can reach 100%, and the hydrogen yield is more than or equal to 95%.
Meanwhile, the hydrogen in the residual carbon dioxide gas is recovered because the hydrogen is aimed at a direct consumption customer, and the selling price is saved compared with the factory hydrogen, so that the theoretical 100% yield can be realized, the actual yield is more than 90-99%, and the theoretical yield of CO2 is recovered at the same time, and the actual yield is 90-99%. The process is combined with the hydrogenation station, so that high yield of hydrogen can be realized, CO2 is more recovered, economic benefit is obtained, safety (reduction of high-pressure hydrogen storage) is truly realized, economy is realized (because the transport cost of methanol 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 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.
The ultrahigh pressure hydrogen production system combines the reformer and the hydrogen separation device in the traditional hydrogen production system into one device, so that the reforming reaction of methanol vapor 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, and the whole hydrogen production system structure is optimized and simplified, thereby being capable of being made into small-sized hydrogen production equipment by means of the hydrogen production system.
Drawings
The invention is further described below with reference to the accompanying drawings.
FIG. 1 is a diagram of an integrated ultrahigh pressure hydrogen production system for reforming methanol and steam and separating hydrogen according to the present invention;
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 31A, an inner catalytic filler, a 31B, an outer catalytic filler, a 32, a hydrogen absorption pipe 33, a heating cavity 4, a carbon dioxide separation device 5, a water gas reforming device 6, a water-cooled heat exchanger 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 views illustrating the basic structure of the present invention by way of illustration only, and thus show only the constitution related to the present invention.
Example 1
As shown in fig. 1, the integrated ultrahigh pressure hydrogen system for reforming methanol and separating hydrogen comprises a reforming separation device 3, a three-phase heat exchange device 2, a steam trap 7, a water-cooling heat exchanger 6, a carbon dioxide separation device 4 and a water gas reforming device 5, wherein the reforming separation device 3 comprises a methanol and 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-cooling heat exchanger 6, the carbon dioxide separation device 4 and the water gas reforming device 5, the water-cooling heat exchanger 6 is connected with a water-cooling tower, and the operation temperature of the water-cooling heat exchanger 6 is 18-30.8 ℃; the outlet of the water gas reforming device 5 is connected with a reforming mixed gas outlet pipe, the reforming mixed gas outlet pipe is connected with the inlet of the reforming separation device 3, and an air pump 8 for lifting the conveying pressure of the reforming mixed gas in the pipe is arranged on the reforming mixed gas outlet pipe;
the methanol water vapor inlet pipe and the hydrogen outlet pipe are connected with the three-phase heat exchange device 2; the methanol vapor inlet pipe is connected with the liquid pump 1, the pumping pressure of the liquid pump 1 is 40-100 MPa, and pure hydrogen in the hydrogen outlet pipe is sent into the hydrogen storage tank under the pumping pressure of the liquid pump 1.
Specifically, as shown in fig. 2, the reforming separation device 3 comprises a reaction cavity, and the reactor comprises a methanol vapor inlet and a carbon dioxide mixed residual gas outlet;
the reaction cavity is filled with catalyst filler, and methanol vapor is input into the reaction cavity from a methanol vapor inlet for catalytic reaction to generate mixed gas of hydrogen, carbon dioxide and carbon monoxide;
a hydrogen absorption pipe 32 is inserted into the catalyst filler 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 pure hydrogen and carbon dioxide mixed residual gas; 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 tube 32 is a niobium tube, the catalyst filler includes an inner catalytic filler 31A and an outer catalytic filler 31B, the niobium tube is inserted into the inner catalytic filler 31A, and the outer catalytic filler 31B wraps the inner catalytic filler 31A;
the inner layer filler is copper-based filler, and the outer layer filler is zirconium-based filler;
the temperature of the catalytic reaction of the methanol vapor is 200-500 ℃, and the temperature of the niobium pipe for separating hydrogen is 200-500 ℃.
Or, the hydrogen absorption tube 32 is a palladium membrane tube or a palladium alloy membrane tube, the catalyst filler comprises an inner catalytic filler 31A and an outer catalytic filler 31B, the niobium tube is inserted into the inner catalytic filler 31A, and the outer catalytic filler 31B wraps the inner catalytic filler 31A; the inner layer filler is copper-based filler, and the outer layer filler is zirconium-based filler; the temperature of the catalytic reaction of the methanol vapor is 200-500 ℃, and the temperature of the palladium membrane tube or the palladium alloy membrane tube for separating hydrogen 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.
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 reaction cavity for other equipment to supply heat can be reduced, and the cost is reduced.
The pure hydrogen outlet pipe is connected with the hydrogen storage tank, pure hydrogen is sent into the hydrogen storage tank under the pumping pressure of the liquid pump, 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, the methanol water is vaporized into methanol water vapor through the three-phase heat exchange device 2, the methanol water vapor enters the reaction cavity, the heating cavity 33 is heated to control the temperature in the reaction cavity, and the methanol water vapor is subjected to catalytic reaction under the corresponding temperature and the catalyst filler, so that the catalyst is a multi-component and multi-reaction gas-solid catalytic reaction system;
the reaction equation is:
CH 3 OH→CO+2H 2 the method comprises the steps of carrying out a first treatment on the surface of the (reversible reaction)
H 2 O+CO→CO 2 +H 2 The method comprises the steps of carrying out a first treatment on the surface of the (reversible reaction)
CH 3 OH+H 2 O→CO 2 +3H 2 The method comprises the steps of carrying out a first treatment on the surface of the (reversible reaction)
2CH 3 OH→CH 3 OCH 3 +H 2 O; (side reaction)
CO+3H 2 →CH 4 +H 2 O; (side reaction)
The reforming reaction produces a mixed gas of hydrogen, carbon dioxide and carbon monoxide. The mixed gas of hydrogen, carbon dioxide and carbon monoxide moves upwards to pass through the hydrogen absorption pipe 32, the hydrogen in the mixed gas is separated by the hydrogen absorption pipe 32, pure hydrogen is collected into the 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 the reaction cavity, the carbon dioxide mixed residual gas is cooled by the three-phase heat exchange device 2, moisture in the mixed gas is removed by the steam trap 7, the pressure and the temperature of the mixed gas enter the carbon dioxide separation device 4 are controlled by the liquid pump 1 and the water-cooling heat exchanger 6, then the carbon dioxide mixed residual gas enters the carbon dioxide separation device 4 for liquefaction and separation, the separated liquid carbon dioxide is collected, the separated hydrogen mixed residual gas is sent into the water gas reforming device 5, the hydrogen mixed residual gas is converted into reformed mixed gas after being reformed by the water gas, the gas phase component of the reformed mixed gas is close to the mixed gas component proportion of the hydrogen, the carbon dioxide and the carbon monoxide generated by the reforming reaction, and therefore, the reformed mixed gas is sent into the hydrogen through the circulation absorption in the reaction cavity, and the hydrogen yield of the whole ultrahigh-pressure hydrogen system is improved. The delivery of the reformed mixture is achieved by an air pump 8 provided at the reformed mixture outlet pipe.
The ultrahigh pressure hydrogen production system combines the reformer and the hydrogen separation device in the traditional hydrogen production system into one device, so that the reforming reaction of methanol vapor 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, and the whole hydrogen production system structure is optimized and simplified, thereby being capable of being made into small-sized hydrogen production equipment by means of the hydrogen production system.
The working method of the methanol-water ultrahigh pressure hydrogen production system is characterized in that the pressure of the methanol water pumped by the liquid pump is controlled to be in an ultrahigh pressure (40-100 MPa) at the source of the hydrogen production system, the whole hydrogen production can be operated 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 working pressure of the whole hydrogen production system can be controlled by the liquid pump at the inlet, and the pure hydrogen conveying pressure output in the separated pure hydrogen output pipe can be provided by the liquid pump in the ultrahigh pressure (40-100 MPa) environment, so that the inconvenience that the pure hydrogen is required to be collected by the compressor on the pure hydrogen output pipe in the past 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 aims at treating carbon dioxide mixed residual gas, only one water-cooling heat exchanger 6 is needed to control the temperature of the carbon dioxide mixed residual gas in a carbon dioxide liquefying device to be less than or equal to 30.8 ℃, the pressure of the carbon dioxide mixed residual gas in the carbon dioxide liquefying device is directly controlled from the source by the liquid pump 1, an air compressor (the air compressor is needed to be independently configured for providing liquefying pressure for the carbon dioxide mixed residual gas for low-pressure hydrogen) can be omitted from the ultrahigh-pressure hydrogen production system, and the ultrahigh-pressure hydrogen production system is simplified and optimized; compared with an ultrahigh-pressure hydrogen production system, the temperature control can be performed by changing a traditional refrigerator into the existing water-cooling heat exchanger 6, the operation temperature of the carbon dioxide mixed residual gas entering the carbon dioxide separator is controlled by the water-cooling heat exchanger 6 and the water-cooling tower, the temperature is controlled to be 18-30.8 ℃, the water-cooling heat exchanger 6 and the water-cooling tower have the advantages of low cost and stable and reliable operation, and the hydrogen production system is suitable for being installed in regions with 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 refrigerator, 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 5.
Example two
The ultrahigh pressure hydrogen production system for methanol water adopts the ultrahigh 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 40-100 MPa, heating and vaporizing the methanol water through a three-phase heat exchange device 2 to form methanol water vapor, and then feeding the methanol water vapor into a reaction cavity of a reforming separation device 3, wherein the methanol water vapor is decomposed into mixed gas of hydrogen, carbon dioxide and carbon monoxide;
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 mixed gas of hydrogen, carbon dioxide and carbon monoxide by the hydrogen absorption pipe 32, outputting the separated pure hydrogen from the hydrogen absorption pipe 32, and sending the pure hydrogen into a hydrogen storage tank under the pump 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;
the pressure of the carbon dioxide mixed residual gas is controlled by a source liquid pump 1, the temperature of the carbon dioxide mixed residual gas is controlled by a water-cooling heat exchanger 6, 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 delivering the carbon dioxide mixed residual gas into a carbon dioxide separation device 4 for carbon dioxide liquefaction and separation;
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%, the pressure of the carbon dioxide liquefying device is 40-100 MPa when the device works, 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, and preparing reformed mixed gas by water distribution, wherein the water distribution is carried out according to the content of carbon monoxide, and the water distribution ratio (carbon monoxide: water) is 1:1-20;
the water gas reforming reaction device reforms the fed hydrogen mixed residual gas into reforming mixed gas by distributing water, and the gas phase components of the reforming mixed gas comprise 62-77% of hydrogen, 22-27% of carbon dioxide and 0.5-1.5% of carbon monoxide;
the 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, sending the reforming mixed gas into the reaction cavity to be mixed with the mixed gas of the hydrogen, the carbon dioxide and the carbon monoxide, and sending the reforming mixed gas into the reaction cavity again along with the mixed gas of the hydrogen, the carbon dioxide and the carbon monoxide to separate the hydrogen.
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 ultrahigh-pressure hydrogen production method, by means of the ultrahigh-pressure hydrogen production system of the methanol water in the first embodiment, the methanol water is used as a hydrogen production raw material, the liquid pump 1 provides ultrahigh pressure (40-100 MPa) at the source to pump the methanol water into the reaction cavity, the methanol water vapor after the vaporization of the methanol water reacts in the reaction cavity to generate 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 the hydrogen absorption pipe 32 in the reaction cavity to absorb hydrogen, pure hydrogen can be directly output and collected, and under the ultrahigh pressure (40-100 MPa) environment, the pure hydrogen conveying pressure output in the separated pure hydrogen output pipe can also be provided by the liquid pump, so that the inconvenience that a compressor is required to be arranged on the pure hydrogen output pipe to collect pure hydrogen in the past is avoided.
For the transportation of the generated carbon dioxide mixed residual gas, the temperature is controlled by a water-cooling heat exchanger 6, the pressure 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 by a liquid pump 1, 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 carbon dioxide molar ratio in the hydrogen mixed residual gas is lower than 26%, and the hydrogen mixed residual gas is prepared as a reforming mixed gas of a subsequent step; and finally, the hydrogen mixed residual gas is reformed by water gas distribution, so that the carbon monoxide in the hydrogen mixed residual gas is reduced to 0.5-1.5% from original 3-9%, and the gas phase components of the reformed mixed gas are as follows: 62-77% of hydrogen, 22-27% of carbon dioxide and 0.5-1.5% of carbon monoxide; the gas phase component of the reforming mixed gas is 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 membrane separation and purification device again to carry out hydrogen purification and separation hydrogen production operation, the gas in the system is circularly purified, the theoretical yield can reach 100%, and the hydrogen yield is more than 95-99%.
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 (6)
1. The integrated ultrahigh pressure hydrogen system for reforming methanol and separating water vapor and hydrogen is characterized by comprising a reforming and separating device, a three-phase heat exchange device, a steam trap, a water-cooling 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 operation 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 reforming mixed gas outlet pipe, and the reforming mixed gas outlet pipe is connected with the inlet of the reforming separation device; an air pump for raising the conveying pressure of the reformed mixed gas in the pipe is arranged on the reformed mixed gas outlet pipe;
the methanol water vapor inlet pipe and the hydrogen outlet pipe are connected with the 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 40-100 MPa; pure hydrogen in the hydrogen outlet pipe is sent into a hydrogen storage tank under the pumping pressure of a liquid pump;
the reforming separation device comprises a reaction cavity, wherein the reaction cavity comprises a methanol vapor inlet and a carbon dioxide mixed residual gas outlet;
the reaction cavity is filled with catalyst filler, and methanol vapor is input into the reaction cavity from the air inlet to perform catalytic reaction to generate mixed gas of hydrogen, carbon dioxide and carbon monoxide;
a hydrogen absorption pipe is inserted into the catalyst filler of the reaction cavity, and is suitable for separating 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 an outlet of the hydrogen absorption pipe, and carbon dioxide mixed residual gas is output from an outlet of the carbon dioxide mixed residual gas;
the hydrogen absorption pipe is a niobium pipe, the catalyst filler comprises an inner catalytic filler and an outer catalytic filler, the niobium pipe is inserted into the inner catalytic filler, and the outer catalytic filler wraps the inner catalytic filler;
the inner catalytic filler is copper-based filler, and the outer catalytic filler is zirconium-based filler;
the temperature of the catalytic reaction of the methanol vapor is 200-500 ℃, and the temperature of the niobium pipe for separating hydrogen is 200-500 ℃.
2. The integrated ultrahigh pressure hydrogen system for reforming methanol and separating hydrogen as recited in claim 1, wherein the hydrogen absorption tube is replaced by a palladium membrane tube or a palladium alloy membrane tube,
the temperature of the palladium membrane tube or the palladium alloy membrane tube for separating hydrogen is 250-550 ℃.
3. The ultra-high pressure hydrogen system of claim 1, wherein a heating chamber is arranged outside the reaction chamber for providing working heat to the reaction chamber, and the heat of the heating chamber is provided by the heat generated by the combustion of the carbon dioxide mixed residual gas.
4. The ultra-high pressure hydrogen system integrated with steam reforming and hydrogen separation of methanol as set forth in claim 1, wherein the pure hydrogen outlet pipe is connected to a hydrogen storage tank, pure hydrogen is fed into the hydrogen storage tank under the pumping pressure of a liquid pump, and the hydrogen storage tank is connected to a hydrogenation machine.
5. A method for ultrahigh pressure hydrogen production from methanol water, characterized in that the method adopts the integrated ultrahigh pressure hydrogen production system for reforming methanol water vapor and separating hydrogen according to any one of the claims 1-4, and 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 40-100 MPa, heating and vaporizing the methanol water into methanol water vapor, and then enabling the methanol water vapor to enter a reaction cavity of a reforming and separating device, and decomposing the methanol water vapor into mixed gas of hydrogen, carbon dioxide and carbon monoxide;
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, separating the mixed gas of the hydrogen, the carbon dioxide and the carbon monoxide by the 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; outputting the residual carbon dioxide mixed residual gas from the reaction cavity, controlling the temperature of the carbon dioxide mixed residual gas by a water-cooling heat exchanger, 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 0.3-5% of carbon monoxide, and the sum of the components is 100%;
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 operation temperature of the water-cooling heat exchanger is less than or equal to 30.8 ℃;
s3, preparing liquid carbon dioxide and hydrogen mixed residual gas from the carbon dioxide mixed residual gas in a carbon dioxide separator, 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, feeding the hydrogen mixed residual gas into a water gas reforming device for reforming, preparing reformed mixed gas by water distribution, and carrying out water distribution according to the content of carbon monoxide, wherein the carbon monoxide is in a water distribution ratio: water is 1:1-20;
the water gas reforming reaction device reforms the fed hydrogen mixed residual gas into reforming mixed gas by distributing water, 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, mixing the reforming mixed gas with the mixed gas of the hydrogen, the carbon dioxide and the carbon monoxide, and sending the reforming mixed gas into the reaction cavity again along with the mixed gas of the hydrogen, the carbon dioxide and the carbon monoxide for separating the hydrogen.
6. The ultrahigh-pressure hydrogen production method of methanol water according to claim 5, wherein the output pure hydrogen and carbon dioxide mixed residual gas are output after 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.
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