阅读说明：本技术 甲醇水超高压制氢系统及其制氢方法 (Methanol-water ultrahigh-pressure hydrogen production system and hydrogen production method thereof ) 是由 岳锌 韩涤非 姚婷婷 李佳毅 赵纪军 岳野 李军 于 2019-10-28 设计创作，主要内容包括：本发明涉及一种甲醇水超高压制氢系统,包括重整器、氢分离装置以及二氧化碳分离器；重整器进口连接甲醇水蒸汽管；甲醇水蒸汽管上设置液态泵,液态泵的泵压为40～100MPa；纯氢气在液态泵的泵压下送入氢气储罐；水冷换热器作业温度≤30.8℃。一种甲醇水超高压制氢方法,液态泵将甲醇水送入甲醇水蒸气管进管,泵压为40～100MPa,在重整分离装置的反应腔内分离成纯氢气和混合气体,纯氢气在液态泵的泵压下送入氢气储罐,将氢气混合余气配水重整获得重整混合气,重整混合气再次送入反应腔内进行分离氢气作业。实现对系统内的气体进行循环纯化,理论收率可达到100％,实现氢气收率≥95％。(The invention relates to a methanol-water ultrahigh pressure hydrogen production system, which comprises a reformer, a hydrogen separation device and a carbon dioxide separator; the inlet of the reformer is connected with a methanol-water steam pipe; a liquid pump is arranged on the methanol-water steam pipe, and the pump 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 operation temperature of the water-cooled heat exchanger is less than or equal to 30.8 ℃. A method for preparing hydrogen by methanol water under ultrahigh pressure comprises the steps of feeding methanol water into a methanol steam pipe inlet pipe by a liquid pump, separating the methanol water into pure hydrogen and mixed gas in a reaction cavity of a reforming and separating device under the pump pressure of the liquid pump, feeding the pure hydrogen into a hydrogen storage tank under the pump pressure of the liquid pump, distributing and reforming hydrogen mixed residual gas to obtain reformed mixed gas, and feeding the reformed mixed gas into the reaction cavity again to separate hydrogen. 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.)

1. A methanol water ultrahigh 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-water steam pipe and is suitable for conveying methanol steam into the reformer; a liquid pump is arranged on the methanol-water steam pipe, and the pump pressure of the liquid pump is 40-100 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 pure hydrogen output pipe is connected with a hydrogen storage tank, and the pure hydrogen in the pure hydrogen output pipe is pumped into the hydrogen storage tank by a liquid pump;

the carbon dioxide mixed residual gas output pipe is connected with the carbon dioxide separator and 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 conveyed carbon dioxide mixed residual gas, 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 ℃.

2. The methanol-water ultrahigh 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 water steam pipe is connected with the first three-phase heat exchange device and is suitable for vaporizing input methanol water into methanol water vapor;

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 producing hydrogen by methanol water ultrahigh pressure according to claim 1, wherein the hydrogen gas 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 reformed mixed gas conveying pipe is connected with a first mixed gas conveying pipe, and an air pump for increasing the conveying pressure of gas in the pipe is arranged on the second reformed mixed gas conveying pipe.

4. The system 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 to the two-phase heat exchanger, and are adapted to exchange heat between the hydrogen mixed residual gas and the carbon dioxide mixed residual gas.

5. The system of claim 1, wherein a steam trap is arranged on the carbon dioxide mixed residual gas output pipe.

6. The system for producing hydrogen by methanol water under ultrahigh pressure as claimed in claim 1, wherein the pure hydrogen output pipe is connected with a hydrogen storage tank, the pure hydrogen is pumped into the hydrogen storage tank by a liquid pump, and the hydrogen storage tank is connected with a hydrogenation machine.

7. A methanol water ultrahigh pressure hydrogen production method is characterized in that the methanol water ultrahigh pressure hydrogen production system adopting any one of the above 1-6 comprises the following steps:

s1, feeding methanol water into a methanol water steam pipe through a liquid pump, wherein the pump pressure is 40-100 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 through the second three-phase heat exchange device and the first three-phase heat exchange device in sequence, and inputting the pure hydrogen into a hydrogen storage tank under the pump pressure of a liquid pump;

the carbon dioxide mixed residual gas is sequentially subjected to heat exchange by the second three-phase heat exchange device, the first three-phase heat exchange device and the 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 less than or equal to 30.8 ℃ by a water-cooling heat exchanger, and the pressure is controlled to be 40-100 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 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 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.

Technical Field

The invention relates to a methanol-water ultrahigh-pressure hydrogen production system and a hydrogen production method thereof.

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 car 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 the hydrogen is transported back from outside by an energy storage tank, 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 water ultrahigh pressure hydrogen production system and the hydrogen production method thereof are 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 station are solved.

The technical scheme adopted by the invention for solving the technical problems is as follows:

a methanol water ultrahigh 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-water steam pipe and is suitable for conveying methanol steam into the reformer; a liquid pump is arranged on the methanol-water steam pipe, and the pump pressure of the liquid pump is 40-100 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 pure hydrogen output pipe is connected with a hydrogen storage tank, and the pure hydrogen in the pure hydrogen output pipe is pumped into the hydrogen storage tank by a liquid pump;

the carbon dioxide mixed residual gas output pipe is connected with the carbon dioxide separator and 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 conveyed carbon dioxide mixed residual gas, 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 system further comprises a first three-phase heat exchange device and a second three-phase heat exchange device;

the methanol water steam pipe is connected with the first three-phase heat exchange device and is suitable for vaporizing input methanol water into methanol water vapor;

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.

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 methanol-water ultrahigh pressure hydrogen production method is provided, wherein the methanol-water ultrahigh pressure hydrogen production system comprises the following steps:

s1, feeding methanol water into a methanol water steam pipe through a liquid pump, wherein the pump pressure is 40-100 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 through the second three-phase heat exchange device and the first three-phase heat exchange device in sequence, and inputting the pure hydrogen into a hydrogen storage tank under the pump pressure of a liquid pump;

the carbon dioxide mixed residual gas is sequentially subjected to heat exchange by the second three-phase heat exchange device, the first three-phase heat exchange device and the 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 less than or equal to 30.8 ℃ by a water-cooling heat exchanger, and the pressure is controlled to be 40-100 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 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 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.

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 conveying pressure of separated pure hydrogen and pure hydrogen output from an output pipe can be provided by the liquid pump under the ultrahigh-pressure (40-100 MPa) environment, so that the inconvenience of collecting the pure hydrogen by arranging the compressor on a pure hydrogen output pipe in the past is avoided.

When the carbon dioxide mixed residual gas generated in the hydrogen production system is separated into liquid carbon dioxide, 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, and the refrigeration temperature is controlled to be less than or equal to 30.8 ℃ (the temperature is selected to be 30.8 ℃ because the CO is selected to be 30.8 DEG C₂The critical temperature) of the hydrogen gas mixture, the carbon dioxide component in the separated hydrogen gas mixture residual gas can reach 20-26%, and the carbon dioxide component in the hydrogen gas mixture residual gas reaching 20-26% means that the carbon dioxide component ratio in the mixed gas of the hydrogen gas, the carbon dioxide and the carbon monoxide from the reformer is close to, and one step is satisfied for the 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.

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, and more CO can be recovered₂And obtaining economic benefits, really realizing safety (reducing high-pressure hydrogen storage), and being economical (due to the fact thatMuch lower methanol transportation cost than hydrogen), and also recover CO₂Zero emission is realized, and ecological benefits are 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.

Drawings

The invention is further described below with reference to the accompanying drawings.

FIG. 1 is a diagram of a methanol-water ultrahigh pressure hydrogen production system according to 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 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.