CN112028016A - Method for preparing hydrogen and food-grade dry ice for fuel cell by LNG - Google Patents
Method for preparing hydrogen and food-grade dry ice for fuel cell by LNG Download PDFInfo
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- CN112028016A CN112028016A CN202010984398.2A CN202010984398A CN112028016A CN 112028016 A CN112028016 A CN 112028016A CN 202010984398 A CN202010984398 A CN 202010984398A CN 112028016 A CN112028016 A CN 112028016A
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- carbon dioxide
- lng
- dry ice
- hydrogen
- natural gas
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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
- C01B3/22—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds
- C01B3/24—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds of hydrocarbons
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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
- C01B3/56—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with solids; Regeneration of used solids
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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
- C01B32/00—Carbon; Compounds thereof
- C01B32/50—Carbon dioxide
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/50—Carbon dioxide
- C01B32/55—Solidifying
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F28—HEAT EXCHANGE IN GENERAL
- F28D—HEAT-EXCHANGE APPARATUS, NOT PROVIDED FOR IN ANOTHER SUBCLASS, IN WHICH THE HEAT-EXCHANGE MEDIA DO NOT COME INTO DIRECT CONTACT
- F28D21/00—Heat-exchange apparatus not covered by any of the groups F28D1/00 - F28D20/00
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F28—HEAT EXCHANGE IN GENERAL
- F28D—HEAT-EXCHANGE APPARATUS, NOT PROVIDED FOR IN ANOTHER SUBCLASS, IN WHICH THE HEAT-EXCHANGE MEDIA DO NOT COME INTO DIRECT CONTACT
- F28D21/00—Heat-exchange apparatus not covered by any of the groups F28D1/00 - F28D20/00
- F28D2021/0019—Other heat exchangers for particular applications; Heat exchange systems not otherwise provided for
- F28D2021/0043—Other heat exchangers for particular applications; Heat exchange systems not otherwise provided for for fuel cells
Abstract
The invention discloses a method for preparing hydrogen and food-grade dry ice for a fuel cell by LNG. The method comprises the following steps: after entering a carbon dioxide dry ice production working section, the pressurized LNG exchanges heat with purified carbon dioxide or exchanges heat with nitrogen or mixed refrigerant and is heated; heating the heated natural gas and then entering a natural gas conversion section; in the natural gas conversion section, natural gas is concentrated through conversion, transformation and pressure swing adsorption, and the concentrated gas is hydrogen-rich gas; and a purge gas outlet of a pressure swing adsorption working section in the natural gas conversion working section is a mixture rich in carbon dioxide gas, purified carbon dioxide is obtained after the mixture passes through a carbon dioxide purification working section, and then the mixture enters a carbon dioxide dry ice production working section to exchange heat with LNG and cool to prepare food-grade dry ice. The invention organically combines the processes of LNG gasification, hydrogen preparation, carbon dioxide purification and dry ice preparation, energy is mutually utilized, the obtained hydrogen can be conveniently transported and utilized, and the food-grade dry ice can be widely applied to the fields of food and medicine and has good economy.
Description
Technical Field
The invention relates to a method for preparing hydrogen and food-grade dry ice for a fuel cell by LNG.
Background
The global energy industry is undergoing the third energy revolution with low carbonization, no carbonization and low pollution as the direction, and with the increasing global energy demand and obvious global electrification trend, the power energy structure with the largest renewable energy growth range will be continuously changed in the future, and further diversified energy structures mainly comprising petroleum, natural gas, coal and renewable energy are formed.
The hydrogen energy is used as a clean, efficient, safe and sustainable secondary energy, can be obtained through various ways such as primary energy, secondary energy and the industrial field, can also be widely applied to industries such as industry, building, traffic and electric power, is an important carrier for constructing a multi-energy supply system mainly based on clean energy in the future, the development and utilization technology of the hydrogen energy becomes an important direction of a new round of world energy technology change, is also a strategic high point of future development of the automobile industry, the development of the hydrogen energy is beneficial to accelerating and promoting the energy production and consumption revolution of China, and has great significance for the energy transformation development of a new era.
Hydrogen energy development planning is made in the United states, Japan, Canada, European Union and the like, at present, governments at all levels in China also pay high attention to the development of the hydrogen energy industry, and a top-down policy support system is formed. At present, the key factor influencing the development of the hydrogen energy industry is the price of hydrogen, and the price of hydrogen determines the economy of hydrogen utilization, and further determines the economy and feasibility of the whole industry. The hydrogen energy industry comprises three main links of hydrogen production, hydrogen storage and transportation and hydrogen utilization, wherein the key for realizing the development of the hydrogen energy industry is the high-efficiency hydrogen production technology and reducing the hydrogen operation cost.
Disclosure of Invention
The invention provides a method for preparing hydrogen and food-grade dry ice for a fuel cell by LNG (liquefied natural gas), aiming at the problems of high energy consumption and liquid hydrogen manufacturing cost of hydrogen liquefaction. The invention greatly reduces the preparation cost of the hydrogen and the food-grade dry ice, the prepared hydrogen can be applied to hydrogen for fuel cell traffic, and the food-grade dry ice can be widely applied to the fields of food and medicine.
Specifically, the method for preparing hydrogen and food-grade dry ice for the fuel cell by using LNG provided by the invention comprises the following steps:
1) after entering a carbon dioxide dry ice production working section, the pressurized LNG exchanges heat with purified carbon dioxide;
2) heating the natural gas after heat exchange and then entering a natural gas conversion section;
3) in the natural gas conversion section, the natural gas is subjected to conversion, transformation and pressure swing adsorption concentration, and the concentrated gas is hydrogen-rich gas meeting the requirement of hydrogen used by the fuel cell;
4) a purge gas outlet of a pressure swing adsorption section in the natural gas conversion section is a carbon dioxide-rich gas mixture, and the carbon dioxide-rich gas mixture is purified by a carbon dioxide purification section to obtain purified carbon dioxide; the total sulfur content in the purified gas is less than 0.1ppm, the benzene content is less than 0.02ppm, the total hydrocarbon content is less than 50ppm, and the carbon dioxide concentration is more than 99.99%;
the pressure swing adsorption unit divides the inlet gas into two streams, one is concentrated gas (hydrogen-rich gas meeting the requirements of the fuel cell), and the other is gas rich in carbon dioxide;
5) and after passing through a carbon dioxide purification working section, the purified carbon dioxide enters a carbon dioxide dry ice production working section, and exchanges heat with the LNG for cooling to prepare food-grade dry ice.
In the method, in the step 1), the LNG is pressurized to 0.3-5 MPaG by adopting a low-temperature LNG booster pump;
and heating the LNG to-20-0 ℃.
In the method, the LNG and the purified carbon dioxide exchange heat, and the temperature of the carbon dioxide is reduced to minus 80 ℃ to minus 40 ℃ after heat exchange.
In the method, in the step 2), the natural gas is heated to 600-1000 ℃;
in the step 3), the concentration of hydrogen in the hydrogen-rich gas is more than 99.9%.
The device directly and organically combines the LNG gasification process, the hydrogen preparation process, the carbon dioxide purification process and the dry ice preparation process, the energy is mutually utilized, the prepared hydrogen can be conveniently transported and utilized, the food-grade dry ice can be widely applied to the fields of food and medicine, the economy is good, the device has the advantages of simple process flow, high automation degree, reliable adopted equipment and remarkable economic benefit.
Drawings
Fig. 1 is a schematic flow diagram of an apparatus for preparing hydrogen and food grade dry ice for a fuel cell by using LNG according to the present invention.
Detailed Description
The experimental procedures used in the following examples are all conventional procedures unless otherwise specified.
Materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
In the embodiment, the LNG enters a nitrogen (or mixed refrigerant) cooling section to exchange heat with low-temperature refrigerant hydrogen after being pressurized, or the pressurized LNG directly enters a carbon dioxide dry ice production section to exchange heat; after heat exchange, the natural gas is heated and enters a natural gas conversion section to be converted into hydrogen-rich gas; the hydrogen-rich gas is concentrated by a pressure swing adsorption working section to prepare high-purity hydrogen; and (4) carrying out carbon dioxide-enriched gas at the outlet of the pressure swing adsorption working section to prepare the food-grade dry ice at the carbon dioxide dry ice making working section.
Examples 1,
(1) And after the pressurized LNG (3MPaG) enters a carbon dioxide dry ice production working section, exchanging heat with purified carbon dioxide, and heating to 0 ℃ (material flow 2-5-6).
(2) The heated natural gas is heated to 800 ℃ by a combustion furnace and then enters a natural gas conversion section (material flow 7-9).
(3) In the natural gas conversion section, after natural gas is converted, transformed and subjected to pressure swing adsorption concentration, a hydrogen-rich gas mixture (stream 9-10-12-14-16-19) with the hydrogen concentration of 99.99% is prepared.
(4) The outlet of the pressure swing adsorption working section is rich in carbon dioxide gas mixture, after passing through the carbon dioxide purification working section, the total sulfur content in the high-purity carbon dioxide gas mixture is 0.07ppm, the benzene content is 0.015ppm, the total hydrocarbon content is 350ppm, and the carbon dioxide concentration is more than 99.99% (material flow 15-14).
(5) After carbon dioxide concentrated by the carbon dioxide purification section enters the carbon dioxide dry ice production section, the carbon dioxide dry ice production section exchanges heat with LNG and is cooled to-79 ℃, and food-grade dry ice (material flow 14-15-19-22-20-17) is prepared.
Examples 2,
(1) And (3) after the pressurized LNG (2MPaG) enters a carbon dioxide dry ice production working section, heating to 5 ℃ (material flow 2-5-6).
(2) The heated natural gas is heated to 700 ℃ by a combustion furnace and then enters a natural gas conversion section (material flow 6-7).
(3) In the natural gas conversion section, after natural gas is converted, transformed and subjected to pressure swing adsorption concentration, a hydrogen-rich gas mixture (stream 9-10-14-16-17-19) with the hydrogen concentration of 99.99% is prepared.
(4) The outlet of the pressure swing adsorption section is rich in carbon dioxide gas mixture, and after passing through the carbon dioxide purification section, the total sulfur content in the high-purity carbon dioxide gas mixture is 0.06ppm, the benzene content is 0.012ppm, the total hydrocarbon content is less than 40ppm, and the carbon dioxide concentration is 99.994% (stream 15-25).
(5) After the high-purity carbon dioxide gas mixture enters a carbon dioxide dry ice production section, the high-purity carbon dioxide gas mixture exchanges heat with mixed refrigerant and is cooled to-50 ℃, and food-grade dry ice (material flow 25-26) is prepared.
Claims (4)
1. A method for preparing hydrogen and food-grade dry ice for a fuel cell by LNG comprises the following steps:
1) after entering a carbon dioxide dry ice production working section, the pressurized LNG exchanges heat with purified carbon dioxide or exchanges heat with nitrogen or mixed refrigerant and is heated;
2) heating the heated natural gas and then entering a natural gas conversion section;
3) in the natural gas conversion section, the natural gas is subjected to conversion, transformation and pressure swing adsorption concentration, and the concentrated gas is hydrogen-rich gas meeting the requirement of hydrogen used by the fuel cell;
4) a purge gas outlet of a pressure swing adsorption section in the natural gas conversion section is a carbon dioxide-rich gas mixture, and the carbon dioxide-rich gas mixture is purified by a carbon dioxide purification section to obtain purified carbon dioxide; the total sulfur content in the purified gas is less than 0.1ppm, the benzene content is less than 0.02ppm, the total hydrocarbon content is less than 50ppm, and the carbon dioxide concentration is more than 99.99%;
5) and the purified carbon dioxide enters the carbon dioxide dry ice production working section, exchanges heat with the LNG and is cooled, and food-grade dry ice is prepared.
2. The method of claim 1, wherein: in the step 1), a low-temperature LNG booster pump is adopted to boost the LNG to 0.3-5 MPaG;
and heating the LNG to-20-10 ℃.
3. The method according to claim 1 or 2, characterized in that: and exchanging heat between the LNG and the purified carbon dioxide, and cooling the carbon dioxide to-80-40 ℃ after heat exchange.
4. The method according to any one of claims 1-3, wherein: in the step 2), heating the natural gas to 600-1000 ℃;
in the step 3), the concentration of hydrogen in the hydrogen-rich gas is more than 99.9%.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010984398.2A CN112028016A (en) | 2020-09-16 | 2020-09-16 | Method for preparing hydrogen and food-grade dry ice for fuel cell by LNG |
| CN202011303976.8A CN112265960A (en) | 2020-09-16 | 2020-11-19 | Method for preparing hydrogen and food-grade dry ice for fuel cell by LNG |
| CN202022694965.9U CN214780743U (en) | 2020-09-16 | 2020-11-19 | Device of hydrogen and food grade dry ice for LNG preparation fuel cell |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010984398.2A CN112028016A (en) | 2020-09-16 | 2020-09-16 | Method for preparing hydrogen and food-grade dry ice for fuel cell by LNG |
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| CN112028016A true CN112028016A (en) | 2020-12-04 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN202010984398.2A Pending CN112028016A (en) | 2020-09-16 | 2020-09-16 | Method for preparing hydrogen and food-grade dry ice for fuel cell by LNG |
| CN202011303976.8A Pending CN112265960A (en) | 2020-09-16 | 2020-11-19 | Method for preparing hydrogen and food-grade dry ice for fuel cell by LNG |
| CN202022694965.9U Active CN214780743U (en) | 2020-09-16 | 2020-11-19 | Device of hydrogen and food grade dry ice for LNG preparation fuel cell |
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| Application Number | Title | Priority Date | Filing Date |
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| CN202011303976.8A Pending CN112265960A (en) | 2020-09-16 | 2020-11-19 | Method for preparing hydrogen and food-grade dry ice for fuel cell by LNG |
| CN202022694965.9U Active CN214780743U (en) | 2020-09-16 | 2020-11-19 | Device of hydrogen and food grade dry ice for LNG preparation fuel cell |
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Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112875644A (en) * | 2021-03-03 | 2021-06-01 | 中海石油气电集团有限责任公司 | System and method for hydrogen production and liquid carbon dioxide production by LNG |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| RU2085476C1 (en) * | 1993-04-22 | 1997-07-27 | Совместное предприятие Уральский научно-инженерный центр "Водород" | Method and installation for preparing extra-pure hydrogen |
| US20030021743A1 (en) * | 2001-06-15 | 2003-01-30 | Wikstrom Jon P. | Fuel cell refueling station and system |
| FR2877939B1 (en) * | 2004-11-16 | 2007-02-02 | Air Liquide | PROCESS AND PLANT FOR THE COMBINED PRODUCTION OF HYDROGEN AND CARBON DIOXIDE |
| CN104236252B (en) * | 2014-08-27 | 2016-06-22 | 华南理工大学 | LNG cold energy is utilized to prepare method and the device of liquid CO 2 and dry ice |
| CN110950304A (en) * | 2019-12-16 | 2020-04-03 | 简阳绿杉新能源设备有限公司 | Method for preparing high-purity hydrogen by using natural gas |
| CN110980646B (en) * | 2019-12-30 | 2023-08-18 | 华南理工大学 | System and method for preparing hydrogen from liquefied natural gas with CCS |
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2020
- 2020-09-16 CN CN202010984398.2A patent/CN112028016A/en active Pending
- 2020-11-19 CN CN202011303976.8A patent/CN112265960A/en active Pending
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| CN214780743U (en) | 2021-11-19 |
| CN112265960A (en) | 2021-01-26 |
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Application publication date: 20201204 |