CN114653166A

CN114653166A - Composition containing carboxylic acid, preparation method and application thereof

Info

Publication number: CN114653166A
Application number: CN202011530227.9A
Authority: CN
Inventors: 马守涛; 姜杰; 张长胜; 朱云峰; 孙峰; 徐伟
Original assignee: China Petroleum and Chemical Corp; Sinopec Qingdao Safety Engineering Institute
Current assignee: China Petroleum and Chemical Corp; Sinopec Safety Engineering Research Institute Co Ltd
Priority date: 2020-12-22
Filing date: 2020-12-22
Publication date: 2022-06-24
Anticipated expiration: 2040-12-22
Also published as: CN114653166B

Abstract

The invention relates to the field of gas purification treatment, and discloses a composition containing carboxylic acid and a preparation method and application thereof. The composition contains a hydrogen bond donor and a hydrogen bond acceptor, wherein the hydrogen bond donor is carboxylic acid, and the hydrogen bond acceptor is selected from quaternary ammonium salt and/or quaternary phosphonium salt. Through the synergistic action of the hydrogen bond donor and the hydrogen bond acceptor, the composition has the advantages of low saturated vapor pressure, easy recovery, simple synthesis, low price, difficult degradation and environmental friendliness, and is used for treating CO₂Has higher selectivity and dissolving capacity, and the composition can be recycled, saves the cost and can be industrially applied.

Description

Composition containing carboxylic acid, preparation method and application thereof

Technical Field

The invention relates to the field of gas purification treatment, in particular to a composition containing carboxylic acid and a preparation method and application thereof.

Background

In recent years, human over-dependence on fossil fuels has led to large amounts of CO₂And, CO₂Has a long life cycle, which can be 200 years in the atmosphere, and causes a series of environmental problems, such as global warming, greenhouse effect, and the like. Carbon Capture and Storage (CCS) technology is aimed at reducing atmospheric CO₂Concentration, controlling the rate of global warming.

At present, CO₂The trapping technology mainly comprises three types of trapping before combustion, trapping after combustion and oxygen-enriched combustion. After combustion, the flue gas (mainly N) is captured by absorption, adsorption, membrane separation and other methods₂、CO₂、H₂O and O₂) CO in₂And (4) separating and recovering. Because of the advantages of simple operation, flexible operation conditions, low energy consumption and the like, the method is used for capturing CO in the flue gas of the power plant at present₂The preferred embodiment of (1). Monoethanolamine (MEA) is the most effective traditional solvent from post-combustion capture technologies, and organic amine MEA-based post-combustion capture technologies that have been successfully commercially operated are considered to be the most mature CO at present₂Provided is a technique. However, the method has the defects of high energy consumption, corrosion of equipment by the solvent and the like. Therefore, research on the use of novel solvents with high selectivity and good dissolving capacity for removing CO in a waste gas system₂Is always the hot point of the study of scholars at home and abroad.

CN109432990A discloses a desulfurization and decarburization absorbent, which comprises complex iron, an organic solvent and an organic base. The organic solvent comprises dimethyl sulfoxide or polyethylene glycol dimethyl ether or a mixture of dimethyl sulfoxide and polyethylene glycol dimethyl ether, and the organic base can be dissolved in the organic solvent and specifically comprises 1-butyl-3-methylimidazole hydroxide. The absorbent has good effect on sulfide and CO₂Has absorption effect. The organic solvent dimethyl sulfone or ethylene glycol dimethyl ether in the solvent is easy to volatilize and can be recovered with high recovery rateLarge loss amount, environmental pollution and the like. The organic base is an ionic liquid solvent, and has the defects of difficult synthesis, high price and the like.

CN103007690A discloses a CO₂The absorbent consists of organic amine and alkaline metal oxide, and the mass ratio of the organic amine to the alkaline metal oxide is 0.01-100: 1. although the absorbent can absorb CO₂However, the organic amine in the solvent is expensive to operate, and meanwhile, the organic amine is easy to degrade and cause secondary pollution, so that the organic amine needs to be subjected to stable treatment.

Disclosure of Invention

The invention aims to overcome the technical problems of environment pollution caused by easy volatilization, high recovery capacity, large loss amount, difficult synthesis, high price, large energy consumption, solvent corrosion on equipment and easy degradation and instability of organic amine in the prior art, and provides a composition containing carboxylic acid and a preparation method and application thereof.

In order to achieve the above objects, according to one aspect of the present invention, there is provided a carboxylic acid-containing composition comprising a hydrogen bond donor and a hydrogen bond acceptor, wherein the hydrogen bond donor is a carboxylic acid, and the hydrogen bond acceptor is selected from a quaternary ammonium salt and/or a quaternary phosphonium salt.

The composition containing carboxylic acid provided by the invention contains a hydrogen bond donor, a hydrogen bond acceptor and a solvent, and has the advantages of low saturated vapor pressure, easiness in recovery, simplicity in synthesis, low price, difficulty in degradation and environmental friendliness through the synergistic effect of the hydrogen bond donor and the hydrogen bond acceptor, and the composition is used for CO₂Has higher selectivity and dissolving capacity, and the composition can be recycled, saves the cost and can be industrially applied.

In a second aspect, the present invention provides a process for preparing the above composition, which process comprises mixing, under stirring, a hydrogen bond donor, a hydrogen bond acceptor and optionally a solvent to obtain the composition.

In a third aspect, the invention provides a method for removing CO from exhaust gas₂By contacting the exhaust gas with an absorbent to obtain a gas containing CO₂Wherein the absorption isThe agent is the composition or the composition prepared by the method.

The method for preparing the composition is simple and convenient, is easy to operate and is convenient for industrial application.

The invention provides a method for removing CO in waste gas₂The above composition is used for CO in exhaust gas₂Of the composition to CO₂Has higher selectivity and dissolving capacity, and the composition can be recycled, saves the cost and can be industrially applied.

Drawings

FIG. 1 is a schematic diagram of CO removal from exhaust gas according to one embodiment of the present invention₂Schematic diagram of the system structure of (1).

Description of the reference numerals

101 first compressor, 102 second compressor, 103 third compressor, 201 first absorption tower, 202 second absorption tower, 301 first mixer, 302 second mixer, 303 third mixer, 401 first flash tank, 402 second flash tank, 500 pump, 600 cooler.

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.

The invention provides a composition containing carboxylic acid, which contains a hydrogen bond donor and a hydrogen bond acceptor, wherein the hydrogen bond donor is carboxylic acid, and the hydrogen bond acceptor is selected from quaternary ammonium salt and/or quaternary phosphonium salt.

In some embodiments of the invention, the molar ratio of the hydrogen bond donor to the hydrogen bond acceptor is from 0.2 to 5: 1, preferably 0.5 to 2: 1.

in some embodiments of the present invention, the carboxylic acid preferably has 2 to 20 carbon atoms, and more preferably at least one of a monobasic acid, a dibasic acid and a tribasic acid. Further preferably, the monobasic acid is selected from at least one of 3, 4-dihydroxycinnamic acid, 4-hydroxycinnamic acid, stearic acid and linoleic acid. Further preferably, the dibasic acid is selected from at least one of itaconic acid, oxalic acid and glutamic acid. Further preferably, the triacid is selected from at least one of 1,3, 5-pentanetricarboxylic acid, 1,2, 4-benzenetricarboxylic acid, and 1,3, 5-benzenetricarboxylic acid.

In some embodiments of the present invention, preferably, the quaternary ammonium salt has the formula R₁R₂R₃R₄NX, wherein R₁、R₂、R₃And R₄Identical or different and are each independently selected from alkyl groups, more preferably alkyl groups having 1 to 6 carbon atoms. X is halogen, more preferably selected from F, Cl, Br or I. Further preferably, the quaternary ammonium salt is selected from at least one of butyltrimethylammonium chloride, tetramethylammonium chloride and tetraethylammonium chloride.

In some embodiments of the present invention, preferably, the quaternary phosphonium salt has the formula R₁’R₂’R₃’R₄'PX', wherein R₁’、R₂’、R₃' and R₄' are the same or different and are each independently selected from alkyl groups or phenyl groups, more preferably alkyl groups having 1 to 6 carbon atoms or phenyl groups. X' is halogen, more preferably selected from F, Cl, Br or I; further preferably, the quaternary phosphonium salt is at least one selected from the group consisting of methyltriphenylphosphonium chloride, tetraphenylphosphonium bromide and tributylmethylphosphonium iodide.

In some embodiments of the invention, the composition may further comprise a solvent, and the molar ratio of the hydrogen bond donor to the solvent is preferably 1-5: 1, more preferably 2 to 4: 1.

in some embodiments of the present invention, preferably, the solvent is an organic solvent or an inorganic solvent. More preferably, the organic solvent is a saturated monohydric alcohol of C1-C4, more preferably methanol and/or ethanol; the organic solvent is methanol and/or ethanol. More preferably, the inorganic solvent is water, and even more preferably deionized water.

In some embodiments of the invention, preferably, the composition is free of dimethyl sulfoxide, dimethyl ether of polyethylene glycol, or an organic amine. Specifically, the organic amine refers to monoethanolamine and/or diethanolamine.

According to a preferred embodiment of the invention, the composition consists solely of the above ingredients.

In some embodiments of the invention, the temperature of the mixing is preferably 70 to 130 ℃, more preferably 80 to 120 ℃ in order to further facilitate the dissolution of the hydrogen bond donor and the hydrogen bond acceptor.

According to a preferred embodiment of the present invention, the hydrogen bond donor and the hydrogen bond acceptor are mixed under stirring (rotation speed 200-.

In a third aspect, the invention provides a method for removing CO from exhaust gas₂The method of (3), contacting the exhaust gas with an absorbent to obtain a gas containing CO₂Wherein the absorbent is the composition or the composition prepared by the method.

In the present invention, the exhaust gas is derived from exhaust gas of a thermal power plant.

In some embodiments of the invention, the feed volume ratio of the off-gas to the absorbent is preferably 5 to 10: 1.

in some embodiments of the present invention, the feed volume flow of the off-gas is preferably 1000-³/h。

In some embodiments of the invention, the temperature of the contacting is preferably from 25 to 40 ℃. The pressure of the contact is preferably 0.5 to 1.5MPa, more preferably 0.8 to 1.2 MPa.

In some embodiments of the invention, the method is used to achieve recycling of the absorbentThe method further comprises subjecting the mixture to flash evaporation to separate the absorbent and CO₂。

In some embodiments of the invention, the temperature of the flash is preferably in the range of 40 to 60 ℃. The pressure of the flash is preferably 0.05 to 0.1 MPa.

According to a preferred embodiment of the invention, the CO in the exhaust gas₂The removal is performed using the system shown in fig. 1. Specifically, the method comprises the following steps: will contain CO₂The waste gas is compressed by the first compressor 101 and then enters the first absorption tower 201, the absorbent is sprayed from the top of the first absorption tower 201, and the CO in the first absorption tower 201₂Is subjected to mass exchange with the absorbent in the first absorption tower 201, wherein the exhaust gas containing CO₂The feed volume ratio of off-gas to absorbent is 5-10: 1, containing CO₂The feeding volume flow of the waste gas is 1000-5000m³H, containing CO₂The contact temperature of the waste gas and the absorbent is 25-40 ℃, the contact pressure is 0.5-1.5MPa, preferably 0.8-1.2MPa, the obtained purified gas is discharged after being mixed with the gas discharged from the top of the second absorption tower 202 through the first mixer 301 from the top of the first absorption tower 201, and the gas containing CO is obtained from the bottom of the first absorption tower 201₂The absorbent enters the first flash tank 401, the absorbent discharged from the top of the first flash tank 401 enters the second absorption tower 202 through the second compressor 102, and the CO-containing gas in the second absorption tower 202₂Is subjected to mass exchange with the absorbent in the first absorption tower 201, wherein the exhaust gas containing CO₂The feed volume ratio of off-gas to absorbent is 5-10: 1, containing CO₂The feeding volume flow of the waste gas is 1000-³H, containing CO₂The contact temperature of the waste gas with the absorbent is 25 to 40 ℃, the contact pressure is 0.5 to 1.5MPa, preferably 0.8 to 1.2MPa, the flash evaporation temperature in the first flash tank 401 is 40 to 60 ℃, the flash evaporation pressure is 0.05 to 0.1MPa, purified gas obtained in the second absorption tower 202 is discharged after passing through the first mixer 301, and CO contained in the bottom of the first flash tank 401₂And CO-containing at the bottom of the second absorption tower 202₂The absorbent is mixed by the second mixer 302 and enters the second flash tank 402, the flash in the second flash tank 402The steaming temperature is 40-60 ℃, the pressure of the flash evaporation is 0.05-0.1MPa, and the obtained gas at the top of the second flash evaporation tank 402 is high-purity CO₂And discharged through the third compressor 103. The absorbent recovered at the bottom of the second flash tank 402 is cooled by a pump 500 and a cooler 600 and then enters a third mixer 303, and the absorbent in the third mixer 303 respectively enters the first absorption tower 201 and the second absorption tower 202 for recycling, wherein the number of theoretical plates of the first absorption tower is 5-10, and the number of theoretical plates of the second absorption tower is 5-15.

In the present invention, the pressure means gauge pressure.

The present invention will be described in detail below by way of examples. In the examples and comparative examples, the reagents used were all commercially available analytical reagents. The used waste gas is self-made and contains CO₂The simulated flue gas comprises the following components: CO 2₂: 20.25 volume%; o is₂: 8.27 volume%; h₂O: 10.12 volume%; n is a radical of hydrogen₂: 59.01 volume%; CO: 2.35 volume%; trace amounts of sulfides and nitrogen oxides. The room temperature means 25 ℃.

Preparation example 1

Weighing hydrogen bond donor linoleic acid and hydrogen bond acceptor tetramethylammonium chloride, and adding a small amount of solvent deionized water to reduce the viscosity of the compound. Heating a mixture of linoleic acid and tetramethylammonium chloride at a heating temperature of 80 ℃, stirring while heating, adding a small amount of deionized water, stopping heating after a clear transparent liquid is formed in a container, and stopping stirring when the temperature of a solution in the container is reduced to room temperature to obtain a composition, wherein the molar ratio of a hydrogen bond donor to a hydrogen bond acceptor to a solvent is 2: 3: 1.

preparation example 2

A composition was prepared according to the method of preparation example 1, except that the hydrogen bond donor was itaconic acid, the hydrogen bond acceptor was tetraethylammonium chloride, and the solvent was methanol, wherein the molar ratio of hydrogen bond donor, hydrogen bond acceptor, and solvent was 4: 2: 1. the heating temperature was 100 ℃.

Preparation example 3

A composition was prepared according to the method of preparation example 1, except that the hydrogen bond donor was oxalic acid, the hydrogen bond acceptor was tetraphenylphosphonium bromide, and the hydrogen bond acceptor was tetraethylammonium chloride, wherein the molar ratio of hydrogen bond donor, hydrogen bond acceptor, and solvent was 3: 3: 1. the heating temperature was 120 ℃.

Preparation example 4

A composition was prepared according to the method of preparation example 1, except that the hydrogen bond donor was 1,3, 5-pentanetricarboxylic acid and the hydrogen bond acceptor was butyltrimethylammonium chloride. Wherein the molar ratio of the hydrogen bond donor to the hydrogen bond acceptor to the solvent is 1: 5: 1.

preparation example 5

A composition was prepared according to the method of preparation 1 except that the hydrogen bond donor was 3, 4-dihydroxycinnamic acid and the hydrogen bond acceptor was tetraethylammonium chloride. Wherein the molar ratio of the hydrogen bond donor to the hydrogen bond acceptor to the solvent is 5: 1: 1.

example 1

As shown in FIG. 1, will contain CO₂The waste gas enters a first absorption tower 201 after being compressed by a first compressor 101, an absorbent is sprayed from the top of the first absorption tower 201, wherein the absorbent is the composition obtained in the preparation example 1, and the CO is contained in the first absorption tower 201₂The waste gas and the absorbent are subjected to substance exchange in the first absorption tower 201, the obtained purified gas is discharged after being mixed with the gas discharged from the top of the second absorption tower 202 from the top of the first absorption tower 201 through the first mixer 301, and the gas containing CO is obtained at the bottom of the first absorption tower 201₂The absorbent enters the first flash tank 401, the absorbent discharged from the top of the first flash tank 401 enters the second absorption tower 202 through the second compressor 102, and the CO-containing gas in the second absorption tower 202₂The waste gas and the absorbent are subjected to substance exchange in the first absorption tower 201, the purified gas obtained in the second absorption tower 202 is discharged through the first mixer 301, and the gas containing CO in the bottom of the first flash tank 401 is discharged₂And CO-containing at the bottom of the second absorption tower 202₂The absorbent is mixed by the second mixer 302 and then enters the second flash tank 402, and high-purity CO is obtained at the top of the second flash tank 402₂And discharged through the third compressor 103, and the absorbent recovered at the bottom of the second flash tank 402 enters the third mixer after being cooled by the pump 500 and the cooler 600303, the absorbent in the third mixer 303 is respectively taken as the absorbent and enters the first absorption tower 201 and the second absorption tower 202 for recycling, and the purified gas is collected. The specific operating parameters of each device are shown in table 1:

TABLE 1

Example 2

CO in the exhaust gas was carried out in accordance with the method of example 1₂Except that the absorbent was the composition obtained in preparation example 2 and the specific operating parameters of each unit are as shown in table 2:

TABLE 2

Example 3

CO in the exhaust gas was carried out in accordance with the procedure of example 1₂Except that the absorbent was the composition obtained in preparative example 3 and the specific operating parameters of each unit are shown in table 3:

TABLE 3

Example 4

CO in the exhaust gas was carried out in accordance with the method of example 1₂Except that the absorbent was the composition obtained in preparation example 4.

Example 5

CO in the exhaust gas was carried out in accordance with the procedure of example 1₂Except that the absorbent was the composition obtained in preparation example 5.

Example 6

The separation of the azeotrope was carried out according to the method of example 1, except that the molar ratio of hydrogen bond donor, hydrogen bond acceptor and solvent was 6: 1: 1.

comparative example 1

CO in the exhaust gas was carried out in accordance with the procedure of example 1₂Except that the absorbent is a composition of urea and choline chloride according to a molar ratio of 1: 2.

Comparative example 2

The separation of the azeotrope was carried out according to example 1, except that the hydrogen bond donor used was ethylene glycol.

Comparative example 3

The separation of the azeotrope was carried out according to example 1, except that the hydrogen bond acceptor used was betaine.

Test example 1

CO in the purified gas obtained in examples and comparative examples₂The content of the (D) is measured, the adopted test instrument is a refinery gas system, an Agilent 7890B, a 4-valve 6-column system, the type of the column is a hayesep-Q molecular sieve column, the temperature of a column box adopts temperature programming, the initial temperature is 60 ℃, the temperature is kept for 1min, the temperature is then programmed, the temperature raising rate is 20 ℃/min, the temperature is kept for 5min after being raised to 150 ℃, the checker is TCD, the temperature is 250 ℃, the temperature of a sample injector is 70 ℃, and the obtained test results are shown in table 4.

CO₂Removal rate/% (CO in the exhaust gas before purification)₂Content of-CO in purified gas₂Content of)/CO in exhaust gas before purification₂Content of (2). times.100%.

TABLE 4

As can be seen from Table 4, examples 1 to 6 andcomparative examples 1 to 3 compositions for removing CO from exhaust gas₂In the purified gases of examples 1-6, CO₂Low content of CO₂All of the removal rates of (A) were 99.9 vol% or more, and CO in the purified gases of comparative examples 1 to 3₂Is higher in content of CO₂All of the removal rates were less than 99.9% by volume, indicating that the compositions of the present invention were used to remove CO from exhaust gas₂The removal effect is good, and the industrial application is facilitated.

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

1. A composition containing carboxylic acid is characterized by comprising a hydrogen bond donor and a hydrogen bond acceptor, wherein the hydrogen bond donor is carboxylic acid, and the hydrogen bond acceptor is selected from quaternary ammonium salt and/or quaternary phosphonium salt.

2. The composition of claim 1, wherein the molar ratio of the hydrogen bond donor to the hydrogen bond acceptor is from 0.2 to 5: 1, preferably 0.5 to 2: 1.

3. the composition according to claim 1 or 2, wherein the carboxylic acid has 2 to 20 carbon atoms, and is preferably at least one of a monobasic acid, a dibasic acid and a tribasic acid;

more preferably, the monobasic acid is selected from at least one of 3, 4-dihydroxycinnamic acid, 4-hydroxycinnamic acid, stearic acid and linoleic acid;

more preferably, the dibasic acid is selected from at least one of itaconic acid, oxalic acid and glutamic acid;

more preferably, the triacid is selected from at least one of 1,3, 5-pentanetricarboxylic acid, 1,2, 4-benzenetricarboxylic acid, and 1,3, 5-benzenetricarboxylic acid.

4. The composition of any of claims 1-3, wherein the quaternary ammonium salt has the formula R₁R₂R₃R₄NX, wherein R₁、R₂、R₃And R₄Identical or different and are each independently selected from alkyl, preferably alkyl having 1 to 6 carbon atoms, X is halogen, preferably selected from F, Cl, Br or I; more preferably, the quaternary ammonium salt is selected from at least one of butyltrimethylammonium chloride, tetramethylammonium chloride and tetraethylammonium chloride.

5. The composition of any of claims 1-4, wherein the quaternary phosphonium salt has the general formula R₁ ^’R₂ ^’R₃ ^’R₄ ^’PX^’Wherein R is₁ ^’、R₂ ^’、R₃ ^’And R₄ ^’Identical or different and are each independently selected from alkyl or phenyl, preferably alkyl or phenyl having 1 to 6 carbon atoms, X^’Is halogen, preferably selected from F, Cl, Br or I; more preferably, the quaternary phosphonium salt is selected from at least one of methyltriphenylphosphonium chloride, tetraphenylphosphonium bromide and tributylmethylphosphonium iodide.

6. The composition according to any one of claims 1 to 5, wherein the composition further comprises a solvent, and the molar ratio of the hydrogen bond donor to the solvent is 1 to 5: 1, preferably 2 to 4: 1;

preferably, the solvent is an organic solvent or an inorganic solvent;

preferably, the organic solvent is a saturated monohydric alcohol of C1-C4, more preferably methanol and/or ethanol;

preferably, the inorganic solvent is water, more preferably deionized water;

preferably, the composition is free of dimethyl sulfoxide, dimethyl ether of polyethylene glycol or an organic amine.

7. A method of preparing the composition of any one of claims 1 to 6, comprising: the hydrogen bond donor, hydrogen bond acceptor and optional solvent are mixed under stirring to obtain the composition.

8. The process according to claim 7, wherein the temperature of the mixing is 70-130 ℃, preferably 80-120 ℃.

9. Removing CO in waste gas₂Characterized in that the exhaust gas is contacted with an absorbent to obtain a gas containing CO₂Wherein the absorbent is the composition of any one of claims 1 to 6 or the composition prepared by the method of claim 7 or 8.

10. The method of claim 9, wherein the feed volume ratio of the off-gas to the absorbent is 5-10: 1.

11. the process as claimed in claim 9 or 10, wherein the feed volume flow of the off-gas is 1000-³/h。

12. The process according to any one of claims 9 to 11, wherein the contacting temperature is from 25 to 40 ℃ and the contacting pressure is from 0.5 to 1.5MPa, preferably from 0.8 to 1.2 MPa.

13. The method of any one of claims 9-12, wherein the method further comprises subjecting the mixture to flash evaporation to separate the absorbent and CO₂。

14. The process according to claim 13, wherein the temperature of the flash is 40-60 ℃ and the pressure of the flash is 0.05-0.1 MPa.