CN212559453U - High-pressure hydrogen production system by using methanol water - Google Patents
High-pressure hydrogen production system by using methanol water Download PDFInfo
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- CN212559453U CN212559453U CN201921826131.XU CN201921826131U CN212559453U CN 212559453 U CN212559453 U CN 212559453U CN 201921826131 U CN201921826131 U CN 201921826131U CN 212559453 U CN212559453 U CN 212559453U
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Abstract
The utility model relates to a methanol water high-pressure hydrogen production system, which comprises a reformer, a hydrogen separation device and a carbon dioxide separator; the conveying pressure of the methanol steam in the methanol steam pipe is 18-50 MPa; and a water-cooling heat exchanger is arranged on the carbon dioxide mixed residual gas output pipe, and the operating temperature of the refrigerator is 18-30.8 ℃. 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 utility model relates to a methanol-water high 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.
SUMMERY OF THE UTILITY MODEL
The to-be-solved technical problem of the utility model is: the defects of the prior art are overcome, the methanol water high-pressure hydrogen production system is provided, and the problems of high potential safety hazard and long-distance high-cost hydrogen transportation caused by the fact that a large amount of hydrogen needs to be stored in the existing hydrogen adding station are solved.
The utility model provides a technical scheme that its technical problem adopted is: a methanol water high pressure hydrogen production system comprises a reformer, a hydrogen separation device and a carbon dioxide separator;
the inlet of the reformer is connected with a methanol steam pipe and is suitable for conveying methanol steam into the reformer; the conveying pressure of the methanol steam in the methanol steam pipe is 18-50 MPa;
the outlet of the reformer and the inlet of the hydrogen separation device are connected with a first mixed gas conveying pipe, and the first mixed gas conveying pipe is suitable for conveying the mixed gas of hydrogen, carbon dioxide and carbon monoxide produced in the reformer into the hydrogen separation device for hydrogen separation;
the hydrogen separation device is connected with a pure hydrogen output pipe and a carbon dioxide mixed residual gas output pipe, the carbon dioxide mixed residual gas output pipe is connected with a carbon dioxide separator, and the carbon dioxide mixed residual gas output pipe is suitable for sending the carbon dioxide mixed residual gas into the carbon dioxide separator for carbon dioxide liquefaction and separation;
the carbon dioxide separator is connected with a carbon dioxide output pipe and a hydrogen mixed residual gas output pipe;
the carbon dioxide mixed residual gas output pipe is provided with a water-cooling heat exchanger which is suitable for carrying out water-cooling on the carbon dioxide mixed residual gas to be conveyed, the water-cooling heat exchanger is connected with a water-cooling tower, and the operating temperature of the water-cooling heat exchanger is 18-30.8 ℃.
The system further comprises a first three-phase heat exchange device and a second three-phase heat exchange device;
the methanol steam pipe is connected with the first three-phase heat exchange device and is suitable for vaporizing input methanol water into methanol steam;
the first mixed gas conveying pipe is connected with the second three-phase heat exchange device and is suitable for conveying the prepared mixed gas of hydrogen, carbon dioxide and carbon monoxide into the hydrogen separation device after heat exchange;
the pure hydrogen output pipe is sequentially connected with the second three-phase heat exchange device and the first three-phase heat exchange device, and the pure hydrogen is output after being subjected to heat exchange and temperature reduction through the two three-phase heat exchange devices respectively;
the carbon dioxide mixed residual gas output pipe is sequentially connected with the second three-phase heat exchange device and the first three-phase heat exchange device, and the carbon dioxide mixed residual gas is output after being subjected to heat exchange and cooling through the two three-phase heat exchange devices respectively.
Further, the hydrogen mixed residual gas output pipe is connected with a water gas reforming device, the water gas reforming device is connected with a second mixed gas conveying pipe, the second mixed gas conveying pipe is connected with a first mixed gas conveying pipe, and an air pump used for lifting the gas conveying pressure in the pipe is arranged on the second mixed gas conveying pipe.
And the hydrogen mixed residual gas output pipe and the carbon dioxide mixed residual gas output pipe are both connected with the two-phase heat exchange device, so that heat exchange is performed between the hydrogen mixed residual gas and the carbon dioxide mixed residual gas.
Further, an inlet of the methanol steam pipe is connected with a liquid pump for conveying methanol water, and the working pump pressure of the liquid pump is 18-50 MPa;
furthermore, a steam trap is arranged on the carbon dioxide mixed residual gas output pipe.
Furthermore, the pure hydrogen output pipe is connected with a hydrogen storage tank, the pure hydrogen 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 method for producing hydrogen from methanol water under high pressure is provided, which comprises the following steps:
s1, feeding methanol water into a methanol steam pipe through a liquid pump, wherein the pump pressure is 18-50 MPa, the methanol water is vaporized into methanol steam after passing through a first three-phase heat exchange device and enters a reformer, and the methanol steam is used for preparing a mixed gas of hydrogen, carbon dioxide and carbon monoxide in the reformer;
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 into pure hydrogen and carbon dioxide mixed residual gas through a hydrogen separation device;
the gas phase components of the carbon dioxide mixed residual gas comprise 25-45% of hydrogen, 55-75% of carbon dioxide, 0-3% of water and 0.3-3% of carbon monoxide;
s3, outputting the pure hydrogen after heat exchange and temperature reduction of the pure hydrogen sequentially through a second three-phase heat exchange device and a first three-phase heat exchange device; the carbon dioxide mixed residual gas is sequentially subjected to heat exchange by a second three-phase heat exchange device and a first three-phase heat exchange device, and is cooled to 18-30.8 ℃ by a water-cooled heat exchanger, and then is input into a carbon dioxide separator, the carbon dioxide mixed residual gas is prepared into liquid carbon dioxide and hydrogen mixed residual gas in the carbon dioxide separator, and the liquid carbon dioxide is output and collected;
the components of the hydrogen mixed residual gas comprise 65-75% of hydrogen, 20-26% of carbon dioxide and 3-9% of carbon monoxide;
the working temperature of the carbon dioxide mixed residual gas in the carbon dioxide separator is controlled to be 18-30.8 ℃ by a water-cooling heat exchanger, and the pressure is controlled to be 18-50 MPa by a liquid pump;
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 the hydrogen, the carbon dioxide and the carbon monoxide in the reforming mixed gas corresponds to the proportion of the hydrogen, the carbon dioxide and the carbon monoxide in the mixed gas of the hydrogen, the carbon dioxide and the carbon monoxide;
and S5, mixing the reformed mixed gas with the mixed gas of the hydrogen, the carbon dioxide and the carbon monoxide, and enabling the reformed mixed gas to enter the hydrogen separation device again along with the mixed gas of the hydrogen, the carbon dioxide and the carbon monoxide for hydrogen purification and separation.
Further, the methanol water is replaced by natural gas.
The utility model has the advantages that:
the utility model discloses a high pressure hydrogen manufacturing system adopts the methanol-water as the raw materials, hydrogen manufacturing system's operating pressure is controlled by the liquid pump, control hydrogen manufacturing under high pressure (18 ~ 50MPa) environment, and, come control carbon dioxide mixture residual gas at the operating temperature who gets into the carbon dioxide separator through water-cooled heat exchanger and water-cooling tower, temperature control is at 18 ~ 30.8 ℃, the advantage of water-cooled heat exchanger and water-cooling tower accuse temperature lies in with low costs, the operation is reliable and stable, be fit for installing this hydrogen manufacturing system in the area of 18 ~ 30.8 ℃ of outdoor temperature throughout the year.
The utility model discloses a hydrogen manufacturing is efficient, realizes the gas to the system in the purification that circulates, and theoretical yield can reach 100%, realizes that hydrogen yield is greater than or equal to 95%.
The utility model discloses a methanol-water high pressure hydrogen production system's working method is the biggest characteristics lie in, through at the hydrogen production system source, the pressure of control liquid pump income methanol-water, control is at high pressure (18 ~ 50MPa), whole hydrogen production all can be in this high pressure range operation, make whole hydrogen production system need not to go to set up again and be used for in addition to the system increase operating pressure's equipment such as air compressor machine or compressor, the whole hydrogen production system operating pressure can be mastered to a liquid pump of import department, under this high pressure (18 ~ 50MPa) environment, when to the mixed residual gas separation liquid carbon dioxide of carbon dioxide that generates in the hydrogen production system, only need to control the mixed residual gas of carbon dioxide through water-cooling heat exchanger and water-cooling tower and enter the operating temperature of carbon dioxide separator, refrigeration temperature control is at 18 ~ 30.8 ℃, just can reach 20 ~ 26 with the component of carbon dioxide in the mixed residual gas of hydrogen that separates out, the fact that the carbon dioxide component in the hydrogen mixed residual gas reaches 20-26% means that the carbon dioxide component in the mixed gas of the hydrogen, the carbon dioxide and the carbon monoxide which is discharged from the reformer accounts for the ratio, and one step is met for recycling of 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.
On the one hand, hydrogen production is harmless and zero-state emission; on the other hand, the carbon dioxide emission reduction is made into methanol, greenhouse gas is changed into useful methanol liquid fuel, the methanol liquid fuel is taken as a hydrogenation station, the solar fuel has rich sources, light, wind, water and nuclear energy are all available, the carbon dioxide hydrogenation is used for preparing the methanol, and the methanol can be transported, stored and transported. The problems of manufacture, storage, transportation, installation and the like are solved in the whole view,
firstly, the liquid sunlight hydrogen station solves the safety problem of the high-pressure hydrogen station; secondly, the problems of storage, transportation and safety of hydrogen are solved; thirdly, hydrogen can be used as renewable energy to realize the aim of cleaning the whole process; fourthly, the liquid sunlight hydrogenation station can recover carbon dioxide, so that carbon dioxide emission reduction is realized, no further carbon dioxide is generated, and the carbon dioxide is always circulated therein; fifthly, the liquid sunlight hydrogenation station technology can be expanded to other chemical synthesis fields and can also be used for chemical hydrogenation; sixth, the system can be shared with a gas station and a methanol adding station. The system is particularly suitable for community distributed thermoelectric combined energy supply and the existing gas stations.
Drawings
The present invention will be further explained with reference to the accompanying drawings.
FIG. 1 is a diagram of a methanol-water high-pressure hydrogen production system of the present invention;
the system comprises a reformer 1, a reformer 2, a hydrogen separation device 31, a first three-phase heat exchange device 32, a second three-phase heat exchange device 33, a two-phase heat exchange device 4, a steam trap 5, a water-cooling heat exchanger 6, a carbon dioxide separator 7, a water gas reforming device 8, a liquid pump 9 and an air pump.
Detailed Description
The invention will now be further described with reference to specific embodiments. The drawings are simplified schematic diagrams only illustrating the basic structure of the present invention in a schematic manner, and thus show only the components related to the present invention.
Example one
As shown in fig. 1, a methanol-water high-pressure hydrogen production system comprises a reformer 1, a hydrogen separation device 2 and a carbon dioxide separator 6; an inlet of the reformer 1 is connected with a methanol steam pipe, an inlet of the methanol steam pipe is connected with a liquid pump 8, and the working pump pressure of the liquid pump 8 is 18-50 MPa; the conveying pressure of the methanol steam in the methanol steam pipe is 18-50 MPa.
The outlet of the reformer 1 and the inlet of the hydrogen separation device 2 are connected with a first mixed gas conveying pipe which is suitable for conveying the mixed gas of hydrogen, carbon dioxide and carbon monoxide produced in the reformer 1 into the hydrogen separation device 2 for hydrogen separation; the hydrogen separation device 2 is connected with a pure hydrogen output pipe and a carbon dioxide mixed residual gas output pipe, the carbon dioxide mixed residual gas output pipe is connected with a carbon dioxide separator 6, and the carbon dioxide mixed residual gas output pipe is suitable for sending the carbon dioxide mixed residual gas into the carbon dioxide separator 6 for carbon dioxide liquefaction and separation; the carbon dioxide separator 6 is connected with a carbon dioxide output pipe and a hydrogen mixed residual gas output pipe; the carbon dioxide mixed residual gas output pipe is provided with the water-cooling heat exchanger 5 which is suitable for carrying out water-cooling on the carbon dioxide mixed residual gas to be conveyed, the water-cooling heat exchanger 5 is connected with a water-cooling tower, and the operation temperature of the water-cooling heat exchanger 5 is 18-30.8 ℃.
Specifically, in order to realize effective utilization of the system during operation, the system further comprises a first three-phase heat exchange device 31 and a second three-phase heat exchange device 32; the methanol steam pipe is connected with the first three-phase heat exchange device 31 and is suitable for vaporizing input methanol water into methanol steam; the first mixed gas conveying pipe is connected with the second three-phase heat exchange device 32 and is suitable for conveying the prepared mixed gas of hydrogen, carbon dioxide and carbon monoxide into the hydrogen separation device 2 after heat exchange;
the pure hydrogen output pipe is sequentially connected with the second three-phase heat exchange device 32 and the first three-phase heat exchange device 31, and pure hydrogen is output after being subjected to heat exchange and temperature reduction through the two three-phase heat exchange devices respectively; the carbon dioxide mixed residual gas output pipe is sequentially connected with the second three-phase heat exchange device 32 and the first three-phase heat exchange device 31, and the carbon dioxide mixed residual gas is output after being subjected to heat exchange and cooling through the two three-phase heat exchange devices respectively.
The pure hydrogen output pipe is connected with a hydrogen storage tank, the pure hydrogen 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.
Operation principle of the reformer 1: a catalyst is arranged in a reforming chamber of the reformer 1, the temperature of the reforming chamber is 220-320 ℃, methanol and steam pass through the catalyst under the pressure condition of 18-50M Pa in the reforming chamber, and a methanol cracking reaction and a carbon monoxide shift reaction are carried out under the action of the catalyst to generate a mixed gas of hydrogen, carbon dioxide and carbon monoxide, which is a multi-component and multi-reaction gas-solid catalytic reaction system;
the reaction equation is: CH (CH)3OH→CO+2H2(reversible reaction);
H2O+CO→CO2+H2(reversible reaction);
CH3OH+H2O→CO2+3H2(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 operating principle of the hydrogen separation device 2: the hydrogen purification device adopts a membrane separation device, the membrane separation device is a membrane separation device for vacuum plating of palladium-silver alloy on the surface of porous ceramic, a plating film layer is the palladium-silver alloy, the mass percentages of the palladium-silver alloy are respectively 75% -78% of palladium and 22% -25% of silver, and the manufacturing process of the membrane separation device can refer to the utility model patent 201210563913.5 applied by Shanghai Heyu dynamic hydrogen machine Limited company in 12.21.2012, the membrane separator of the methanol-water hydrogen production equipment and the preparation method thereof. The temperature of the hydrogen separation device 2 is about 400 ℃ when in operation;
specifically, for realizing hydrogen production system hydrogen yield, hydrogen mixed residual gas output pipe connects water gas reforming unit 7, water gas reforming unit 7 connects the second gas mixture conveyer pipe, the first gas mixture conveyer pipe of second gas mixture conveyer pipe connection, set up the air pump 9 that is used for promoting intraductal gas delivery pressure on the second gas mixture conveyer pipe. This allows the reformed gas mixture to be mixed with the gas mixture output from the reformer 1 and to be fed again to the hydrogen separation device 2 for hydrogen purification. The lifting system circularly processes the residual gas, and the hydrogen yield of the whole system is improved.
Specifically, in order to realize the efficient utilization of heat energy, the hydrogen production system further comprises a two-phase heat exchange device 33, and the hydrogen mixed residual gas output pipe and the carbon dioxide mixed residual gas output pipe are both connected with the two-phase heat exchange device 33 and are suitable for heat exchange between the hydrogen mixed residual gas and the carbon dioxide mixed residual gas. And (4) cooling the carbon dioxide mixed residual gas, and heating the hydrogen mixed residual gas.
Specifically, in order to reduce the moisture in the carbon dioxide mixed residual gas, a steam trap 4, also called a moisture separator, is disposed on the carbon dioxide mixed residual gas output pipe.
The molar ratio of carbon dioxide in the gaseous phase components 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 during working is shown in the following table:
the utility model discloses a high pressure (18 ~ 50MPa) hydrogen manufacturing system, rely on methanol-water to carry out the hydrogen manufacturing as the raw materials, the hydrogen yield is greater than or equal to 95%, heat realization cyclic utilization during hydrogen manufacturing system work, make the system more energy-conserving, entire system is because liquid pump 8 carries out high pressure (18 ~ 50MPa) control at the source, make hydrogen manufacturing system, to carbon dioxide mixture residual gas separation carbon dioxide, through water-cooled heat exchanger 5 and water-cooled tower control carbon dioxide mixture residual gas at the operating temperature who gets into carbon dioxide separator 6, temperature control is at 18 ~ 30.8 ℃, make carbon dioxide mixture residual gas obtain a target partial pressure value in carbon dioxide separator 6, separate carbon dioxide mixture residual gas into liquid carbon dioxide and hydrogen mixture residual gas, at pressure 18 ~ 50MPa, the temperature is when 18 ~ 30.8 ℃, the hydrogen mixture residual gas component of separating satisfies the requirement of carrying out the water gas reforming, the component proportion of the reformed mixed gas prepared by the hydrogen mixed residual gas after water gas reforming is equivalent to that of the mixed gas of hydrogen, carbon dioxide and carbon monoxide prepared by the reformer 1, so that the hydrogen and the mixed gas can be mixed and then enter a membrane separation and purification device for hydrogen purification and separation to prepare hydrogen.
The utility model discloses hydrogen manufacturing system adopts water-cooled heat exchanger 5 and water-cooling tower accuse temperature's advantage lie in with low costs, the operation is reliable and stable, is fit for installing this hydrogen manufacturing system in the area of outdoor temperature 18 ~ 30.8 ℃ throughout the year.
Example two
A method for preparing hydrogen from methanol water at high pressure comprises the following steps:
s1, the liquid pump 8 sends the methanol water into a methanol steam pipe, the pump pressure is 18-50 MPa, the methanol water is vaporized into methanol steam after passing through the first three-phase heat exchange device 31 and enters the reformer 1, and the methanol steam is prepared into mixed gas of hydrogen, carbon dioxide and carbon monoxide in the reformer 1; the ratio of methanol to water in the methanol water is 1: 1;
the working temperature of the reformer 1 is 220-320 ℃; the gas phase component of the mixed gas of hydrogen, carbon dioxide and carbon monoxide is 65-75% of hydrogen, 20-26% of carbon dioxide and 0.3-3% of carbon monoxide;
s2, separating the mixed gas of hydrogen, carbon dioxide and carbon monoxide into pure hydrogen and carbon dioxide mixed residual gas through a hydrogen separation device 2;
the working temperature of the hydrogen separation device 2 is 380-420 ℃, and the gas phase components of the carbon dioxide mixed residual gas are 25-45% of hydrogen, 55-75% of carbon dioxide, 0-3% of water and 0.3-3% of carbon monoxide;
s3, outputting the pure hydrogen after heat exchange and temperature reduction through the second three-phase heat exchange device 32 and the first three-phase heat exchange device 31 in sequence; the carbon dioxide mixed residual gas is sequentially subjected to heat exchange by a second three-phase heat exchange device 32 and a first three-phase heat exchange device 31, and is cooled to 18-30.8 ℃ by a water-cooled heat exchanger 5, and then is input into a carbon dioxide separator 6, the carbon dioxide mixed residual gas is prepared into liquid carbon dioxide and hydrogen mixed residual gas in the carbon dioxide separator 6, and the liquid carbon dioxide is output and collected;
the components of the hydrogen mixed residual gas comprise 65-75% of hydrogen, 20-26% of carbon dioxide and 3-9% of carbon monoxide;
the working temperature of the carbon dioxide mixed residual gas in the carbon dioxide separator 6 is controlled to be 18-30.8 ℃ by the water-cooling heat exchanger 5, the water-cooling heat exchanger 5 is connected with a cooling tower, the cooling tower exchanges heat with outdoor air to reduce the temperature, and the pressure is controlled to be 18-50 MPa by the liquid pump 8;
the molar ratio of carbon dioxide in the gaseous phase components 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 during working is shown in the following table:
| scheme(s) | Pressure (Mpa) | Temperature (. degree.C.) |
| Scheme 1 | 18 | 18 |
| |
25 | 25 |
| Scheme 3 | 50 | 30.8 |
S4, feeding the hydrogen mixed residual gas into a water gas reforming device 7 for reforming, and preparing reformed mixed gas by water distribution, wherein the working temperature of the water gas reforming reaction device is 200-280 ℃, 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 a reformed mixed gas by water distribution, and the gas phase components of the reformed mixed gas comprise 62-77% of hydrogen, 22-27% of carbon dioxide and 0.5-1.5% of carbon monoxide;
the water gas reforming reaction formula is as follows: CO + H2O→CO2+H2；
So that the proportion of the hydrogen, the carbon dioxide and the carbon monoxide in the reforming mixed gas corresponds to the proportion of the hydrogen, the carbon dioxide and the carbon monoxide in the mixed gas of the hydrogen, the carbon dioxide and the carbon monoxide;
and S5, mixing the reformed mixed gas with the mixed gas of the hydrogen, the carbon dioxide and the carbon monoxide, and enabling the reformed mixed gas to enter the hydrogen separation device 2 again along with the mixed gas of the hydrogen, the carbon dioxide and the carbon monoxide for hydrogen purification and separation.
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 utility model discloses a biggest characteristics of working method of methanol-water high pressure hydrogen manufacturing system lie in, through at the hydrogen manufacturing system source, the pressure of 8 pump income methanol-water of control liquid pump, control is at high pressure (18 ~ 50MPa), whole hydrogen manufacturing all can be operated at this high pressure range, make whole hydrogen manufacturing system need not to go to set up again and be used for in addition to the equipment such as air compressor machine or the compressor that increases operating pressure to the carbon dioxide liquefaction system, a liquid pump 8 of import department can control whole hydrogen manufacturing system operating pressure, under this high pressure (18 ~ 50MPa) environment, when separating liquid carbon dioxide to the mixed residual gas of carbon dioxide that generates in the hydrogen manufacturing system, control the operating temperature that the mixed residual gas of carbon dioxide is getting into carbon dioxide separator 6 through water-cooled heat exchanger 5 and water-cooled tower, temperature control is at 18 ~ 30.8 ℃, just can reach 20 ~ 26 with the component of carbon dioxide in the mixed residual gas of hydrogen that separates, the fact that the carbon dioxide component in the hydrogen mixed residual gas reaches 20-26% means that the carbon dioxide component in the mixed gas of the hydrogen, the carbon dioxide and the carbon monoxide which is discharged from the reformer 1 accounts for the ratio, and one step is met for recycling of 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 components of the reformed mixed gas are equivalent to the components of the mixed gas of hydrogen, carbon dioxide and carbon monoxide prepared by the reformer 1, 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.
In light of the foregoing, it will be apparent to those skilled in the art from this disclosure that various changes and modifications can be made 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 (7)
1. A methanol water high pressure hydrogen production system is characterized by comprising a reformer, a hydrogen separation device and a carbon dioxide separator;
the inlet of the reformer is connected with a methanol steam pipe and is suitable for conveying methanol steam into the reformer; the conveying pressure of the methanol steam in the methanol steam pipe is 18-50 MPa;
the outlet of the reformer and the inlet of the hydrogen separation device are connected with a first mixed gas conveying pipe, and the first mixed gas conveying pipe is suitable for conveying the mixed gas of hydrogen, carbon dioxide and carbon monoxide produced in the reformer into the hydrogen separation device for hydrogen separation;
the hydrogen separation device is connected with a pure hydrogen output pipe and a carbon dioxide mixed residual gas output pipe, the carbon dioxide mixed residual gas output pipe is connected with a carbon dioxide separator, and the carbon dioxide mixed residual gas output pipe is suitable for sending the carbon dioxide mixed residual gas into the carbon dioxide separator for carbon dioxide liquefaction and separation;
the carbon dioxide separator is connected with a carbon dioxide output pipe and a hydrogen mixed residual gas output pipe;
the carbon dioxide mixed residual gas output pipe is provided with a water-cooling heat exchanger which is suitable for carrying out water-cooling on the carbon dioxide mixed residual gas to be conveyed, the water-cooling heat exchanger is connected with a water-cooling tower, and the operating temperature of the water-cooling heat exchanger is 18-30.8 ℃.
2. The methanol-water high-pressure hydrogen production system according to claim 1, further comprising a first three-phase heat exchange device and a second three-phase heat exchange device;
the methanol steam pipe is connected with the first three-phase heat exchange device and is suitable for vaporizing input methanol water into methanol steam;
the first mixed gas conveying pipe is connected with the second three-phase heat exchange device and is suitable for conveying the prepared mixed gas of hydrogen, carbon dioxide and carbon monoxide into the hydrogen separation device after heat exchange;
the pure hydrogen output pipe is sequentially connected with the second three-phase heat exchange device and the first three-phase heat exchange device, and the pure hydrogen is output after being subjected to heat exchange and temperature reduction through the two three-phase heat exchange devices respectively;
the carbon dioxide mixed residual gas output pipe is sequentially connected with the second three-phase heat exchange device and the first three-phase heat exchange device, and the carbon dioxide mixed residual gas is output after being subjected to heat exchange and cooling through the two three-phase heat exchange devices respectively.
3. The system for high-pressure hydrogen production by methanol water according to claim 2, wherein the hydrogen gas mixing residual gas output pipe is connected with a water gas reforming device, the water gas reforming device is connected with a second gas mixture conveying pipe, the second gas mixture conveying pipe is connected with a first gas mixture conveying pipe, and an air pump for increasing the conveying pressure of gas in the pipe is arranged on the second gas mixture conveying pipe.
4. The system for high-pressure hydrogen production by methanol water according to claim 3, further comprising a two-phase heat exchanger, wherein the hydrogen mixed residual gas output pipe and the carbon dioxide mixed residual gas output pipe are both connected with the two-phase heat exchanger, and are suitable for exchanging heat between the hydrogen mixed residual gas and the carbon dioxide mixed residual gas.
5. The system for high-pressure hydrogen production by methanol water according to claim 3, wherein an inlet of the methanol-water vapor pipe is connected with a liquid pump for conveying methanol water, and the working pump pressure of the liquid pump is 18-50 MPa.
6. The system for producing hydrogen from methanol-water under high pressure as in claim 1, wherein a steam trap is arranged on the carbon dioxide mixed residual gas output pipe.
7. The system for producing hydrogen from methanol water under high pressure as claimed in claim 5, wherein the pure hydrogen gas output pipe is connected with a hydrogen storage tank, the pure hydrogen gas is pumped into the hydrogen storage tank by a liquid pump, and the hydrogen storage tank is connected with a hydrogenation machine.
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2019
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