CN110624363B - Pressurization regeneration method for capturing carbon dioxide in flue gas by alcohol amine method - Google Patents
Pressurization regeneration method for capturing carbon dioxide in flue gas by alcohol amine method Download PDFInfo
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
Abstract
The invention belongs to the technical field of gas separation, and relates to a pressurized regeneration method for capturing carbon dioxide in flue gas by an alcohol amine method. The method provided by the invention has the advantages of high thermal efficiency of regeneration reaction, remarkably reduced regeneration energy consumption, simple flow, no need of introducing external high-pressure gas for stripping, high heat utilization efficiency, high pressure of regenerated carbon dioxide and the like, and has good application prospect in the field of carbon dioxide capture.
Description
Technical Field
The invention belongs to the technical field of gas separation, and relates to a pressurizing regeneration method for capturing carbon dioxide in flue gas by an alcohol amine method.
Background
Consumption of fossil energy generates a large amount of carbon dioxide. Particularly, after the human beings have entered the industrial revolution, with the increasing consumption of fossil energy, more and more carbon dioxide is emitted into the atmosphere, so that the concentration of carbon dioxide in the atmosphere is continuously increased. On day 9 of 2019, the historically highest concentration of carbon dioxide in air recorded at the monnaura astronomical stage in hawaii has reached 414.27 ppm. Since carbon dioxide has a greenhouse effect, the increase of the concentration thereof has caused a series of serious environmental problems such as melting of glaciers in north and south, increase of extreme severe weather, and acidification of seawater. Thus, the abatement of carbon dioxide has attracted general attention from countries around the world.
The emission reduction of carbon dioxide mainly comprises the technologies of improving energy efficiency, using new energy, capturing carbon dioxide and the like. Wherein, the carbon dioxide capture technology after combustion is the most effective carbon dioxide emission reduction method aiming at the current global carbon dioxide maximum emission source, namely the flue gas of a coal-fired power plant. In the conventional technology for capturing carbon dioxide after flue gas combustion, the most widely applied technology is an alcohol amine absorption-heat regeneration process represented by Monoethanolamine (MEA). In order to obtain a high solvent absorption capacity, regeneration of the alkanolamine solvent is often carried out at a low (normal) pressure to ensure sufficient regeneration of the absorbed carbon dioxide.
However, in a low (normal) pressure state, the boiling point of the alcohol amine rich solution absorbing carbon dioxide is low, which makes the regeneration reaction rate low and the retention time required for the rich solution regeneration longer on one hand, and makes the water content in the gas regenerated under normal pressure high and makes a large amount of heat used for water gasification, reduces the heat utilization efficiency of the system, makes the process energy consumption for capturing carbon dioxide in the flue gas by the alcohol amine method higher, and cannot meet the needs of industrial production. Therefore, in view of the improvement of the operation pressure of the regeneration column, the development of a pressurized regeneration process of carbon dioxide by reducing the process energy consumption has been attracting attention of researchers.
Several gas pressure desorption techniques are disclosed in patents US Patent 20120009114 and US Patent 20140017622 by Carbon Capture Scientific, LLC. The company considers that the energy consumption of the desorption process mainly comprises three parts of sensible heat, reaction heat and stripping heat. Wherein, sensible heat is a damping of the heat exchange process, has no benefit to the desorption process and needs to be eliminated; the reaction heat is used for regenerating carbon dioxide, is a power source for desorption and must be utilized to the maximum extent; the gas stripping heat is mainly used for evaporating the water vapor brought out of the tower by the product carbon dioxide and should be reduced as much as possible. According to the company's patents, the high pressure stripping gas used may be any gas that is not detrimental to the solvent in the liquid and that does not interfere with the stripping system, including inorganic gases such as He, Ar, O2, N2, air, and mixtures thereof, or organic gases such as CH4, C2H6, C3H8, C4H10, C5H12, and mixtures thereof. The gas regenerated from the pressurized desorber often requires further treatment (rectification or reabsorption) to obtain CO2 of higher purity, but the partial pressure of CO2 is significantly higher than the partial pressure of CO2 in the acid gas regenerated from the conventional desorber. The examples show that the use of the pressure desorption process can effectively reduce the energy required by the regeneration process, compared with the traditional regeneration process of MEA, the total energy consumption of the MEA process using the pressure desorption can be reduced by 14%, and the total energy consumption of the MEA/MDEA composite process using the pressure desorption can be reduced by 25%.
The patent CN1089263, CN102641653, CN102675248 and the like of the Ministry of China disclose a pressure swing regeneration process, the process is mainly developed aiming at the hot potash decarburization technology, and in a decarburization solution regeneration system, a double-tower pressure swing regeneration flow consisting of a pressure flash evaporation section and a pressure stripping section of a pressure regeneration tower, an atmospheric pressure stripping section, a lean solution flash drum and a subsonic speed ejector is adopted in the process. Wherein the pressure range of the top of the pressurized regeneration tower is 0.14-0.18 MPa (absolute pressure), and CO2 regenerated gas from the top of the pressurized regeneration tower is used as power gas of a subsonic ejector to extract the normal-pressure stripping regeneration tower, so that the pressure range of the top of the normal-pressure stripping regeneration tower is 0.095-0.105 MPa (absolute pressure). The examples show that the process can reduce the regeneration energy consumption of the solution by 30 percent.
Although the gas pressure desorption technology developed by the carbon capture and utilization technology development company in the united states can obtain higher desorption pressure, external high-pressure stripping gas needs to be introduced, and the high-pressure stripping gas is further separated subsequently, so that the energy consumption of the regeneration process can be reduced by the technology, but the reduction of the total energy consumption of the process is very limited. Although the pressure swing regeneration process developed by the Ministry of chemistry research is widely applied, the hot potash decarburization technology is aimed at, the raw material gas is a pressurized circulating gas system, and the process is not suitable for a normal-pressure flue gas raw material system by firstly performing high-pressure regeneration and then performing normal-pressure regeneration and combining with an ejector extraction means, and is not applied to the alcohol amine method trapping process.
Therefore, the invention develops a pressurized regeneration process aiming at the process of capturing carbon dioxide in flue gas by an alcohol amine method from the aspects of improving the thermal efficiency of the regeneration process and reducing the regeneration energy consumption, can greatly reduce the energy consumption of the current flue gas carbon dioxide capturing process, and has wide application prospect.
Disclosure of Invention
1. The technical problem to be solved is as follows:
in the conventional technology for capturing carbon dioxide after flue gas combustion, the most widely applied technology is an alcohol amine absorption-heat regeneration process represented by Monoethanolamine (MEA). However, the process for capturing carbon dioxide in flue gas by the alcohol amine method has high energy consumption and cannot meet the requirements of industrial production.
For the gas pressure desorption technology developed by the carbon capture and utilization technology development company in the united states, the technology can reduce the energy consumption of the regeneration process, but the reduction of the total energy consumption of the process is very limited.
Although the pressure swing regeneration process developed by the Ministry of chemistry and research institute is widely applied, the process aims at the hot potash decarburization technology, the raw material gas is a pressurized circulating gas system, and the process is not suitable for a normal-pressure flue gas raw material system by firstly regenerating at high pressure and then regenerating at normal pressure and combining with an ejector extraction means.
2. The technical scheme is as follows:
in order to solve the problems, the invention provides a pressurized regeneration method for capturing carbon dioxide in flue gas by an alcohol amine method, which comprises the following steps: the carbon dioxide catching alcohol amine solution absorbs carbon dioxide in an absorption tower to obtain alcohol amine rich solution; step two: sending the alcohol amine rich solution to a normal pressure regeneration tower after heat exchange and heating; step three: desorbing part of the absorbed carbon dioxide in a normal-pressure regeneration tower, and desorbing oxygen dissolved in the pregnant solution to obtain semi-pregnant solution; step four: the semi-rich liquid is pressurized and subjected to heat exchange and then sent to a pressurizing regeneration tower; step five: and desorbing the residual carbon dioxide in the pressurized regeneration tower, and heating the desorbed solution and then circulating the solution to the absorption tower.
And the bottoms of the pressurizing regeneration tower and the normal-pressure regeneration tower are provided with regeneration heat sources, and the regeneration heat sources are steam with the pressure of 0.6MPa or more.
In the third step, the operating pressure of the atmospheric regeneration tower is 0-20 kPaG.
In the third step, the operating temperature of the normal pressure regeneration tower is 80-110 ℃.
In the fifth step, the operating pressure of the pressurized regeneration tower is 100-200 kPaG.
In the fifth step, the operating temperature of the pressurized regeneration tower is 100-150 ℃.
CO is generated by the normal pressure regeneration tower and the pressurization regeneration tower2The ratio of (A) to (B) is 0.05-0.3: 1.
The solute of the carbon dioxide capture alcohol amine solution is one or More of Ethanolamine (MEA), Diethanolamine (DEA), Triethanolamine (TEA), Diisopropanolamine (DIPA), N-Methyldiethanolamine (MDEA) and steric hindrance amine, and the mass content of the solute in the solvent is 50-90%.
The raw material gas is power plant flue gas, chemical plant flue gas and steel plant flue gas.
The content of carbon dioxide in the applicable raw materials is 5-25%.
3. Has the advantages that:
the pressure regeneration method for capturing the carbon dioxide in the flue gas by the alcohol amine method provided by the invention has the following advantages:
the heat required by water gasification in the regeneration process is reduced, so that the heat efficiency of the regeneration reaction is improved, and the regeneration energy consumption is reduced; the process is simple, external high-pressure gas is not required to be introduced for lifting gas, and subsequent separation operation is avoided; the heat utilization efficiency is high, the heating steam heats the tower kettle of the pressurized regeneration tower and the tower kettle of the normal pressure regeneration tower in sequence, and the waste heat of the heating steam can be fully utilized; the pressure of the regenerated carbon dioxide is high, and the power consumption required by the subsequent carbon dioxide compression can be reduced.
Drawings
FIG. 1 is a process flow diagram of the present invention.
FIG. 2 is a flow chart of a conventional process.
Detailed Description
The present invention will be described in detail below with reference to the drawings and examples.
The percentages in the examples are mass ratios.
Example 1
Example 1 is a prior art process having the following steps:
the first step is as follows: the apparatus shown in fig. 2 is used for carrying out an atmospheric regeneration test, only the atmospheric regeneration tower 2 is used, and the regenerated solution is directly sent to the absorption tower 1 after heat exchange by a pump, which is a traditional atmospheric regeneration process.
The second step is that: the raw material gas is simulated flue gas and CO2Content 10v%, O2The content is 6v%, and the rest is N2，CO2The trapping rate was 90%, the solution used was a 30w% aqueous monoethanolamine solution, the absorption temperature was 40 ℃ and the absorption pressure was normal pressure.
The third step: the pressure at the top of the normal pressure regeneration tower 2 is 2 KPaG, the temperature at the bottom of the tower is 101 ℃, the temperature at the top of the tower is 90 ℃, and the pressure of heating steam is 0.6 MPa.
The fourth step: CO obtained by testing2The unit trapping energy consumption is 56.9 KWH/Kmol CO2。
Example 2
The first step is as follows: a pressurized regeneration test was performed using the apparatus shown in fig. 1.
The second step is that: the raw material gas is simulated flue gas and CO2Content 10v%, O2The content is 6v%, and the rest is N2，CO2The trapping rate was 90%, the solution used was a 30w% aqueous monoethanolamine solution, the absorption temperature was 40 ℃ and the absorption pressure was normal pressure.
The third step: the pressure at the top of the normal pressure regeneration tower 2 is 2 KPaG, the temperature at the bottom of the tower is 101 ℃, the temperature at the top of the tower is 90 ℃, the pressure at the top of the pressurized regeneration tower 3 is 180 KPaG, the temperature at the bottom of the tower is 132 ℃, the temperature at the top of the tower is 120 ℃, and the pressure of heating steam is 0.6 MPa. Regenerating CO from the atmospheric regeneration tower 2 and the pressurized regeneration tower 32In a ratio of 0.09: 1.
The fourth step: CO obtained by testing2The unit trapping energy consumption is 33.5 KWH/Kmol CO2。
Example 3
The first step is as follows: a pressurized regeneration test was performed using the apparatus shown in fig. 1.
The second step is that: the raw material gas is simulated flue gas, the content of CO2 is 15v%, the content of O2 is 5v%, the balance is N2, the CO2 trapping rate is 90%, the used solution is 30w% monoethanolamine aqueous solution, the absorption temperature is 40 ℃, and the absorption pressure is normal pressure.
The third step: the pressure at the top of the normal pressure regeneration tower 2 is 5KPaG, the temperature at the bottom of the tower is 102 ℃, the temperature at the top of the tower is 92 ℃, the pressure at the top of the pressurized regeneration tower 3 is 190KPaG, the temperature at the bottom of the tower is 133 ℃, the temperature at the top of the tower is 121 ℃, and the pressure of heating steam is 0.6 MPa. The ratio of CO2 regenerated by the atmospheric regeneration tower 2 and the pressurized regeneration tower 3 is 0.12: 1.
The fourth step: the CO2 unit energy consumption for capture obtained by the test is 30.1 KWH/Kmol CO 2.
Example 4
The method of the embodiment has the following steps:
the first step is as follows: a pressurized regeneration test was performed using the apparatus shown in fig. 1.
The second step is that: the raw material gas is simulated flue gas and CO2Content 8v%, O2The content is 9v%, and the rest is N2，CO2The trapping rate was 90%, and the solution used was a 30w% aqueous solution of alkanolamine (in which the content of monoethanolamine was 20w% and the content of N-methyldiethanolamine was 10%), the absorption temperature was 40 ℃ and the absorption pressure was normal pressure.
The third step: the pressure at the top of the normal pressure regeneration tower 2 is 10 KPaG, the temperature at the bottom of the tower is 104 ℃, the temperature at the top of the tower is 93 ℃, the pressure at the top of the pressure regeneration tower 3 is 150 KPaG, the temperature at the bottom of the tower is 128 ℃, the temperature at the top of the tower is 117 ℃, and the pressure of heating steam is 0.6 MPa. Regenerating CO from the atmospheric regeneration tower 2 and the pressurized regeneration tower 32In a ratio of 0.25: 1.
The fourth step: CO obtained by testing2The unit trapping energy consumption is 28.6 KWH/Kmol CO2。
Example 5
The method of the embodiment has the following steps:
the first step is as follows: a pressurized regeneration test was performed using the apparatus shown in fig. 1.
The second step is that: the raw material gas is simulated flue gas and CO2Content 10v%, O2The content is 6v%, and the rest is N2，CO2The trapping rate is 90%, the solution used is 30w% aqueous solution of alcohol amine (wherein the content of monoethanolamine is 15w%, the content of N-methyldiethanolamine is 5%, the content of sterically hindered amine 2-amino-2-methyl-1-propanol is 10%), the absorption temperature is 40 ℃, and the absorption pressure is normal pressure.
The third step: the pressure at the top of the normal pressure regeneration tower 2 is 5KPaG, the temperature at the bottom of the tower is 102 ℃, the temperature at the top of the tower is 91 ℃, the pressure at the top of the pressurized regeneration tower 3 is 120 KPaG, the temperature at the bottom of the tower is 125 ℃, the temperature at the top of the tower is 113 ℃, and the pressure of heating steam is 0.6 MPa. Regenerating CO from the atmospheric regeneration tower 2 and the pressurized regeneration tower 32In a ratio of 0.22: 1.
The fourth step: CO obtained by testing2The unit trapping energy consumption is 29.8 KWH/Kmol CO2。
Example 6
The method of the embodiment has the following steps:
the first step is as follows: a pressurized regeneration test was performed using the apparatus shown in fig. 1.
The second step is that: the raw material gas is simulated flue gas and CO2Content 12v%, O2The content is 8v%, and the rest is N2，CO2The trapping rate is 90%, the solution used is 30w% aqueous solution of alcohol amine (wherein the content of monoethanolamine is 15w%, the content of sterically hindered amine 2-piperidine ethanol is 15%), the absorption temperature is 40 ℃, and the absorption pressure is normal pressure.
The third step: the pressure at the top of the normal pressure regeneration tower 2 is 15KPaG, the temperature at the bottom of the tower is 106 ℃, the temperature at the top of the tower is 94 ℃, the pressure at the top of the pressure regeneration tower 3 is 150 KPaG, the temperature at the bottom of the tower is 127 ℃, the temperature at the top of the tower is 116 ℃, and the pressure of heating steam is 0.6 MPa. Regenerating CO from the atmospheric regeneration tower 2 and the pressurized regeneration tower 32In a ratio of 0.27: 1.
The fourth step: CO obtained by testing2The unit trapping energy consumption is 31.5 KWH/Kmol CO2。
Example 7
The method of the embodiment has the following steps:
the first step is as follows: the apparatus of the figure was used to perform a pressurized regeneration test.
The second step is that: the raw material gas is simulated flue gas and CO2Content 20v%, O2The content is 8v%, and the rest is N2，CO2The trapping rate was 90%, and the solution used was a 30w% MEA solution (in which the monoethanolamine content was 30w%, the water content was 40%, and the N-methylpyrrolidone content was 30%), the absorption temperature was 40 ℃ and the absorption pressure was normal pressure.
The third step: the pressure at the top of the normal pressure regeneration tower 2 is 4 KPaG, the temperature at the bottom of the tower is 100 ℃, the temperature at the top of the tower is 85 ℃, the pressure at the top of the pressure regeneration tower 3 is 160 KPaG, the temperature at the bottom of the tower is 121 ℃, the temperature at the top of the tower is 110 ℃, and the pressure of heating steam is 0.6 MPa. Regenerating CO from the atmospheric regeneration tower 2 and the pressurized regeneration tower 32In a ratio of 0.17: 1.
The fourth step: CO obtained by testing2The unit trapping energy consumption is 27.7 KWH/Kmol CO2。
As can be seen from examples 2 to 7, CO2The unit trapping energy consumption is not more than 33.5 KWH/Kmol CO2，CO obtained in best example 72The unit trapping energy consumption is 27.7 KWH/Kmol CO2. Is far lower than 56.9 KWH/Kmol CO obtained by the prior traditional technology2。
The invention develops a pressurized regeneration process aiming at the process of capturing carbon dioxide in flue gas by an alcohol amine method from the aspects of improving the thermal efficiency of the regeneration process and reducing the regeneration energy consumption, can greatly reduce the energy consumption of the current flue gas carbon dioxide capture process, and has wide application prospect.
Although the present invention has been described with reference to the preferred embodiments, it should be understood that various changes and modifications can be made therein by those skilled in the art without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (8)
1. A pressurizing and regenerating method for capturing carbon dioxide in flue gas by an alcohol amine method comprises the following steps: the carbon dioxide catching alcohol amine solution absorbs carbon dioxide in an absorption tower (1) to obtain alcohol amine rich solution; step two: the alcohol amine rich solution is sent to a normal pressure regeneration tower (2) after heat exchange and heating; step three: desorbing part of absorbed carbon dioxide in an atmospheric pressure regeneration tower (2), and desorbing oxygen dissolved in the pregnant solution to obtain a semi-pregnant solution, wherein the operating pressure of the atmospheric pressure regeneration tower (2) is 2-15 kPaG; step four: the semi-rich liquid is pressurized and subjected to heat exchange and then is sent into a pressurized regeneration tower (3); step five: and desorbing the residual carbon dioxide in the pressurized regeneration tower (3), heating the desorbed solution, and circulating the solution to the absorption tower, wherein the operating pressure of the pressurized regeneration tower (3) is 120-190 kPaG.
2. The method of claim 1, wherein: and the bottoms of the pressurized regeneration tower (3) and the normal-pressure regeneration tower (2) are provided with regeneration heat sources, and the regeneration heat sources are steam with the pressure of 0.6 MPa.
3. The method of claim 1, wherein: in the third step, the operating temperature of the normal pressure regeneration tower (2) is 80-110 ℃.
4. The method of claim 1, wherein: in the fifth step, the operating temperature of the pressurized regeneration tower (3) is 100-150 ℃.
5. The method of any one of claims 1-4, wherein: CO is generated by the atmospheric regeneration tower (2) and the pressurized regeneration tower (3)2The ratio of (A) to (B) is 0.05-0.3: 1.
6. The method of any one of claims 1-4, wherein: the solute of the carbon dioxide capture alcohol amine solution is one or more of ethanolamine, diethanolamine, triethanolamine, diisopropanolamine, N-methyldiethanolamine and steric hindrance amine, and the mass content of the solute in the solvent is 50-90%.
7. The method of any one of claims 1-4, wherein: the raw material gas is power plant flue gas, chemical plant flue gas and steel plant flue gas.
8. The method of claim 7, wherein: the content of carbon dioxide in the applicable raw materials is 5-25%.
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| CN102641653B (en) * | 2012-04-25 | 2014-05-21 | 中国石油化工股份有限公司 | Technology of carbon dioxide removal from reaction recycle gas of vinyl acetate monomer |
| CN102895860B (en) * | 2012-09-29 | 2015-01-07 | 华北电力大学 | Method and system for reducing consumption in capturing process of CO2 through chemical absorption |
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| CN1091332A (en) * | 1993-02-25 | 1994-08-31 | 南京化学工业(集团)公司研究院 | Polyamine process removes carbon dioxide and sulfide in the gas |
| CN102553396A (en) * | 2011-12-23 | 2012-07-11 | 武汉凯迪工程技术研究总院有限公司 | Method for trapping carbon dioxide in flue gas of power station with high efficiency and low energy consumption and equipment adopting same |
| CN103768895A (en) * | 2012-10-23 | 2014-05-07 | 中国石油化工股份有限公司 | Method for low-energy consumption removal of carbon dioxide by hot potash |
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