CN112387072A - CO capture by absorption2Method and system of - Google Patents
CO capture by absorption2Method and system of Download PDFInfo
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- CN112387072A CN112387072A CN201910760615.7A CN201910760615A CN112387072A CN 112387072 A CN112387072 A CN 112387072A CN 201910760615 A CN201910760615 A CN 201910760615A CN 112387072 A CN112387072 A CN 112387072A
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- 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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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- 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
- B01D53/1418—Recovery of products
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- 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
- B01D53/1425—Regeneration of liquid absorbents
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- 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
- B01D53/18—Absorbing units; Liquid distributors therefor
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- B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
- B01D2252/20—Organic absorbents
- B01D2252/202—Alcohols or their derivatives
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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
- B01D2252/20—Organic absorbents
- B01D2252/204—Amines
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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
- B01D2252/20—Organic absorbents
- B01D2252/204—Amines
- B01D2252/20478—Alkanolamines
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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
- B01D2252/30—Ionic liquids and zwitter-ions
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01D2258/00—Sources of waste gases
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
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- Y02C20/40—Capture or disposal of greenhouse gases of CO2
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Abstract
The invention relates to the field of carbon dioxide capture, and discloses a method for capturing CO by an absorption method2Methods and systems of (1). The method comprises the following steps: (1) mixing the absorption liquid containing absorbent with CO2Flue gas contact for CO2The decarbonized flue gas is obtained, and the absorption liquid is used for capturing CO2Becoming absorption pregnant solution; (2) the absorption rich solution is contacted with the carried gas phase for desorption and regeneration to obtain CO2Stripping gas and CO removal2The absorption lean solution of (3); (3) the desorption gas is recovered, and the absorption barren solution is returned to the step (1) to participate in the absorption and capture; wherein the amount of the absorbent and/or water contained in the absorption liquid in the controlling step (1) is determined by measuring the electrical conductivity of the absorption rich liquid and the absorption lean liquid on line. Can improve the CO capture by a measuring absorption method2The measurement efficiency of the parameters is controlled in the process, and better long-period CO monitoring is realized2Trapping process and low energy consumption.
Description
Technical Field
The invention relates to the field of carbon dioxide capture, in particular to CO capture by an absorption method2Methods and systems of (1).
Background
The global warming is more and more serious, and particularly in 2018, the high temperature of more than 30 ℃ is rare in the arctic, so that carbon emission reduction is imperative. Solvent method for capturing CO2Is the most mature CO which is most likely to be popularized on a large scale at present2Trapping technology, concentration of absorption liquid to CO in solution method trapping technology2The trapping effect is greatly affected, and the concentration of the absorbent is always affected by various factors in actual operation, so that the concentration of the absorbent is difficult to keep constant.
CN102553396A provides a method for capturing carbon dioxide in power station flue gas with high efficiency and low energy consumption, which comprises the following steps: 1) mixing organic amine, ionic liquid and water according to the molar ratio of the organic amine to the ionic liquid (1-1.1):1 to obtain a composite absorbent aqueous solution, wherein the concentration of the composite absorbent aqueous solution is 20-40 wt%; taking a composite absorbent aqueous solution consisting of organic amine and ionic liquid as CO2The absorbent is used for uniformly spraying the composite absorbent aqueous solution into the tail flue gas of the power station boiler subjected to conventional dust removal and desulfurization treatment, so that the upward flue gas is fully and reversely contacted with the downward sprayed composite absorbent aqueous solution, and CO in the flue gas2The gas and the composite absorbent are subjected to gas-liquid two-phase chemical reaction and absorbed; controlling the liquid-gas ratio at 5-25L/m3Range of (1), CO in flue gas2The reaction temperature of the composite absorbent and the aqueous solution of the composite absorbent is in the range of 40-55 ℃, and the reaction pressure is 0.01-10 atm; to generate rich A.CO2And B. CO2Wherein A is organic amine and B is ionic liquid; 2) rich in A.CO2And B. CO2The liquid is formed by self-coagulation and standing clarificationA liquid layer; rich in A.CO2And B. CO2The liquid is in the lower layer, the composite absorbent aqueous solution is in the upper layer, and then the lower layer solution is separated to obtain the solution rich in A and CO2And B. CO2The mixed liquid of (4); the separated rich A and CO2And B. CO2The mixed liquid is subjected to heat exchange and is rich in A and CO2And B. CO2Part of CO dissolved or adsorbed by the composite absorbent aqueous solution in the mixed liquid2The gas is evaporated to obtain heat exchange gas rich in A and CO2And B. CO2The mixed liquid of (4); 3) the heat exchange is carried out to obtain rich A.CO2And B. CO2The mixed liquid of (2) is subjected to heating desorption treatment to chemically absorb CO2Is resolved out and regenerated to obtain high-concentration CO2Gas and composite absorbent aqueous solution; 4) returning the composite absorbent aqueous solution obtained in the step 3) to the step 1) as CO2The absorbent is continuously recycled; 5) for the high concentration CO separated in the step 3)2Cooling the gas to condense hot water vapor contained in the gas; 6) for the high concentration CO cooled in the step 5)2Gas-liquid separation treatment is carried out on the gas to remove condensed water in the gas, and CO with the purity of more than or equal to 99 percent is obtained2A gas; 7) CO with the purity of more than or equal to 99 percent obtained in the step 6)2And further drying the gas, compressing and condensing the gas to change the gas into liquid, and preparing the high-concentration industrial liquid carbon dioxide finished product. However, during the regeneration of the absorbent, the patent uses direct heating to absorb the CO2And (4) carrying out desorption. Although the patent reduces the energy consumption by a new absorbent, the patent does not relate to the influence of carrying gas on the energy consumption of the regeneration process, and limits the method to large-scale CO2Use of a trapping process.
《Results from MEA testing at the CO2Technology Centre Mongstad. part II: Verification of Baseline results (in MongstadCO)2Results of MEA tests performed by technical center, second section: verification of baseline results, David Thimsen, etc., Energy Procedia 63(2014)5938-2In the case of CO2In the process of trapping, the concentration of the solution, the water balance and the CO in the absorption liquid2The amount of load will vary. In the article, the concentration of MEA in ethanolamine solution is analyzed by using acid-base titration in a laboratory, whether water is supplemented into the system or the MEA solvent is determined by the concentration of the MEA, and CO in absorption liquid is analyzed by using acid-base titration2The amount of the supported.
CN104772021B provides a method for capturing CO in gas generated in industrial production process by using polyalcohol-ethylenediamine aqueous solution2The main carbon capturing component in the polyhydric alcohol-ethylenediamine aqueous solution is ethylenediamine, the polyhydric alcohol is a fixing agent of the ethylenediamine, the polyhydric alcohol-ethylenediamine aqueous solution and the CO-containing2After the gas is contacted, absorbing CO in the gas2Purifying the gas; the main component of the polyalcohol-ethylenediamine aqueous solution is ethylenediamine, and polyalcohol is added simultaneously to form the polyalcohol-ethylenediamine aqueous solution, which comprises the following components: the mass percentage of the ethylenediamine is as follows: ethylene diamine is more than or equal to 3.00 percent and less than 15.00 percent; 4.00 percent or more and less than 30.00 percent of polyol; the water comprises the following components in percentage by mass: 55.00 percent < water is less than or equal to 93.00 percent; the polyhydric alcohol comprises at least one of ethylene glycol, glycerol, butanediol, diethylene glycol, triethylene glycol, polyethylene glycol 100, polyethylene glycol 200, polyethylene glycol 300, polyethylene glycol 400 and polyethylene glycol 600. Can be well suitable for CO in the industrial production process2Trapping and reducing the volatilization of amine, and can obviously reduce the trapping cost. However, this patent does not deal with the effect of the carrier gas on the capture regeneration process, which would restrict the industrial CO in the process2Further popularization in the trapping process.
《A parametric study of CO2Capture from Gas-fired power plants using Monoethanolamine (MEA) study of parameters for carbon dioxide capture from Gas power plants, and regeneration temperature, regeneration pressure, reboiler power, absorbent concentration, CO-2Concentration isoparametric pair of CO2The influence of the trapping rate and the energy consumption is shown by experiments when the CO is used2When the collection rate is 85 percent, the energy consumption of the collection device reaches 3.7GJ/tCO2. However, the CO obtained in this study2The capture rate is less than 90% of the normal requirement of industrial grade, and the energy consumption is increased significantly to meet the requirement of industrial grade, but the deep investigation is not carried out in the literature. In addition, the article adopts steam as stripping gas, so that a part of steam energy consumption can be increased, and other gases in a power plant are not considered as carrying gas to investigate the regeneration energy consumption.
It can be seen that the absorption method traps CO2Improved monitoring of long-term CO2Method of a capture process to enhance the capture of CO by absorption2The process of (1) for the absorbent concentration and CO in the lean and rich liquor2The measurement efficiency of the load and the problem of how to reduce the energy consumption.
Disclosure of Invention
The invention aims to improve the CO capture by an absorption method2The method of (1) solves the problems of controlling the concentration of the absorbent in the lean and rich solution and reducing the energy consumption, and provides an absorption method for capturing CO2Methods and systems of (1).
In order to achieve the above object, the first aspect of the present invention provides a method for capturing CO by controlled absorption2The method of (1), comprising:
(1) mixing the absorption liquid containing absorbent with CO2Flue gas contact for CO2The decarbonized flue gas is obtained, and the absorption liquid is used for capturing CO2Becoming absorption pregnant solution;
(2) desorbing and regenerating the absorption rich solution to obtain CO-containing gas2Stripping gas and CO removal2The absorption lean solution of (3);
(3) the desorption gas is recovered, and the absorption barren solution is returned to the step (1) to participate in the absorption and capture;
wherein the amount of the absorbent and/or water contained in the absorption liquid in the controlling step (1) is determined by measuring the electrical conductivity of the absorption rich liquid and the absorption lean liquid on line.
A second aspect of the invention provides a system for implementing the method of the invention, comprising:
an absorption tower for absorbing liquid containing absorbent and CO2Flue gas contact for CO2The obtained decarbonized flue gas is discharged outside, and the absorption liquid captures CO2Becoming absorption pregnant solution;
a regeneration tower for desorbing and regenerating the absorption rich liquid to obtain CO2The stripping gas is discharged from the exhaust line, resulting in CO-depleted gas2The absorption barren solution returns to the absorption tower; and
and the conductivity tester is arranged on a pipeline for conveying the absorption rich solution or a pipeline for conveying the absorption lean solution and is used for measuring the conductivity of the absorption rich solution or the absorption lean solution on line.
Through the technical scheme, the method provided by the invention realizes monitoring of the concentration of the absorbent in the absorption liquid and better long-period monitoring of CO by means of online measurement of the conductivity of the absorption rich liquid or the absorption lean liquid2Trapping process and increasing CO in desorbed gas2The concentration of (A) is more than 98 volume percent, which is beneficial to reducing CO capture2Energy consumption of (2). Further adopting the carrier gas to participate in desorption regeneration, the method provided by the invention can ensure the realization of CO2The highest energy consumption can reach less than 3.9GJ/tCO under the requirement that the capture removal rate is more than 90 percent2。
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
In a first aspect, the invention provides an absorption process for capturing CO2The method of (1), comprising:
(1) mixing the absorption liquid containing absorbent with CO2Flue gas contact for CO2The decarbonized flue gas is obtained, and the absorption liquid is used for capturing CO2Becoming absorption pregnant solution;
(2) subjecting the absorption rich solution toDesorption and regeneration to obtain CO2Stripping gas and CO removal2The absorption lean solution of (3);
(3) the desorption gas is recovered, and the absorption barren solution is returned to the step (1) to participate in the absorption and capture;
wherein the amount of the absorbent and/or water contained in the absorption liquid in the controlling step (1) is determined by measuring the electrical conductivity of the absorption rich liquid and the absorption lean liquid on line.
According to a preferred embodiment of the desorption regeneration in step (2), the desorption regeneration method comprises: heating the absorption rich solution to enable CO to be generated2Desorbing from the absorption rich liquid; the stripping gas also contains water. The desorption gas contains CO2。
In this embodiment, the desorbed gas is condensed and separated into CO and gas2Product gas and condensed water.
Preferably, the condensed water is returned to the absorption trapping of the step (1) or the desorption regeneration of the step (2); or washing the decarbonized flue gas by the condensed water to remove the absorbent contained in the decarbonized flue gas, and returning the obtained washing water to the absorption and trapping in the step (1) or the desorption and regeneration in the step (2).
According to the present invention, preferably, the heating conditions include: the temperature is 110 ℃ and 150 ℃, and the pressure is 0.1-0.5 MPa.
The invention provides another specific implementation mode of desorption regeneration, and preferably, the desorption regeneration method in the step (2) is as follows: contacting the absorption rich solution with a carrier gas to make CO contact2Desorbing from the absorption rich liquid; wherein the desorption gas also contains a carrier gas. And can desorb CO in gas2The concentration reaches more than 98 volume percent. Has better CO2And (4) a trapping effect.
According to the invention, preferably, the carrier gas is selected from N2Air, flue gas, CO of different concentrations2One or more of the gases.
According to the invention, the flow rate of the carrier gas is preferably 0.1 to 50L/min.
According to the invention, the contact time is preferably 1 to 20min, the contact temperature is 100 ℃ to 130 ℃, and the contact pressure is 0.1 to 0.5 MPa.
In the present invention, preferably, the desorption regeneration in step (2) is performed in a regeneration tower, and the desorption regeneration comprises: heating the regeneration tower, introducing a certain amount of carrier gas from the tower bottom, and making the carrier gas in the regeneration tower be in countercurrent contact with the absorption rich liquid sprayed from the tower top of the regeneration tower to make CO be in countercurrent contact with the absorption rich liquid2Desorbing from the absorption rich solution to obtain CO-containing gas at the tower top2The absorption barren solution is obtained at the bottom of the tower.
According to the present invention, preferably, the absorbent is selected from one or more of ethanolamine, triethanolamine, N-methyldiallylamine, N-methyldiethanolamine, diethylenetriamine, triethylenetetramine, pentaethylenehexamine, 2-amino-2-methyl-1-propanol, piperazine, ionic liquid and alcohol. One or more of ethanolamine, triethanolamine, piperazine, ionic liquid and alcohol are preferred. Wherein the ionic liquid is at least one of triethylene tetramine nitrate, triethylene tetramine lactate, tetraethylenepentamine pentamine nitrate and tetraethylenepentamine lactate. The alcohol is selected from at least one of methanol, ethanol, ethylene glycol and propanol.
According to the present invention, preferably, the concentration of the absorbing solution is 5 to 60% by weight. I.e. the content of the absorbent in the absorption liquid.
According to the present invention, preferably, the conditions of absorption trapping include: the absorption liquid and the CO-containing component2The mass ratio of the smoke is 1:1-5: 1; the absorption and trapping temperature is 20-60 ℃; the absorption and trapping pressure is normal pressure, for example, 0.1 to 0.2 MPa.
According to the invention, preferably, the CO is contained2The composition of the flue gas comprises: 6-85% by volume CO2The content is not higher than 35mg/m3SO of (A)xThe content of the active carbon is not higher than 50mg/m3NO ofxThe content of the sodium hydroxide is not higher than 5mg/m3The dust of (2). Treating such CO-containing2The method provided by the invention can effectively realize CO2Can be CO2Trapping and removing rateGreater than 90%.
In the embodiment provided by the invention, the on-line measurement of the conductivity of the absorption rich liquid or the absorption lean liquid can be realized by installing a line conductivity measuring instrument on a pipeline for conveying the absorption rich liquid or the absorption lean liquid respectively, then the concentration of the absorbent in the absorption rich liquid or the absorption lean liquid is fed back according to the relation between the conductivity and the concentration of the absorbent (additionally preparing the absorption liquid with different absorbent concentrations, measuring the conductivity, then carrying out calculation fitting on the conductivity value and the absorbent concentration in the absorption liquid to obtain a fitting equation of the relation between the conductivity and the absorbent concentration), and further the dosage adjustment of the absorbent or water for the absorption liquid is controlled.
When the measured conductivity reflects that the concentration of the absorbent in the absorption rich liquid or the absorption lean liquid is lower than that in the initial absorption liquid, the absorption liquid needs to be supplemented with the absorbent;
when the measured conductivity reflects that the concentration of the absorbent in the absorption rich liquid or the absorption lean liquid is higher than the concentration of the absorbent in the initial absorption liquid, the absorption liquid needs makeup water.
The method provided by the invention can obtain CO2In the stripping gas of (2), CO2The concentration is higher and reaches more than 98 percent by volume, which is higher than the requirement of common industrial grade, and better CO is obtained2And (4) a trapping effect.
A second aspect of the invention provides a system for implementing the method of the invention, comprising:
an absorption tower for absorbing liquid containing absorbent and CO2Flue gas contact for CO2The obtained decarbonized flue gas is discharged outside, and the absorption liquid captures CO2Becoming absorption pregnant solution;
a regeneration tower for desorbing and regenerating the absorption rich liquid to obtain CO2The stripping gas is discharged from the exhaust line, resulting in CO-depleted gas2The absorption barren solution returns to the absorption tower; and
and the conductivity tester is arranged on the pipeline for conveying the absorption rich solution and the pipeline for conveying the absorption lean solution and is used for measuring the conductivity of the absorption rich solution and the absorption lean solution on line.
In a specific embodiment provided by the present invention, the system further includes: and the heat exchanger is communicated with the absorption tower and the regeneration tower and is used for carrying out heat exchange on the absorption rich liquid and the absorption lean liquid.
In another embodiment provided by the present invention, the system further comprises: and the carrying gas inlet pipeline is communicated with the regeneration tower and is provided with an inlet valve, and the air inlet quantity of the carrying gas is controlled through the inlet valve.
The present invention will be described in detail below by way of examples.
Preparing a plurality of absorption liquids with different absorbent concentrations, measuring the conductivity of the absorption liquids by using a conventional conductivity meter (American Hash HQ14D), and performing data correlation calculation on the different absorbent concentrations and the corresponding measured conductivities to obtain a fitting equation of the absorbent concentrations and the conductivities.
And (3) carrying out online monitoring on the absorption lean solution or the absorption rich solution by using a conductivity meter.
Example 1
1) Introducing CO into 100L of 30 wt% ethanolamine solution2In the capture system, with 12 vol% CO2Contact of flue gases (ethanolamine solution with CO-containing2The mass ratio of the flue gas is 3: 1) CO is carried out at an absorption temperature of 40 ℃ and a pressure of 0.1MPa2Absorption and trapping; obtaining decarbonized flue gas and absorption rich liquid; the conductivity of the absorption rich solution is monitored on line, and the concentration of ethanolamine in the ethanolamine solution is controlled according to a fitting equation of the concentration of the absorbent and the conductivity so as to meet the requirement of CO2Absorption and trapping;
2) introducing compressed air (flow rate of 2L/min, contact time of 4min) into a regeneration tower for desorption regeneration, wherein the contact temperature is 115 ℃ and the contact pressure is 0.18 MPa; obtaining absorption barren solution and desorption gas, and CO in the desorption gas2The content of (A) is 98% by volume or more;
3) and adjusting the pressure of the regeneration tower to restore the pressure of the regeneration tower to the pressure before the carrier gas is not introduced. As shown in table 1.
Example 2
1) 100L of 30% by weight ethanol are takenIntroducing CO into the amine solution2With 12 vol% CO in the capture system2Contact of flue gases (ethanolamine solution with CO-containing2The mass ratio of the flue gas is 3: 1) CO absorption at 40 ℃ under atmospheric pressure2Absorption and trapping; obtaining decarbonized flue gas and absorption rich liquid;
2) introducing compressed air (flow rate of 2L/min, introduction time of 4min) into a regeneration tower for desorption regeneration at 120 deg.C and pressure of 0.2 MPa; obtaining absorption barren solution and desorption gas; the conductivity of the absorption barren solution is monitored on line, and the concentration of ethanolamine in the ethanolamine solution is controlled according to a fitting equation of the concentration of the absorbent and the conductivity so as to meet the requirement of CO2Absorption and trapping; CO in desorption gas2The content of (A) is 98% by volume or more;
3) and adjusting the pressure of the regeneration tower to restore the pressure of the regeneration tower to the pressure before the carrier gas is introduced. As shown in table 1.
Example 3
1) Introducing CO into 100L of 30 wt% ethanolamine solution2With 12 vol.% CO in the capture system2Contact of flue gases (ethanolamine solution with CO-containing2The mass ratio of the flue gas is 3: 1) CO absorption at 40 ℃ under atmospheric pressure2Absorption and trapping; obtaining decarbonized flue gas and absorption rich liquid; the conductivity of the absorption rich solution is monitored on line, and the concentration of ethanolamine in the ethanolamine solution is controlled according to a fitting equation of the concentration of the absorbent and the conductivity so as to meet the requirement of CO2Absorption and trapping;
2) introducing the flue gas (flow rate of 2L/min, introduction time of 4min) of the power plant into a regeneration tower for desorption regeneration, wherein the temperature is 120 ℃, and the pressure is 0.2 MPa; obtaining absorption barren solution and desorption gas, and CO in the desorption gas2The content of (A) is 98% by volume or more;
3) and adjusting the pressure of the regeneration tower to restore the pressure of the regeneration tower to the pressure before the carrier gas is introduced. As shown in table 1.
Example 4
1) Introducing CO into 100L of 30 wt% triethanolamine solution2With 12 vol% CO in the capture system2Contact of flue gas (triethanolamine solution with CO-containing)2The mass ratio of the flue gas is 3.6:1), CO is carried out at an absorption temperature of 20 ℃ and under normal pressure2Absorption and trapping; obtaining decarbonized flue gas and absorption rich liquid; the conductivity of the absorption rich solution is monitored on line, and the concentration of ethanolamine in the ethanolamine solution is controlled according to a fitting equation of the concentration of the absorbent and the conductivity so as to meet the requirement of CO2Absorption and trapping;
2) introducing compressed air (flow rate of 4L/min, introduction time of 4min) into a regeneration tower for desorption regeneration at 115 ℃ and under 0.2 MPa; obtaining absorption barren solution and desorption gas, and CO in the desorption gas2The content of (A) is 98% by volume or more;
3) and adjusting the pressure of the regeneration tower to restore the pressure of the regeneration tower to the pressure before the carrier gas is not introduced. As shown in table 1.
Example 5
1) Introducing CO into 100L of mixed solution containing 5 wt% of piperazine and 30 wt% of ethanolamine as absorption liquid2With 12 vol.% CO in the capture system2Contacting flue gas (absorbing solution and CO-containing solution)2The mass ratio of the flue gas is 3.6:1), and CO is carried out at the absorption temperature of 60 ℃ and under normal pressure2Absorption and trapping; obtaining decarbonized flue gas and absorption rich liquid; the conductivity of the absorption rich solution is monitored on line, and the concentration of ethanolamine in the ethanolamine solution is controlled according to a fitting equation of the concentration of the absorbent and the conductivity so as to meet the requirement of CO2Absorption and trapping;
2) introducing the flue gas (flow rate of 10L/min, introduction time of 5min) of the power plant into a regeneration tower for desorption regeneration, wherein the temperature is 110 ℃, and the pressure is 0.15 MPa; obtaining absorption barren solution and desorption gas, and CO in the desorption gas2The content of (A) is 98% by volume or more;
3) and adjusting the pressure of the regeneration tower to restore the pressure of the regeneration tower to the pressure before the carrier gas is not introduced. As shown in table 1.
Comparative example 1
1) Introducing CO into 100L of 30 wt% ethanolamine solution2In the capture system, with 12 vol% CO2Contact of flue gases (ethanolamine solution with CO-containing2The mass ratio of the flue gas is 3: 1) CO is carried out at an absorption temperature of 40 ℃ and a pressure of 0.1MPa2Absorption and trapping; to obtain decarbonized smokeGas and absorption pregnant solution; the conductivity of the absorption rich solution is monitored on line, and the concentration of ethanolamine in the ethanolamine solution is controlled according to a fitting equation of the concentration of the absorbent and the conductivity so as to meet the requirement of CO2Absorption and trapping;
2) desorbing and regenerating the absorption rich solution in a regeneration tower at the heating temperature of 115 ℃ and the heating pressure of 0.18 MPa; obtaining absorption barren solution and desorption gas, and CO in the desorption gas2In an amount of 89% by volume;
capturing CO2The structure of (a) is shown in Table 1.
Comparative example 2
1) Introducing CO into 100L of 30 wt% ethanolamine solution2In the capture system, with 12 vol% CO2Contact of flue gases (ethanolamine solution with CO-containing2The mass ratio of the flue gas is 3: 1) CO is carried out at an absorption temperature of 40 ℃ and a pressure of 0.1MPa2Absorption and trapping; obtaining decarbonized flue gas and absorption rich liquid;
2) desorbing and regenerating the absorption rich solution in a regeneration tower at the heating temperature of 115 ℃ and the heating pressure of 0.18 MPa; obtaining absorption barren solution and desorption gas, and CO in the desorption gas2The content of (a) is 87 vol%;
capturing CO2The structure of (a) is shown in Table 1.
TABLE 1
Comparative examples of the above examples, all controlled to achieve CO2The capture removal rate is more than 90 percent. As can be seen from the results in Table 1, the on-line monitoring of the conductivity of the rich absorption liquid or the lean absorption liquid, preferably by adding the carrier gas to the regeneration tower, can be realized in the examples 1 to 5 of the method provided by the present invention, and the CO can be ensured to be realized2The CO is reduced under the requirement that the capture removal rate is more than 90 percent2The energy consumption of the trapping process can be realized and is preferably less than 3.9GJ/tCO2Compared with the comparative examples 1-2, the method has obviously better effect by using the traditional process. Also in the examples, the desorbed gas obtained is CO2The content of (A) is more than 98 volume percent, which is obviously higher than the requirement of the prior common industrial grade.
Meanwhile, the conductivity of the absorption rich solution or the absorption lean solution is monitored on line by a conductivity meter to treat CO2In the trapping process, the real-time monitoring of the absorbent concentration and the water consumption of the absorption liquid can guide the adjustment of the absorption liquid concentration in real time in actual engineering to ensure that CO is absorbed2The trapping process is maintained in an optimum operating state. Compared with the traditional acid-base titration analysis method, the stability of the system is greatly improved, and the method has better large-scale CO2And (4) capturing application prospect.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (13)
1. Absorption method for capturing CO2The method of (1), comprising:
(1) mixing the absorption liquid containing absorbent with CO2Flue gas contact for CO2The decarbonized flue gas is obtained, and the absorption liquid is used for capturing CO2Becoming absorption pregnant solution;
(2) desorbing and regenerating the absorption rich solution to obtain CO-containing gas2Stripping gas and CO removal2The absorption lean solution of (3);
(3) the desorption gas is recovered, and the absorption barren solution is returned to the step (1) to participate in the absorption and capture;
wherein the amount of the absorbent and/or water contained in the absorption liquid in the controlling step (1) is determined by measuring the electrical conductivity of the absorption rich liquid and the absorption lean liquid on line.
2. The method of claim 1, wherein the desorption regeneration in step (2) is performed by: heating the absorption rich solution to enable CO to be generated2From the absorption rich liquidDesorbing the product;
the stripping gas also contains water.
3. The method according to claim 2, wherein the desorbed gas is condensed and subjected to gas-liquid separation to obtain CO2Product gas and condensed water;
preferably, the condensed water is returned to the absorption trapping of the step (1) or the desorption regeneration of the step (2); or washing the decarbonized flue gas by the condensed water to remove the absorbent contained in the decarbonized flue gas, and returning the obtained washing water to the absorption and trapping in the step (1) or the desorption and regeneration in the step (2).
4. The method of claim 2 or 3, wherein the heating conditions comprise: the temperature is 110 ℃ and 150 ℃, and the pressure is 0.1-0.5 MPa.
5. The method of claim 1, wherein the desorption regeneration in step (2) is performed by: contacting the absorption rich solution with a carrier gas to make CO contact2Desorbing from the absorption rich liquid; wherein the desorption gas also contains the carrier gas;
preferably, the carrier gas is selected from N2Air, flue gas, CO of different concentrations2One or more of the gases.
6. The method of claim 5, wherein the flow rate of the carrier gas is 0.1-50L/min; the contact time is 1-20min, the contact temperature is 100-130 ℃, and the contact pressure is 0.1-0.5 MPa.
7. The method according to any one of claims 1 to 6, wherein the absorbent is selected from one or more of ethanolamine, triethanolamine, N-methyldiallylamine, N-methyldiethanolamine, diethylenetriamine, triethylenetetramine, pentaethylenehexamine, 2-amino-2-methyl-1-propanol, piperazine, ionic liquids and alcohols.
8. A method according to any one of claims 1 to 7, wherein the concentration of the absorption liquid is 5 to 60% by weight.
9. The method of any one of claims 1-8, wherein the conditions for absorption trapping comprise:
the absorption liquid and the CO-containing component2The mass ratio of the smoke is 1:1-5: 1; the absorption and trapping temperature is 20-60 ℃; the absorption and trapping pressure was normal pressure.
10. The method of any one of claims 1-9, wherein the CO-containing is present2The composition of the flue gas comprises: 6-85% by volume CO2The content is not higher than 35mg/m3SO of (A)xThe content of the active carbon is not higher than 50mg/m3NO ofxThe content of the sodium hydroxide is not higher than 5mg/m3The dust of (2).
11. CO for carrying out the method according to any one of claims 1 to 102A capture system, comprising:
an absorption tower for absorbing liquid containing absorbent and CO2Flue gas contact for CO2The obtained decarbonized flue gas is discharged outside, and the absorption liquid captures CO2Becoming absorption pregnant solution;
a regeneration tower for desorbing and regenerating the absorption rich liquid to obtain CO2The stripping gas is discharged from the exhaust line, resulting in CO-depleted gas2The absorption barren solution returns to the absorption tower; and
and the conductivity tester is arranged on a pipeline for conveying the absorption rich solution or a pipeline for conveying the absorption lean solution and is used for measuring the conductivity of the absorption rich solution or the absorption lean solution on line.
12. The system of claim 11, wherein the system further comprises:
and the heat exchanger is communicated with the absorption tower and the regeneration tower and is used for carrying out heat exchange on the absorption rich liquid and the absorption lean liquid.
13. The system of claim 11, wherein the system further comprises:
and the carrying gas inlet pipeline is communicated with the regeneration tower and is provided with an inlet valve, and the air inlet quantity of the carrying gas is controlled through the inlet valve.
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