CN111603895A - CO added with eutectic solvent2Absorption liquid and preparation method and application thereof - Google Patents
CO added with eutectic solvent2Absorption liquid and preparation method and application thereof Download PDFInfo
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- CN111603895A CN111603895A CN202010478787.8A CN202010478787A CN111603895A CN 111603895 A CN111603895 A CN 111603895A CN 202010478787 A CN202010478787 A CN 202010478787A CN 111603895 A CN111603895 A CN 111603895A
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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
- 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
-
- 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
- B01D2252/20415—Tri- or polyamines
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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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- 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
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
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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]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/40—Capture or disposal of greenhouse gases of CO2
Abstract
The invention belongs to the technical field of preparation of gas absorption liquid, and particularly relates to CO added with eutectic solvent2An absorption liquid and a preparation method and application thereof. The CO is2The absorption liquid comprises ethyleneamine and eutectic solvent, and the CO is2The absorption liquid contains a plurality of amino groups, which can increase CO2Storage capacity of (2), eutectic solvent and CO at the same time2Has strong affinity and can improve CO2Efficiency of capturing absorption liquid in CO2In the process of trapping, the eutectic solvent is responsible for rapidly capturing CO2Molecule, and then capturing CO2Transfer to ethyleneamines, take advantage of their large number of amine reactive sites for CO2"constraint" to achieve rapid, large-scale absorption of CO2. In addition, during desorption, the hydrogen bond between the eutectic solvent and the ethylene amine can inhibit the volatilization loss of the ethylene amine, reduce the volatilization of the ethylene amine and improve CO2The service cycle and utilization rate of the absorption liquid.
Description
Technical Field
The invention belongs to the technical field of preparation of gas absorption liquid, and particularly relates to CO added with eutectic solvent2An absorption liquid and a preparation method and application thereof.
Background
In recent years, global continuous warming caused by greenhouse effect has a considerable influence on human life, and the global scope is actively moved to achieve the goal of controlling the global warming not to exceed 1.5 ℃ proposed by Paris protocol. The control of global temperature rise to be not more than 1.5 ℃ requires great force to carry out carbon emission reduction and carbon fixation, and on one hand, the emission of CO into the environment by human activities is reduced2And on the other handThe CO in the atmosphere needs to be reduced2Fixing and utilizing. CO 22The capture, utilization and sequestration technology (CCUS) of (A) is a major means and approach to control the exacerbation of the greenhouse effect. Wherein, to CO2The centralized capture of emissions sources is one approach that is commonly used.
In recent years, the eutectic solvent becomes CO capture because of the advantages of simple synthesis process, good stability, cheap and easily available raw materials, difficult volatilization and the like2The ideal solvent of (2) and the eutectic solvent also have excellent biocompatibility, can be completely decomposed and has no pollution to the environment. However, eutectic solvents are limited by the number of hydrogen bonding ligands, with the relative molecular mass of the monomers being as high as several hundred, resulting in CO absorption per unit mass of eutectic solvent2Is limited in its ability to perform. Chinese patent document CN107398143A discloses a non-aqueous absorbent for removing carbon dioxide from a gas mixture, the absorbent is composed of amino acids and alcohol solvents, the absorbent has limited ability to absorb carbon dioxide, the eutectic solvents in the absorbent are similar, the absorption capacity of the absorption liquid per unit mass is insufficient, the absorption process is phase-changed and easy to block pipelines, and the solvent has high viscosity, which results in large mass transfer resistance and increases overall energy consumption.
Disclosure of Invention
Therefore, the invention aims to overcome the defects of limited absorption capacity, low capture efficiency and the like of the carbon dioxide absorption liquid in the prior art, thereby providing CO added with the eutectic solvent2An absorption liquid and a preparation method and application thereof.
Therefore, the invention provides the following technical scheme.
The invention provides CO added with eutectic solvent2An absorption liquid comprising an ethyleneamine and a eutectic solvent.
The ethyleneamine is present in the CO2The mass fraction in the absorption liquid is 10-40%;
the eutectic solvent is in the CO2The mass fraction of the absorption liquid is 5-20%.
The eutectic solvent is a hydrophilic eutectic solvent containing a plurality of amino functional groups;
the eutectic solvent is an amino acid/polyalcohol eutectic solvent.
The molar ratio of the amino acid to the polyol is 1: (4-10).
The amino acid is a basic amino acid. The basic amino acid comprises one of arginine, lysine or histidine.
The CO is2The absorption liquid also comprises an antioxidant;
said antioxidant being in said CO2The content of the absorption liquid is 1-5 wt%.
The antioxidant may be, but is not limited to, pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], butanone oxime, acetaldehyde oxime, and acetone oxime.
The ethylene amine is at least one of diethylene triamine, triethylene tetramine and tetraethylene pentamine.
The invention also provides a method for preparing the CO2A method for absorbing a liquid, comprising the steps of,
mixing all the raw materials uniformly to obtain CO2Absorbing the liquid.
The preparation method of the eutectic solvent comprises the steps of mixing amino acid and polyhydric alcohol, uniformly mixing at 70-120 ℃ to form uniform and transparent stable solution, and cooling to obtain the eutectic solvent.
In addition, the invention also provides the CO2Absorbing liquid or CO prepared by the method2Absorption liquid for capturing CO in coal-fired power plant exhaust gas2The use of (1).
The technical scheme of the invention has the following advantages:
1. the invention provides CO added with eutectic solvent2An absorption liquid comprising ethyleneamine and eutectic solvent, the CO2The absorption liquid contains a plurality of amino groups, which can increase CO2Storage capacity of (2), eutectic solvent and CO at the same time2Has strong affinity and can improve CO2Efficiency of capturing absorption liquid in CO2In the process of trapping, the eutectic solvent is responsible for rapidly capturing CO2Molecule, and then capturing CO2Transfer to ethyleneamines, take advantage of their large number of amine reactive sites for CO2"constraint" to achieve rapid, large-scale absorption of CO2. In addition, during desorption, the hydrogen bond between the eutectic solvent and the ethylene amine can inhibit the volatilization loss of the ethylene amine, reduce the volatilization of the ethylene amine and improve CO2The service cycle and utilization rate of the absorption liquid.
2. The invention provides CO added with eutectic solvent2Absorption of liquid by controlling ethylene amine and eutectic solvent in CO2The content of the absorption liquid is beneficial to reducing the loss of the solvent and improving the absorption efficiency.
By controlling the molar ratio of amino acid to polyol in the eutectic solvent, stable CO can be formed2Absorbing liquid and ensuring CO2Absorption liquid to CO2The absorption capacity of (1).
3. The invention provides CO added with eutectic solvent2The preparation method of the absorption liquid is simple to operate and easy to realize, and the preparation method of the eutectic solvent is uniformly mixed at 70-120 ℃, so that hydrogen bond acting force is formed between amino acid and polyhydric alcohol, and a stable eutectic solvent is formed.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is a graph showing CO contents of the absorption liquids obtained in examples 5 and 13 of the present invention and the absorption liquid of comparative example 12Absorption versus time;
FIG. 2 is a graph showing CO contents of absorption liquids prepared in example 5 of the present invention and a comparative example2A plot of absorption rate versus time;
FIG. 3 shows the results of the present invention on CO2The performance of the absorption liquid was testedThe absorbing device of (1);
reference numerals:
1-a buffer bottle; 2-an absorption bottle; 3-constant temperature water bath; 4-gas circulation line.
Detailed Description
The following examples are provided to further understand the present invention, not to limit the scope of the present invention, but to provide the best mode, not to limit the content and the protection scope of the present invention, and any product similar or similar to the present invention, which is obtained by combining the present invention with other prior art features, falls within the protection scope of the present invention.
The examples do not show the specific experimental steps or conditions, and can be performed according to the conventional experimental steps described in the literature in the field. The reagents or instruments used are not indicated by manufacturers, and are all conventional reagent products which can be obtained commercially.
In the following examples, the eutectic solvent was prepared by mixing an amino acid and a polyhydric alcohol, stirring continuously at 80 ℃ until a uniform and transparent pure liquid phase was formed, and cooling to room temperature to obtain the eutectic solvent.
Example 1
This example provides a CO with eutectic solvent2An absorbent solution comprising 20g of diethylenetriamine, 10g of a eutectic solvent (arginine and ethylene glycol in a molar ratio of 1: 6), 1g of tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid]Pentaerythritol ester and 69g water.
CO as described above2A method for preparing an absorption liquid comprises the following steps,
mixing all the raw materials uniformly to obtain CO2Absorbing the liquid.
Example 2
This example provides a CO with eutectic solvent2An absorbent solution comprising 20g of diethylenetriamine, 10g of a eutectic solvent (arginine and glycerol in a molar ratio of 1: 7), and 1g of tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid]Pentaerythritol ester and 69g water.
CO as described above2Absorption ofThe preparation method of the liquid comprises the following steps,
mixing all the raw materials uniformly to obtain CO2Absorbing the liquid.
Example 3
This example provides a CO with eutectic solvent2An absorbent solution comprising 40g of diethylenetriamine, 5g of a eutectic solvent (lysine and ethylene glycol in a molar ratio of 1: 4), and 1g of tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid]Pentaerythritol ester and 54g water.
CO as described above2A method for preparing an absorption liquid comprises the following steps,
mixing all the raw materials uniformly to obtain CO2Absorbing the liquid.
Example 4
This example provides a CO with eutectic solvent2An absorbent solution comprising 20g of diethylenetriamine, 10g of a eutectic solvent (lysine and glycerol in a molar ratio of 1: 6), and 1g of tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid]Pentaerythritol ester and 69g water.
CO as described above2A method for preparing an absorption liquid comprises the following steps,
mixing all the raw materials uniformly to obtain CO2Absorbing the liquid.
Example 5
This example provides a CO with eutectic solvent2An absorbent solution comprising 20g of triethylenetetramine, 20g of a eutectic solvent (arginine/ethylene glycol in a molar ratio of 1: 6), 1g of tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid]Pentaerythritol ester and 59g water.
CO as described above2A method for preparing an absorption liquid comprises the following steps,
mixing all the raw materials uniformly to obtain CO2Absorbing the liquid.
Example 6
This example provides a CO with eutectic solvent2An absorbent solution comprising 20g of triethylenetetramine, 20g of a eutectic solvent (arginine/glycerol at a molar ratio of 1: 7), and 1g of tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid]Pentaerythritol ester and 59g water.
CO as described above2A method for preparing an absorption liquid comprises the following steps,
mixing all the raw materials uniformly to obtain CO2Absorbing the liquid.
Example 7
This example provides a CO with eutectic solvent2An absorbent solution comprising 20g of triethylenetetramine, 20g of a eutectic solvent (lysine/ethylene glycol in a molar ratio of 1: 5), 1g of tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propanoic acid]Pentaerythritol ester and 59g water.
CO as described above2A method for preparing an absorption liquid comprises the following steps,
mixing all the raw materials uniformly to obtain CO2Absorbing the liquid.
Example 8
This example provides a CO with eutectic solvent2An absorbent solution comprising 20g of triethylenetetramine, 20g of a eutectic solvent (lysine/glycerol at a molar ratio of 1: 6), 1g of tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid]Pentaerythritol ester and 59g water.
CO as described above2A method for preparing an absorption liquid comprises the following steps,
mixing all the raw materials uniformly to obtain CO2Absorbing the liquid.
Example 9
This example provides a CO with eutectic solvent2An absorbent solution comprising 20g tetraethylenepentamine, 10g of a eutectic solvent (arginine/ethylene glycol in a 1:6 molar ratio), 1g of tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propanoic acid]Pentaerythritol ester and 69g water.
CO as described above2A method for preparing an absorption liquid comprises the following steps,
mixing all the raw materials uniformly to obtain CO2Absorbing the liquid.
Example 10
This example provides a CO with eutectic solvent2An absorbent solution comprising 10g of tetraethylenepentamine, 15g of a eutectic solvent (arginine/glycerol in a molar ratio of 1: 10), 1g of tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid]Pentaerythritol ester and 70g water.
CO as described above2A method for preparing an absorption liquid comprises the following steps,
mixing all the raw materials uniformly to obtain CO2Absorbing the liquid.
Example 11
This example provides a CO with eutectic solvent2An absorbent solution comprising 20g tetraethylenepentamine, 10g of a eutectic solvent (lysine/ethylene glycol in a 1:5 molar ratio), 1g of tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propanoic acid]Pentaerythritol ester and 69g water.
CO as described above2A method for preparing an absorption liquid comprises the following steps,
mixing all the raw materials uniformly to obtain CO2Absorbing the liquid.
Example 12
This example provides a CO with eutectic solvent2An absorbent solution comprising 20g of tetraethylenepentamine, 10g of a eutectic solvent (lysine/glycerol in a molar ratio of 1: 6), 1g of tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid]Pentaerythritol ester and 69g water.
CO as described above2A method for preparing an absorption liquid comprises the following steps,
mixing all the raw materials uniformly to obtain CO2Absorbing the liquid.
Example 13
This example provides a CO with eutectic solvent2An absorbent solution comprising 20g of diethylenetriamine, 10g of a eutectic solvent (arginine and ethylene glycol in a molar ratio of 1: 12), 1g of tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid]Pentaerythritol ester and 69g water.
CO as described above2A method for preparing an absorption liquid comprises the following steps,
mixing all the raw materials uniformly to obtain CO2Absorbing the liquid.
Test examples
This test example provides the CO prepared in example 52The performance of the absorption liquid was tested, specifically as follows,
a20 wt% triethylenetetramine aqueous solution was used as comparative group 1; the absorption/desorption test of the absorption liquid was carried out by the bubbling method, and the test apparatus shown in FIG. 3 comprises a buffer bottle 1,The absorption bottle 2, the gas circulation pipeline 4 and the constant temperature water bath 3 are arranged in the constant temperature water bath to ensure the constant absorption temperature; introducing carbon dioxide and nitrogen into a buffer bottle, uniformly mixing, then introducing the mixed gas into an absorption bottle, wherein the absorption liquid in the absorption bottle is CO to be tested2Absorbing the liquid. The gas tested was 12% CO by volume2And 88% N2The mixed gas of (2) is compared with the mass change of the absorption liquid in the absorption bottle before and after absorption; wherein the absorption capacity is CO in the absorption liquid2Is obtained by measuring the mass increase of the device, and the unit is g/g, which represents the CO content per gram of the absorption liquid2The quality of (c).
FIG. 1 shows CO contents of the absorbent solutions obtained in examples 5 and 13 and the absorbent solution of comparative example 12The specific numerical values of the graph of the relationship between the absorption amount and the time are shown in the table 1, and the total absorption amount of the absorption liquid provided by the invention is improved as can be seen from the graph 1; FIG. 2 shows an absorption liquid CO2The specific values of the curve of the relationship between the absorption rate and the time are shown in table 2, and it can be seen from fig. 2 that the absorption rate of the absorption liquid provided by example 5 is significantly higher than that of triethylenetetramine within 20-60min of the absorption process, the average absorption rate is increased most significantly within a period of 30-40min, and the absorption liquid is in a certain loading interval and cannot be absorbed to saturation or completely desorbed. The invention has great significance for practical production application because the improvement of the absorption rate is positioned in the middle section of the absorption process.
Table 1 absorption capacity of the absorbent solutions at different times in example 5, example 13 and comparative group 1
Note: the absorption amount is the mass of carbon dioxide absorbed per gram of absorption liquid, and the unit is g/g.
Table 2 absorption rates of the absorbent solutions of example 5 and comparative example 1 at different times
Note: the absorption rate is expressed in mg-g-1·min-1。
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications of the invention may be made without departing from the spirit or scope of the invention.
Claims (10)
1. CO added with eutectic solvent2An absorption liquid characterized by comprising an ethyleneamine and a eutectic solvent.
2. CO according to claim 12An absorption liquid, characterized in that the ethyleneamine is present in the CO2The mass fraction in the absorption liquid is 10-40%;
the eutectic solvent is in the CO2The mass fraction of the absorption liquid is 5-20%.
3. CO according to claim 1 or 22The absorption liquid is characterized in that the eutectic solvent is a hydrophilic eutectic solvent containing a plurality of amino functional groups;
the eutectic solvent is an amino acid/polyalcohol eutectic solvent.
4. CO according to claim 32An absorbent solution, characterized in that the molar ratio of the amino acid to the polyhydric alcohol is 1: (4-10).
5. CO according to claim 3 or 42The absorbent solution is characterized in that the amino acid is a basic amino acid.
6. CO according to any one of claims 1 to 52The absorbent solution of (1), further comprising an antioxidant;
the content of the antioxidant in the absorption liquid is 1-5 wt%.
7. CO according to any one of claims 1 to 62The absorbent liquid is characterized in that the ethylene amine is at least one of diethylene triamine, triethylene tetramine and tetraethylene pentamine.
8. A process for the preparation of a CO according to any one of claims 1 to 72A method for absorbing a liquid, comprising the steps of,
mixing all the raw materials uniformly to obtain CO2Absorbing the liquid.
9. The method as claimed in claim 8, wherein the eutectic solvent is prepared by mixing the amino acid and the polyol, uniformly mixing at 70-120 ℃, and cooling to obtain the eutectic solvent.
10. CO according to any one of claims 1 to 72Absorption liquid or CO produced by the process according to any of claims 8 to 92Absorption liquid for capturing CO in coal-fired power plant exhaust gas2The use of (1).
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Cited By (1)
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| CN114307803A (en) * | 2020-09-30 | 2022-04-12 | 新疆天运化工有限公司 | CO (carbon monoxide)2Absorption liquid and its preparing device and process |
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| CN114307803A (en) * | 2020-09-30 | 2022-04-12 | 新疆天运化工有限公司 | CO (carbon monoxide)2Absorption liquid and its preparing device and process |
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