CN110937573B - Hydrogen mixed residual gas reforming method - Google Patents
Hydrogen mixed residual gas reforming method Download PDFInfo
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- CN110937573B CN110937573B CN201911033569.7A CN201911033569A CN110937573B CN 110937573 B CN110937573 B CN 110937573B CN 201911033569 A CN201911033569 A CN 201911033569A CN 110937573 B CN110937573 B CN 110937573B
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/323—Catalytic reaction of gaseous or liquid organic compounds other than hydrocarbons with gasifying agents
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/12—Feeding the process for making hydrogen or synthesis gas
- C01B2203/1205—Composition of the feed
- C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
- C01B2203/1217—Alcohols
- C01B2203/1223—Methanol
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2210/00—Purification or separation of specific gases
- C01B2210/0043—Impurity removed
- C01B2210/0051—Carbon dioxide
Abstract
The invention relates to a hydrogen mixed residual gas reforming method, which comprises the following steps: the carbon dioxide liquefying device sends the separated hydrogen mixed residual gas into the water gas reforming reaction device for reforming; 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 reforming mixed gas by water distribution, 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 components of the reforming mixed gas are close to the components of the mixed gas of hydrogen, carbon dioxide and carbon monoxide, so that the reforming mixed gas can reenter the hydrogen production system to produce hydrogen again, and the hydrogen production yield of the whole hydrogen production system is improved.
Description
Technical Field
The invention relates to a hydrogen mixed residual gas reforming method.
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.
At present, the system for producing hydrogen by means of methanol water is developed in our hospital, and the principle of the hydrogen production system is as follows: heating methanol water into methanol vapor, preparing the methanol vapor into mixed gas of hydrogen, carbon dioxide and carbon monoxide by a reformer, and separating the mixed gas of the hydrogen, the carbon dioxide and the carbon monoxide into pure hydrogen and carbon dioxide mixed residual gas by a membrane separation and purification device; pure hydrogen is collected by canning, and the other part of the separated carbon dioxide mixed residual gas is mainly discharged directly at the current stage of treating the carbon dioxide mixed residual gas, and is not recycled, so that waste is serious; through careful analysis, the carbon dioxide mixed residual gas can be recovered, and the gas phase components of the carbon dioxide mixed residual gas are as follows: 25-45% of hydrogen, 55-75% of carbon dioxide, 0-3% of water and 0.3-3% of carbon monoxide; in the hydrogen production system, the gas phase components of the mixed gas of the hydrogen, the carbon dioxide and the carbon monoxide entering the membrane separation and purification device are 65-75% of hydrogen, 20-26% of carbon dioxide and 0.3-3% of carbon monoxide; therefore, only two steps are needed, firstly, the carbon dioxide mixed residual gas is separated from pure carbon dioxide and hydrogen mixed residual gas through a carbon dioxide liquefying device, at the moment, the volume ratio of carbon dioxide in the hydrogen mixed residual gas is adjusted to 20-26% from 55-75%, secondly, the hydrogen mixed residual gas is operated, the volume ratio of hydrogen is adjusted to 65-75% from 25-45%, the carbon dioxide mixed residual gas can be gradually changed into reformed mixed gas, and the reformed mixed gas can enter the membrane separation purifying device again for circulation operation due to the fact that the component ratio is equivalent to the gas phase component ratio of the mixed gas of hydrogen, carbon dioxide and carbon monoxide, and the hydrogen production yield of the whole system is improved.
Therefore, the present application mainly solves the problem of how to perform the second step, i.e. how to perform the reaction treatment on the hydrogen mixed residual gas, so that the hydrogen mixed residual gas is close to the gas phase component of the reforming mixed gas, and the hydrogen mixed residual gas is made to perform the cyclic hydrogen production in the hydrogen production system.
Disclosure of Invention
The invention aims to solve the technical problems that: the method for reforming the hydrogen mixed residual gas overcomes the defects of the prior art, so that the hydrogen mixed residual gas is close to the gas phase component of the reformed mixed gas, and the hydrogen mixed residual gas and the reformed mixed gas are subjected to cyclic hydrogen production in a hydrogen production system.
The technical scheme adopted for solving the technical problems is as follows: a hydrogen mixed residual gas reforming method comprises the following steps:
s1, sending the hydrogen mixed residual gas into a water gas reforming reaction device for reforming;
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 working temperature of the water gas reforming reaction device is 200-280 ℃, and water distribution is carried out according to the content of carbon monoxide;
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 water gas reforming reaction formula is: CO+H 2 O→CO 2 +H 2 。
Further, the water distribution ratio (carbon monoxide: water) is 1:1-20.
Further, the hydrogen mixed residual gas is separated by a carbon dioxide liquefying device.
The beneficial effects of the invention are as follows:
the hydrogen mixed residual gas reforming method is characterized in that the components of the hydrogen mixed residual gas are 65-75% of hydrogen, 20-26% of carbon dioxide and 3-9% of carbon monoxide, and the water gas is reformed to generate reformed mixed gas which is composed of 62-77% of hydrogen, 22-27% of carbon dioxide and 0.5-1.5% of carbon monoxide, so that the components of the reformed mixed gas are close to the components of the mixed gas of hydrogen, carbon dioxide and carbon monoxide, and the reformed mixed gas can reenter a hydrogen production system to produce hydrogen again, and the hydrogen production yield of the whole hydrogen production system is improved.
Detailed Description
The invention will now be further described with reference to specific examples.
A hydrogen mixed residual gas reforming method comprises the following steps:
the carbon dioxide liquefying device sends the separated hydrogen mixed residual gas into the water gas reforming reaction device for reforming; 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 working temperature of the water gas reforming reaction device is 200-280 ℃, the temperature is preferably 250 ℃, then water distribution is carried out according to the content of carbon monoxide, and the water distribution ratio (carbon monoxide: water) is 1:1-20;
reforming of water gasThe catalyst used is a copper-based catalyst; the water gas reforming reaction formula is: CO+H 2 O →CO 2 +H 2 ；
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;
in the method according to the embodiment, the temperature and the water distribution ratio are effectively controlled, so that the prepared reforming mixed gas meets the requirement of being capable of reentering the hydrogen production system, and the reforming mixed gas is enabled to carry out cyclic hydrogen production in the hydrogen production system.
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 (2)
1. The hydrogen mixed residual gas reforming method is characterized by comprising the following steps of:
s1, sending the hydrogen mixed residual gas into a water gas reforming reaction device for reforming;
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 working temperature of the water gas reforming reaction device is 200-280 ℃, and water distribution is carried out according to the content of carbon monoxide;
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 water gas reforming reaction formula is: CO+H 2 O→CO 2 +H 2 ；
Carbon monoxide: the water is 1:1-20.
2. The method for reforming a hydrogen-mixed residual gas according to claim 1, wherein the hydrogen-mixed residual gas is separated by a carbon dioxide liquefying device.
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Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1061386A (en) * | 1990-11-16 | 1992-05-27 | 德士古发展公司 | The preparation method of high-purity hydrogen |
| WO2005033003A1 (en) * | 2003-10-06 | 2005-04-14 | Statoil Asa | Hydrogen production from methanol |
| CN1944239A (en) * | 2006-10-24 | 2007-04-11 | 四川亚连科技有限责任公司 | Method for preparing hydrogen by reforming methanol with high recovery rate |
| CN101616865A (en) * | 2006-11-30 | 2009-12-30 | 国际壳牌研究有限公司 | Produce the system and method for hydrogen and carbonic acid gas |
| CN102730637A (en) * | 2012-07-17 | 2012-10-17 | 武汉凯迪工程技术研究总院有限公司 | Comprehensive utilization process for low-carbon-emission Fischer-Tropsch synthesis tail gas |
| CN102849680A (en) * | 2012-08-30 | 2013-01-02 | 苏州金宏气体股份有限公司 | Method for synthesis and purification of hydrogen from natural gas |
| CN104411624A (en) * | 2012-07-04 | 2015-03-11 | 乔治洛德方法研究和开发液化空气有限公司 | Process for recovering hydrogen and capturing carbon dioxide |
| CN106379859A (en) * | 2016-11-15 | 2017-02-08 | 晋城市阿邦迪能源有限公司 | Methanol reforming reactor |
| CN108545696A (en) * | 2018-04-27 | 2018-09-18 | 杨皓 | A kind of Water gas shift/WGS gas manufacture ammonia synthesis gas technique |
| CN109310971A (en) * | 2016-06-14 | 2019-02-05 | 乔治洛德方法研究和开发液化空气有限公司 | The reactor of synthesis gas is generated by steam reformation |
-
2019
- 2019-10-28 CN CN201911033569.7A patent/CN110937573B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1061386A (en) * | 1990-11-16 | 1992-05-27 | 德士古发展公司 | The preparation method of high-purity hydrogen |
| WO2005033003A1 (en) * | 2003-10-06 | 2005-04-14 | Statoil Asa | Hydrogen production from methanol |
| CN1944239A (en) * | 2006-10-24 | 2007-04-11 | 四川亚连科技有限责任公司 | Method for preparing hydrogen by reforming methanol with high recovery rate |
| CN101616865A (en) * | 2006-11-30 | 2009-12-30 | 国际壳牌研究有限公司 | Produce the system and method for hydrogen and carbonic acid gas |
| CN104411624A (en) * | 2012-07-04 | 2015-03-11 | 乔治洛德方法研究和开发液化空气有限公司 | Process for recovering hydrogen and capturing carbon dioxide |
| CN102730637A (en) * | 2012-07-17 | 2012-10-17 | 武汉凯迪工程技术研究总院有限公司 | Comprehensive utilization process for low-carbon-emission Fischer-Tropsch synthesis tail gas |
| CN102849680A (en) * | 2012-08-30 | 2013-01-02 | 苏州金宏气体股份有限公司 | Method for synthesis and purification of hydrogen from natural gas |
| CN109310971A (en) * | 2016-06-14 | 2019-02-05 | 乔治洛德方法研究和开发液化空气有限公司 | The reactor of synthesis gas is generated by steam reformation |
| CN106379859A (en) * | 2016-11-15 | 2017-02-08 | 晋城市阿邦迪能源有限公司 | Methanol reforming reactor |
| CN108545696A (en) * | 2018-04-27 | 2018-09-18 | 杨皓 | A kind of Water gas shift/WGS gas manufacture ammonia synthesis gas technique |
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