CN113134282A - Flue gas decarbonizing agent - Google Patents
Flue gas decarbonizing agent Download PDFInfo
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- CN113134282A CN113134282A CN202110507091.8A CN202110507091A CN113134282A CN 113134282 A CN113134282 A CN 113134282A CN 202110507091 A CN202110507091 A CN 202110507091A CN 113134282 A CN113134282 A CN 113134282A
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- flue gas
- decarbonizer
- diphosphonic acid
- hydroxyethylidene diphosphonic
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
- B01D53/1493—Selection of liquid materials for use as absorbents
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
- B01D53/1456—Removing acid components
- B01D53/1475—Removing carbon dioxide
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
- B01D2252/50—Combinations of absorbents
- B01D2252/504—Mixtures of two or more absorbents
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/02—Other waste gases
- B01D2258/0283—Flue gases
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- General Chemical & Material Sciences (AREA)
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- Treating Waste Gases (AREA)
Abstract
The invention belongs to the technical field of gas treatment through chemical absorption, and discloses a flue gas decarbonizer which comprises, by mass, 39-50 parts of deionized water, 45-50 parts of N-methyldiethanolamine, 5-10 parts of monoethanolamine, 0.1-0.25 part of hydroxyethylidene diphosphonic acid, 0.015-0.06 part of hydroxyethylidene diphosphonic acid, 0.005-0.03 part of polyacrylic acid, 0.1-0.3 part of hydroxyl silicone oil, 0.01-0.03 part of tetradecyl dimethyl benzyl ammonium chloride and 0.3-0.5 part of sodium sulfite. The invention solves the problem that the exhausted flue gas contains more carbon dioxide and thus can cause adverse effect on the environment because the MEA solution is used as a decarbonizing agent at present and the decarbonization efficiency is about 90 percent.
Description
Technical Field
The invention belongs to the field of gas treatment through chemical absorption, and particularly relates to a flue gas decarbonizer.
Background
More power plant flue gas can be generated in a power system, and the main components of the power plant flue gas are carbon dioxide, sulfur dioxide, water vapor, nitrogen and oxygen, so that the direct emission can cause great influence on the environment. In order to meet the national proposed goals, the content of carbon dioxide in the discharged flue gas of the power plant needs to be reduced.
The carbon dioxide content in the power plant flue gas for controlling emission greatly depends on a capturing technology, the capturing technology mainly comprises capturing before combustion, oxygen-enriched combustion and capturing after combustion, wherein the capturing technology after combustion can meet the requirements of the characteristics of the existing power plant flue gas, and the engineering quantity is small, so that the method is used as the existing main carbon dioxide emission reduction method. The post-combustion trapping can be classified into a solvent absorption method, an adsorption method, a membrane separation method and a low-temperature separation method, wherein the solvent absorption method is a method which is widely applied and has a mature technology at present.
The solvent absorption method is to utilize a chemical absorption solvent to perform a reversible chemical reaction with carbon dioxide so as to achieve the purpose of absorbing and desorbing the carbon dioxide, so that the absorption effect of the chemical absorption solvent on the carbon dioxide is particularly important. Chemical absorption solvents commonly used at present include ammonia, ionic liquids, potassium carbonate solutions, and alcohol amine solutions.
The ammonia water has the advantages of low energy consumption and low corrosivity for capturing the carbon dioxide, but the ammonia water has high volatility, so a large amount of ammonia escapes in operation, and secondary pollution to the environment is easily caused. The ionic liquid has the characteristics of difficult combustion, good thermal stability, low steam pressure, excellent catalytic performance, functional group introduction and the like, but the ionic liquid is expensive and cannot be widely applied to the industry at present. The potassium carbonate solution has the characteristics of low cost, low energy consumption, high stability and the like, but the speed of absorbing carbon dioxide by the potassium carbonate is slow, and the corrosion is serious. The alcohol amine solution has the advantages of large load capacity, low price and the like as a chemical absorption solvent which is most widely applied at present, but the alcohol amine solution has defects, the absorption rate of carbon dioxide is about 90%, the absorption effect is poor, the energy consumption for desorbing the carbon dioxide accounts for 70-80% of the total trapping energy consumption, so that the desorption accounts for more than 60% of the whole trapping cost, and the cost of the whole process is high.
Therefore, in order to overcome the current dilemma, the inventor develops a chemical absorption solvent, and can make up for the defects of the existing chemical absorption solvent.
Disclosure of Invention
The invention aims to provide a flue gas decarbonizer to solve the problem that the decarbonizing efficiency of the existing decarbonizer which uses an alcohol amine solution is about 90 percent, so that the discharged flue gas contains more carbon dioxide, thereby causing adverse effect on the environment.
In order to achieve the purpose, the invention provides the following technical scheme that the smoke decarbonizer comprises, by mass, 39-50 parts of deionized water, 45-50 parts of N-methyldiethanolamine, 5-10 parts of monoethanolamine, 0.1-0.25 part of hydroxyethylidene diphosphonic acid, 0.015-0.06 part of hydroxyethylidene diphosphonic acid, 0.005-0.03 part of polyacrylic acid, 0.1-0.3 part of hydroxy silicone oil, 0.01-0.03 part of tetradecyl dimethyl benzyl ammonium chloride and 0.3-0.5 part of sodium sulfite.
The beneficial effects of the technical scheme are as follows:
1. in the technical scheme, through the configuration of the N-methyldiethanolamine and the monoethanolamine, interaction exists in the processes of absorbing and desorbing the carbon dioxide, namely the N-methyldiethanolamine and the monoethanolamine mutually promote absorption, and the absorption effect of the carbon dioxide is improved.
And the interaction is relevant with absorption time, and is crescent along with absorbing, then weakens, consequently at the initial stage with the flue gas contact, can be quick absorb carbon dioxide, and the content of carbon dioxide reduces in the later stage flue gas, and the interaction also reduces, and what slowly again absorbs remaining carbon dioxide, whole process can accomplish and absorb 97% above carbon dioxide in the flue gas.
In the desorption process, the interaction of the N-methyldiethanolamine and the monoethanolamine is completely opposite to that in the absorption process, and in the initial desorption stage, the interaction is rapidly reduced, so that the absorbed carbon dioxide is conveniently separated out, and the carbon dioxide is recycled after the desorption treatment is completed; in the later period of desorption, most of carbon dioxide is separated out, and the interaction rises again, so that the separation speed of the carbon dioxide is reduced; therefore, most of the carbon dioxide can be precipitated, and the precipitation rate of the carbon dioxide is high.
2. In the process of mutually matching and absorbing carbon dioxide by N-methyldiethanolamine and monoethanolamine, the hydroxyl silicone oil is prepared, so that no foaming can be ensured in the absorption process, and the absorption effect of the carbon dioxide is good.
3. The synergistic effect of the hydroxyethylidene diphosphonic acid, the sodium 2 and the polyacrylic acid effectively controls the corrosivity of acid gas generated in the process of absorbing carbon dioxide, is beneficial to prolonging the service life of equipment and reducing the use and maintenance cost of the equipment.
4. Tetradecyl dimethyl benzyl ammonium chloride can effectively control the growth of bacteria in the decarbonizer in the running process, and sodium sulfite in the decarbonizer can reduce the oxidative degradation of the decarbonizer, prolong the life cycle of the decarbonizer and reduce the running cost.
In conclusion, the flue gas decarbonizer prepared by the technical scheme has a good absorption effect on carbon dioxide in flue gas, and can enable the absorption rate of the carbon dioxide to reach more than 97%; meanwhile, the raw materials are configured, so that the preparation cost is low, the loading capacity is large, and the method can be widely popularized and applied in industry.
Further, 39 parts of deionized water, 50 parts of N-methyldiethanolamine, 10 parts of monoethanolamine, 0.1 part of hydroxyethylidene diphosphonic acid, 0.015 part of hydroxyethylidene diphosphonic acid, 0.005 part of polyacrylic acid, 0.1 part of hydroxyl silicone oil, 0.01 part of tetradecyl dimethyl benzyl ammonium chloride and 0.3 part of sodium sulfite.
Has the advantages that: experiments prove that the flue gas decarbonizer prepared according to the proportion has good absorption effect on carbon dioxide in flue gas.
Further, 50 parts of deionized water, 45 parts of N-methyldiethanolamine, 5 parts of monoethanolamine, 0.25 part of hydroxyethylidene diphosphonic acid, 0.06 part of hydroxyethylidene diphosphonic acid, 0.03 part of polyacrylic acid, 0.3 part of hydroxyl silicone oil, 0.03 part of tetradecyl dimethyl benzyl ammonium chloride and 0.5 part of sodium sulfite.
Has the advantages that: experiments prove that the flue gas decarbonizer prepared according to the proportion has good absorption effect on carbon dioxide in flue gas.
Further, 45 parts of deionized water, 47 parts of N-methyldiethanolamine, 8 parts of monoethanolamine, 0.18 part of hydroxyethylidene diphosphonic acid, 0.04 part of hydroxyethylidene diphosphonic acid, 0.015 part of polyacrylic acid, 0.2 part of hydroxyl silicone oil, 0.02 part of tetradecyl dimethyl benzyl ammonium chloride and 0.4 part of sodium sulfite.
Has the advantages that: experiments prove that the flue gas decarbonizer prepared according to the proportion has good absorption effect on carbon dioxide in flue gas.
Further, the preparation method comprises the following steps:
step one, adding N-methyldiethanolamine and monoethanolamine into deionized water in sequence, and mixing uniformly to obtain a primary solution for later use;
step two, uniformly mixing hydroxyethylidene diphosphonic acid, sodium hydroxyethylidene diphosphonate, sodium 2 and polyacrylic acid to obtain a mixed solution, and uniformly mixing the mixed solution with the primary solution to obtain a secondary solution for later use;
step three, adding tetradecyl dimethyl benzyl ammonium chloride and sodium sulfite into the secondary mixed solution, and uniformly mixing to obtain a tertiary mixed solution;
and step four, adding the hydroxyl silicone oil into the tertiary mixed solution, and uniformly mixing to obtain the smoke decarbonizer.
Has the advantages that: during preparation, the raw material components are added into deionized water according to the density from small to large, so that the components in the prepared flue gas decarbonizer are dispersed and balanced and fully dissolved, and the capture efficiency of carbon dioxide reaches an optimal value; and can be when carrying out desorption after the entrapment carbon dioxide, the quick carbon dioxide desorption of desorbing, the consumption of energy saving.
Further, the hydroxyl silicone oil is added into the three mixed solutions when decarburization is needed.
Has the advantages that: the hydroxyl silicone oil has poor solubility and is easy to break emulsion, and the smoke decarbonizer is used with strong mechanical circulation and stirring of liquid, so that the hydroxyl silicone oil is favorably and uniformly dispersed in the three-time mixed solution, and therefore, the hydroxyl silicone oil is added when the smoke decarbonizer is used, the hydroxyl silicone oil can exert the maximum effect, and the capture effect of the smoke decarbonizer on carbon dioxide in smoke can be improved.
In conclusion, the decarbonization rate of the flue gas decarbonizer provided by the invention can reach more than 97%, and the flue gas decarbonizer has the advantages of high use concentration, high acid gas load, foaming resistance, strong degradation resistance, low energy consumption, good chemical stability and low corrosivity. Under the same treatment gas amount, the flue gas decarbonizer provided by the invention has large absorption amount and low solution circulation amount, and can reduce the circulation energy consumption.
Detailed Description
The following is further detailed by way of specific embodiments:
example (b):
a flue gas decarbonizer comprises, by mass, 39-50 parts of deionized water, 45-50 parts of N-methyldiethanolamine, 5-10 parts of monoethanolamine, 0.1-0.25 part of hydroxyethylidene diphosphonic acid, 0.015-0.06 part of hydroxyethylidene diphosphonic acid sodium 2, 0.005-0.03 part of polyacrylic acid, 0.1-0.3 part of hydroxy silicone oil, 0.01-0.03 part of tetradecyl dimethyl benzyl ammonium chloride and 0.3-0.5 part of sodium sulfite.
A preparation method of a flue gas decarbonizer comprises the following steps:
step one, weighing all raw materials according to a ratio for later use, sequentially adding N-methyldiethanolamine and monoethanolamine into deionized water, and uniformly mixing to obtain a primary solution for later use;
step two, uniformly mixing hydroxyethylidene diphosphonic acid, sodium hydroxyethylidene diphosphonate, sodium 2 and polyacrylic acid to obtain a mixed solution, and uniformly mixing the mixed solution with the primary solution to obtain a secondary solution for later use;
step three, adding tetradecyl dimethyl benzyl ammonium chloride and sodium sulfite into the secondary mixed solution, and uniformly mixing to obtain a tertiary mixed solution;
and step four, when in use, adding the hydroxyl silicone oil into the tertiary mixed solution, and uniformly mixing to obtain the smoke decarbonizer.
The preparation is carried out at normal temperature and normal pressure.
Examples 1 to 5 differ only in the ratio of each raw material, and the specific parameters are shown in table 1.
TABLE 1
Experiment:
the following experiment was performed using the flue gas decarbonizers provided in examples 1 to 5 and the chemical absorption solution provided in comparative example, which is the MEA solution.
1. Absorption rate test of carbon dioxide
The test of the absorption rate of carbon dioxide was carried out under the experimental conditions of an experimental temperature of 40 ℃ and an experimental pressure of 5.7 Mpa. The volume ratio of each component in the flue gas for experiments is as follows: 14.15% CO2、6.4％O2、79.45％N2。
The specific experimental results are shown in table 2:
TABLE 2
As can be seen from Table 2, the decarburization effect of the flue gas decarbonizer provided by the invention is better than that of the MEA solution, the decarburization rate of the flue gas decarbonizer provided by the invention can reach more than 97%, and the decarburization rate can reach 98.1% at most, which is far better than that of the existing MEA solution.
2. Oxidation and thermal decomposition experiments
6 identical passivated iron containers were prepared, and 6 containers were charged with equal amounts of the decarburizing agent provided in examples 1-5 and the MEA solution provided in comparative example, respectively, and immersed in water baths, respectively. The water bath temperature is controlled to be 40-80 ℃, and the flue gas (the components of the flue gas are 14.15 percent CO) is introduced according to the same flow velocity2、6.4％O2、79.45％N2) And the outlet end of each iron container is provided with a condensing reflux device. After 400h of continuous operation, the solution was drawn off for detection, and the specific detection results are shown in table 3.
TABLE 3
As can be seen from Table 3, the flue gas decarbonizer provided by the invention has obviously better oxidation resistance and thermal decomposition resistance than the MEA solution.
In conclusion, the decarbonizing rate of the flue gas decarbonizer provided by the invention is higher than 97% under the high pressure of 5.7MPa, the highest decarbonizing rate can reach 98.1%, and the circulation amount of the decarbonizer is about 36% lower than that of an MEA solution. The comprehensive energy consumption of the flue gas decarbonizer in operating unit is 7720 MJ/104m3Compared with other decarbonizer processes, the energy consumption is reduced by more than 40 percent (the regeneration temperature of the process is 70-80 ℃, and the other regeneration temperatures are about 120 ℃).
It will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention, and these changes and modifications should not be construed as affecting the performance of the invention and its practical application.
Claims (6)
1. A kind of flue gas decarbonization agent, characterized by that: the paint comprises, by mass, 39-50 parts of deionized water, 45-50 parts of N-methyldiethanolamine, 5-10 parts of monoethanolamine, 0.1-0.25 part of hydroxyethylidene diphosphonic acid, 0.015-0.06 part of hydroxyethylidene diphosphonic acid, 0.005-0.03 part of polyacrylic acid, 0.1-0.3 part of hydroxyl silicone oil, 0.01-0.03 part of tetradecyl dimethyl benzyl ammonium chloride and 0.3-0.5 part of sodium sulfite.
2. The flue gas decarbonizer according to claim 1, wherein: 39 parts of deionized water, 50 parts of N-methyldiethanolamine, 10 parts of monoethanolamine, 0.1 part of hydroxyethylidene diphosphonic acid, 0.015 part of hydroxyethylidene diphosphonic acid, 0.005 part of polyacrylic acid, 0.1 part of hydroxyl silicone oil, 0.01 part of tetradecyl dimethyl benzyl ammonium chloride and 0.3 part of sodium sulfite.
3. The flue gas decarbonizer according to claim 1, wherein: 50 parts of deionized water, 45 parts of N-methyldiethanolamine, 5 parts of monoethanolamine, 0.25 part of hydroxyethylidene diphosphonic acid, 0.06 part of hydroxyethylidene diphosphonic acid, 0.03 part of polyacrylic acid, 0.3 part of hydroxyl silicone oil, 0.03 part of tetradecyl dimethyl benzyl ammonium chloride and 0.5 part of sodium sulfite.
4. The flue gas decarbonizer according to claim 1, wherein: 45 parts of deionized water, 47 parts of N-methyldiethanolamine, 8 parts of monoethanolamine, 0.18 part of hydroxyethylidene diphosphonic acid, 0.04 part of hydroxyethylidene diphosphonic acid, 0.015 part of polyacrylic acid, 0.2 part of hydroxyl silicone oil, 0.02 part of tetradecyl dimethyl benzyl ammonium chloride and 0.4 part of sodium sulfite.
5. The flue gas decarboniser according to any one of claims 1 to 4, characterised in that its preparation comprises the following steps:
step one, adding N-methyldiethanolamine and monoethanolamine into deionized water in sequence, and mixing uniformly to obtain a primary solution for later use;
step two, uniformly mixing hydroxyethylidene diphosphonic acid, sodium hydroxyethylidene diphosphonate, sodium 2 and polyacrylic acid to obtain a mixed solution, and uniformly mixing the mixed solution with the primary solution to obtain a secondary solution for later use;
step three, adding tetradecyl dimethyl benzyl ammonium chloride and sodium sulfite into the secondary mixed solution, and uniformly mixing to obtain a tertiary mixed solution;
and step four, adding the hydroxyl silicone oil into the tertiary mixed solution, and uniformly mixing to obtain the smoke decarbonizer.
6. The flue gas decarbonizer of claim 5, wherein: and adding the hydroxyl silicone oil into the three-time mixed solution when decarburization is required.
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Citations (6)
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| CN101362974A (en) * | 2007-08-06 | 2009-02-11 | 中国海洋石油总公司 | Absorbent for deeply removing carbon dioxide |
| CN101822932A (en) * | 2010-06-12 | 2010-09-08 | 中国石油集团工程设计有限责任公司 | Composite decarbonization solvent for eliminating carbon dioxide in natural gases |
| CN104513993A (en) * | 2013-10-08 | 2015-04-15 | 中国石油化工股份有限公司 | Corrosion inhibitor used for organic-amine-type acid gas absorption liquid |
| CN104548903A (en) * | 2013-10-09 | 2015-04-29 | 中国石油化工股份有限公司 | Organic amine solvent for capturing carbon dioxide |
| CN105664672A (en) * | 2016-04-05 | 2016-06-15 | 江苏大海能源科技有限公司 | Compound liquid decarbonizing agent for removing high-concentration CO2 in gas |
| US20210039040A1 (en) * | 2018-02-22 | 2021-02-11 | Sogang University Research Foundation | Carbon dioxide absorbent and method for separating out carbon dioxide by using same |
-
2021
- 2021-05-10 CN CN202110507091.8A patent/CN113134282A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101362974A (en) * | 2007-08-06 | 2009-02-11 | 中国海洋石油总公司 | Absorbent for deeply removing carbon dioxide |
| CN101822932A (en) * | 2010-06-12 | 2010-09-08 | 中国石油集团工程设计有限责任公司 | Composite decarbonization solvent for eliminating carbon dioxide in natural gases |
| CN104513993A (en) * | 2013-10-08 | 2015-04-15 | 中国石油化工股份有限公司 | Corrosion inhibitor used for organic-amine-type acid gas absorption liquid |
| CN104548903A (en) * | 2013-10-09 | 2015-04-29 | 中国石油化工股份有限公司 | Organic amine solvent for capturing carbon dioxide |
| CN105664672A (en) * | 2016-04-05 | 2016-06-15 | 江苏大海能源科技有限公司 | Compound liquid decarbonizing agent for removing high-concentration CO2 in gas |
| US20210039040A1 (en) * | 2018-02-22 | 2021-02-11 | Sogang University Research Foundation | Carbon dioxide absorbent and method for separating out carbon dioxide by using same |
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