CN109569196B - Sulfur dioxide gas absorbent - Google Patents
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- CN109569196B CN109569196B CN201910103167.3A CN201910103167A CN109569196B CN 109569196 B CN109569196 B CN 109569196B CN 201910103167 A CN201910103167 A CN 201910103167A CN 109569196 B CN109569196 B CN 109569196B
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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
- B01D53/1493—Selection of liquid materials for use as absorbents
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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
- B01D53/1456—Removing acid components
- B01D53/1481—Removing sulfur dioxide or sulfur trioxide
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Abstract
The invention discloses a sulfur dioxide gas absorbent, which consists of an aqueous solution of an alcohol amine ionic liquid and a furoic acid type functional ionic liquid, wherein the mixed molar ratio of the alcohol amine ionic liquid and the furoic acid type functional ionic liquidThe ratio is 1: 5-10; furfuryl acid is used for replacing traditional carboxylic acid to synthesize bio-based anion functionalized ionic liquid, and the bio-based anion functionalized ionic liquid is compounded with alcohol amine ionic liquid to form a mixed absorbent, oxygen atoms on a furan ring in the furoic acid type functionalized ionic liquid and hydrogen atoms on amino groups in the alcohol amine ionic liquid form hydrogen bonds, SO that the residual hydrogen atoms in the amino groups become more active and can form hydrogen bonds with oxygen atoms in sulfur dioxide, the hydrogen bonds become more urgent, and the absorption of sulfur dioxide gas is better facilitated through the mixed synergistic effect of the alcohol amine type ionic liquid and the furoic acid type functionalized ionic liquid, and the SO provided by the invention2Absorbent pair SO2Has high absorption rate and selectivity, good regenerability and stability, and is beneficial to the recycling of the absorbent.
Description
Technical Field
The invention relates to the technical field of flue gas treatment, in particular to a sulfur dioxide gas absorbent.
Background
With the rapid development of modern industry, the demand of human beings for energy is increasing, and a great amount of fossil fuels such as coal, petroleum and natural gas are exploited and utilized, but a great amount of acid gas (such as SO) is accompanied by the requirement2、CO2、H2S, etc.) are discharged into the atmosphere, and thus air pollution, acid rain, haze, greenhouse effect, etc. are seriously threatening the environment on which humans rely to live and the health of humans themselves.
SO2The method is a gaseous pollutant with larger content and wider influence range in the existing atmospheric pollutants, and mainly comes from the combustion of fossil fuels, and the processes of roasting, smelting and the like of sulfide ores; in addition, SO is discharged from thermal power plants, non-ferrous metal smelting plants, sulfuric acid plants, oil refineries, coal-fired and oil-fired industrial boilers, furnaces and cellars and the like2Flue gas.
SO2The product is colorless and has strong pungent gas, has strong toxic effect on human respiratory organ, and can be invaded into human body through skin via pore or enter human body via alimentary canal via food and drinking water to cause harm; SO (SO)2Is a main pollutant for forming acid rain, and the acid rain has harm to various aspects such as aquatic ecosystem, agricultural ecosystem, building and material, human health and the like; in addition, in recent years, haze weather frequently occurs, and particularly in northern heavy industrial areas, the haze weather not only seriously affects the air qualityThe medicine is harmful to transportation, industrial and agricultural production, and can induce respiratory system, cardiovascular and cerebrovascular diseases and even cancers, so that the health of human bodies is harmed; the haze is a mixture of fog and haze, the haze weather refers to low visibility caused by fine particle aerosol under high humidity conditions, researches show that the haze contains high-concentration sulfate, and NO in moisture adsorbed by atmospheric fine particles2With SO2The chemical reaction of (a) is the main forming path of sulfate in the current haze; SO in air2NOx can pollute the atmosphere, reduce visibility and form haze weather, and secondary haze-causing particles can be formed through atmospheric chemical reaction, so that the probability of the haze weather is increased; more importantly, from SO2The continuous emission of gaseous pollutants and the rapid increase of economic loss cost caused by the aggravation of acid rain, haze and the like become important environmental factors restricting the economic development of China, SO that the novel and efficient SO is developed2The absorbent has economic significance and social significance.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provide a sulfur dioxide gas absorbent.
In order to achieve the purpose, the invention adopts the technical scheme that:
the sulfur dioxide gas absorbent consists of an aqueous solution of an alcohol amine ionic liquid and a furoic acid type functionalized ionic liquid, wherein the mixing molar ratio of the alcohol amine ionic liquid to the furoic acid type functionalized ionic liquid is 1: 5-10.
Preferably, the alcohol amine ionic liquid is any one of N, N-dimethylethanolamine formic acid, N-dimethylethanolamine acetic acid, N-dimethylethanolamine lactic acid, ethanolamine formic acid, ethanolamine acetic acid or diethanolamine formic acid.
Preferably, the alcohol amine ionic liquid is N, N-dimethylethanolamine formic acid.
Preferably, the furoic acid type functionalized ionic liquid is tributyl ethyl furoic acid phosphine ([ P ]4442][FA]) Tetrabutylfuroylphosphine ([ P ])4444][FA]) Or trihexyltetradecylphosphine furoate([P66614][FA]) Any one of them.
The invention also provides a preparation method of the furoic acid type functionalized ionic liquid, which is characterized in that tetraalkyl quaternary phosphine halide is used as a raw material, anion exchange is carried out to obtain tetraalkyl quaternary phosphine hydroxide solution, and then neutralization reaction is carried out on the tetraalkyl quaternary phosphine hydroxide solution and equimolar furoic acid to prepare the furoic acid anion functionalized non-proton ionic liquid.
Preferably, in the preparation method of the furoic acid type functionalized ionic liquid, the neutralization reaction temperature is 35-40 ℃, and the reaction time is 1-2 h.
Preferably, the total concentration of the alcohol amine ionic liquid and the furoic acid type functionalized ionic liquid is 0.1-0.5 mol/L.
Compared with the prior art, the invention has the beneficial effects that:
(1) according to the invention, furoic acid is used for replacing traditional carboxylic acid to synthesize the bio-based anion functionalized ionic liquid, and the bio-based anion functionalized ionic liquid is compounded with the alcohol amine ionic liquid to form the mixed absorbent, and oxygen atoms on a furan ring in the furoic acid type functionalized ionic liquid and hydrogen atoms on amino groups in the alcohol amine ionic liquid form hydrogen bonds, so that the alcohol amine ionic liquid becomes more active, and the absorption of sulfur dioxide gas is facilitated.
(2) The furoic acid has higher boiling point, and when water exists in the furoic acid type ionic liquid or the flue gas, the furoic acid generated by the neutralization reaction can still remain in the system without loss in the process of heating and desorbing sulfur dioxide by the saturated ionic liquid
(3) The carbonyl group and the oxygen atom on the furan ring in the structure of the furoic acid type functionalized ionic liquid can be used as the action site for trapping sulfur dioxide, and the ionic liquid prepared by taking the furoic acid as the raw material has larger sulfur dioxide absorption capacity and lower absorption enthalpy change.
(4) When redundant hydrogen atoms exist on the nitrogen atoms in the alcohol amine ionic liquid, oxygen atoms in sulfur dioxide are combined with the nitrogen atoms to form hydrogen bonds; when no excessive hydrogen atoms exist on the nitrogen atoms, the sulfur atoms in the sulfur dioxide tend to be in the alcohol amine ionic liquid; and the oxygen atom on the furan ring in the furoic acid type functionalized ionic liquid and the hydrogen atom on the amino group in the alcohol amine ionic liquid form a hydrogen bond, so that the residual hydrogen atom in the amino group becomes more active, and the hydrogen bond formed by the residual hydrogen atom and the oxygen atom in the sulfur dioxide becomes more urgent, thereby being more beneficial to the absorption of the sulfur dioxide.
Drawings
FIG. 1 is a graph of temperature vs. N, N-dimethylethanolamine carboxylic acid ionic liquid and tetrabutylphosphonium furoate ([ P ]4444][FA]) And (3) a performance influence diagram of the mixed ionic liquid for absorbing sulfur dioxide.
FIG. 2 is a graph of pressure vs. N, N-dimethylethanolamine carboxylic acid ionic liquid and tetrabutylphosphonium furoate ([ P ]4444][FA]) And (3) a performance influence diagram of the mixed ionic liquid for absorbing sulfur dioxide.
FIG. 3 shows N, N-dimethylethanolamine carboxylic acid ionic liquid and tetrabutylphosphonium furoate ([ P ]4444][FA]) The absorption performance of the mixed ionic liquid to different gases is compared.
FIG. 4 shows N, N-dimethylethanolamine carboxylic acid ionic liquid and tetrabutylphosphonium furoate ([ P ]4444][FA]) Five consecutive sulfur dioxide absorption-desorption cycle diagrams for the mixed ionic liquid.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more clearly apparent, the present invention is further described in detail with reference to the following embodiments; it should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention; reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated.
Example 1
This example provides a sulfur dioxide absorbent, which is prepared from an alcohol amine ionic liquid and tetrabutyl phosphonium furoate ([ P ]4444][FA]) The aqueous solution of the functionalized ionic liquid consists of the alcohol amine ionic liquid and tetrabutyl phosphine furoate ([ P ]4444][FA]) The mixing molar ratio of the functionalized ionic liquid is 1:8, and the total concentration of the alcohol amine ionic liquid and the furoic acid type functionalized ionic liquid is 0.25 mol/L.
The tetrabutyl phosphonium furoate ([ P ]4444][FA]) Preparation method package of functionalized ionic liquidThe method comprises the following steps:
s1, 2.02g (10 mmol) of tetrabutyl phosphine P was added to the flask at room temperature444And 10mL of acetonitrile, then dropwise adding a mixture of 1.50g (11 mmol) of bromobutane and 10mL of acetonitrile into the flask through a constant pressure dropping funnel, continuously stirring, completing the dropwise addition within 30min, stirring the reaction mixture at 60 ℃ overnight after the dropwise addition is completed, removing the acetonitrile by rotary evaporation after the reaction is completed, washing the residue with 3X 20mL of ethyl acetate, and drying the residue in vacuum at 40 ℃ for 24h to finally obtain the tetrabutyl phosphonium bromide [ P ] P444]Br。
S2, preparing tetrabutyl phosphonium bromide [ P ] prepared in the step S1444]Br and equimolar potassium hydroxide ethanol solution can prepare tetrabutyl hydrogen phosphine oxide [ P ] according to an anion exchange method444][OH]Ethanol solution.
S3, mixing equimols of furoic acid FA and tetrabutyl hydrogen phosphine oxide [ P444][OH]Neutralizing to obtain tetrabutyl furoic acid phosphine [ P ]444][FA]The neutralization reaction temperature is 35-40 ℃, and the reaction time is 1-2 h.
The alcohol amine ionic liquid is a series of corresponding alkaline ionic liquids generated by simple neutralization reaction of N, N-dimethylethanolamine, ethanolamine, diethanolamine, triethanolamine and the like with formic acid, acetic acid, lactic acid or carboxylic acid with a similar structure by an ice-water bath method.
Specifically, the preparation method of the alcohol amine ionic liquid comprises the following steps: adding 0.5mol of alcohol amine and 50mL of absolute ethyl alcohol into a flask, putting the flask into an ice water bath, controlling the temperature to be 0-5 ℃, dropwise adding acid at a proper dropping speed, controlling the dropwise adding speed, setting other conditions such as synthesis time and the like, then finishing the reaction, washing a reaction product with acetone for multiple times at 35 ℃ to remove unreacted substances, then carrying out reduced pressure distillation to remove the acetone, and carrying out vacuum drying on the obtained ionic liquid for 48 hours at 60 ℃ to obtain the ionic liquid.
Different alcohol amine ionic liquids and tetrabutyl phosphonium furoate ([ P ]4444][FA]) The absorption effect of the ionic liquid mixed with the functionalized ionic liquid on sulfur dioxide is shown in the following table 1, and the absorption effect takes the time required for researching that the sulfur dioxide in the tail gas reaches 100ppm after absorption as the reference.
TABLE 1 summary of the absorption time of sulfur dioxide by ionic liquids
| Ionic Liquids (ILs) | Absorption time/min for Single ILs | Mixed ILs absorption time/min |
| Tetrabutylfuroylphosphine | 180 | - |
| N, N-dimethylethanolamine carboxylic acid | 299 | 480 |
| N, N-dimethylethanolamine acetic acid | 240 | 470 |
| N, N-dimethylethanolamine | 150 | 410 |
| Ethanolamine carboxylic acid | 109 | 475 |
| Ethanolamine acetic acid | 271 | 420 |
| Ethanolamine lactic acid | 34 | 100 |
| Diethanolamine carboxylic acid | 83 | 478 |
| Diethanolamine acetic acid | 83 | 260 |
| Diethanolamine lactic acid | 67 | 240 |
| Triethanolamine lactic acid | 34 | 115 |
| Triethanolamine acetic acid | 13 | 60 |
From the results in Table 1, it is found that tetrabutylphosphonium furoate ([ P ]4444][FA]) The addition of the functionalized ionic liquid effectively improves the absorption of the alcohol amine ionic liquid to sulfur dioxide, longer absorption time is needed when the sulfur dioxide in tail gas reaches 100ppm, and the N, N-dimethylethanolamine formic acid and tetrabutyl phosphine furoate ([ P)4444][FA]) The functionalized ionic liquid mixed ionic liquid has the best effect on absorbing sulfur dioxide, and 480min is required for the sulfur dioxide in the tail gas to reach 100ppm, which indicates that the tetrabutyl phosphonium furoate ([ P ]4444][FA]) The functionalized ionic liquid has a promoting effect on the absorption of sulfur dioxide by the alcohol amine ionic liquid.
Different alcohol amine ionic liquids and tetrabutyl phosphonium furoate ([ P ]4444][FA]) The results of comparing the absorption capacity of the ionic liquid mixed with the functionalized ionic liquid to sulfur dioxide are shown in the following table 2, wherein the absorption capacity data in the table is calculated by taking absorption at about 550ppm as a standard.
TABLE 2 summary of absorption capacities of mixed ionic liquids
| Ionic liquids | Time/min | CSO2 | ACSO2 |
| N, N-dimethylethanolamine carboxylic acid | 850 | 560.9386 | 0.7210 |
| N, N-dimethylethanolamine acetic acid | 600 | 555.6979 | 0.6641 |
| N, N-dimethylethanolamine lactic acid | 580 | 542.8657 | 0.6214 |
| Ethanolamine carboxylic acid | 660 | 558 | 0.5852 |
| Ethanolamine acetic acid | 580 | 556 | 0.5410 |
| Ethanolamine | 300 | 552 | 0.3123 |
| Diethanolamine carboxylic acid | 700 | 557 | 0.6750 |
| Diethanolamine acetic acid | 480 | 549 | 0.3068 |
| Diethanolamine lactic acid | 350 | 540 | 0.2869 |
| Triethanolamine | 300 | 545 | 0.2156 |
| Triethanolamine acetic acid | 380 | 546 | 0.1086 |
From the above table results, it can be seen that: n, N-Dimethylethanolamine Carboxylic acid Phosphorinate Tetrabutylfuroate ([ P ]4444][FA]) The absorption capacity of the mixed functionalized ionic liquid to sulfur dioxide is the best, and the absorption capacity is 72.10%; diethanolamine carboxylic acid and tetrabutyl furfurylated phosphine ([ P ]4444][FA]) The absorption capacity of the mixed functionalized ionic liquid to sulfur dioxide is 67.50 percent; and N, N-dimethylethanolamine acetic acid, N-dimethylethanolamine lactic acid, ethanolamine carboxylic acid, ethanolamine acetic acid are respectively phosphine-tetra-N-butyl furoate ([ P ]4444][FA]) The compound of the functionalized ionic liquid has better absorption capacity to sulfur dioxide.
Example 2
The embodiment provides a sulfur dioxide gas absorbent, which consists of an N, N-dimethylethanolamine formic acid ionic liquid and a furoic acid type functionalized ionic liquid aqueous solution, wherein the mixing molar ratio of the alcohol amine ionic liquid to the furoic acid type functionalized ionic liquid is 1:8, and the total concentration of the N, N-dimethylethanolamine formic acid ionic liquid and the furoic acid type functionalized ionic liquid is 0.25 mol/L.
The butyl ethyl furoic acid phosphine ([ P ]4442][FA]) The preparation method of the functionalized ionic liquid comprises the following steps:
the flask was charged with 2.02g (10 mmol) of P444And 10mL of acetonitrile, then dropwise adding a mixed solution of 1.20g (11 mmol) of bromoethane and 10mL of acetonitrile into the single-neck flask through a constant-pressure dropping funnel, continuously stirring, wherein the dropwise adding operation is always performed at room temperature and is completed within 30min, after the dropwise adding is completed, the reaction mixed solution is heated to 60 ℃ through a constant-temperature water bath and is subjected to temperature control and stirring for 24 hours, after the reaction is completed, the acetonitrile is removed by rotary evaporation at 70 ℃, the residue is washed by 3 x 20mL of ethyl acetate and is dried in vacuum at 80 ℃ for 24 hours, and finally white solid [ P442]Br。
Will [ P ]4442]Br，[P66614]The [ P ] can be prepared by anion exchange of Br and potassium hydroxide ethanol solution442][OH]，[P6614][OH]Ethanol solution;
further, equimolar amounts of furoic acid FA and [ P ]442][OH]，[P6614][OH]Neutralizing to obtain [ P442][FA]、[P6614][FA]The ionic liquid prepared by the method is clear, transparent and viscous.
The absorption effect of the ionic liquid obtained by mixing different furoic acid type functionalized ionic liquids and the N, N-dimethylethanolamine formic acid ionic liquid on sulfur dioxide is shown in the following table 3, and the absorption effect takes 100ppm of sulfur dioxide in the absorbed tail gas as the reference for research.
TABLE 3 summary of the absorption time of sulfur dioxide by ionic liquids
| Ionic Liquids (ILs) | Absorption time/min for Single ILs | Mixed ILs absorption time/min |
| N, N-dimethylethanolamine carboxylic acid | 299 | - |
| [P4442][FA] | 170 | 468 |
| [P444][FA] | 180 | 480 |
| [P6614][FA] | 165 | 470 |
| [P444][OH] | 120 | 345 |
From the results in table 3, it can be seen that the addition of the N, N-dimethylethanolamine formic acid ionic liquid effectively improves the absorption of the furoic acid type functionalized ionic liquid to sulfur dioxide, a longer absorption time is required for sulfur dioxide in the tail gas to reach 100ppm, and N, N-dimethylethanolamine formic acid and tetrabutyl phosphine furoate ([ P [) are added4444][FA]) The functionalized ionic liquid mixed ionic liquid has the best effect on absorbing sulfur dioxide, and 480min is needed when the sulfur dioxide in tail gas reaches 100ppm, which shows that the N, N-dimethyl ethanolamine methanoic acid alcohol amine ionic liquid has the promotion effect on the furoic acid type functionalized ionic liquid to absorb sulfur dioxide.
Example 3
This example provides a sulfur dioxide absorbent, which is prepared from N, N-dimethylethanolamine formic acid ionic liquid and tetrabutylphosphonium furoate ([ P ]4444][FA]) The functional ionic liquid comprises a functional ionic liquid aqueous solution, the mixing molar ratio of the alcohol amine ionic liquid to the furoic acid type functional ionic liquid is 1:5-10, and the total concentration of the N, N-dimethylethanolamine formic acid ionic liquid and the furoic acid type functional ionic liquid is 0.25 mol/L.
Tetrabutylfuroylphosphine ([ P ]) at various mixing molar ratios4444][FA]) Work (Gong)The absorption effect of the ionic liquid obtained by mixing the functionalized ionic liquid and the N, N-dimethylethanolamine formic acid ionic liquid on sulfur dioxide is shown in the following table 4, and the absorption effect is based on the time required for researching that the sulfur dioxide in the absorbed tail gas reaches 100 ppm.
TABLE 4 summary of the absorption time of sulfur dioxide by ionic liquids with different mixing molar ratios
| Mixed molar ratio | Mixed ILs absorption time/min |
| 1:5 | 472 |
| 1:8 | 480 |
| 1:10 | 475 |
| 1:3 | 350 |
| 2:1 | 210 |
From the results in Table 4, it is found that N, N-dimethylethanolamine carboxylic acid ionic liquid and tetrabutyl phosphonium furoate ([ P ]4444][FA]) The functionalized ionic liquid is mixed according to the molar ratio of 1:8, then the ionic liquid absorbs sulfur dioxide, and longer absorption time is needed when the sulfur dioxide in tail gas reaches 100ppm, which shows that the N, N-dimethylethanolamine formic acid ionic liquid and tetrabutyl phosphine furoate ([ P ]4444][FA]) The functionalized ionic liquid has a molar ratio of 1:8The combination has the best absorption effect on sulfur dioxide, and the change of the mixing molar ratio of the sulfur dioxide and the sulfur dioxide is not beneficial to exerting the best absorption effect on the sulfur dioxide.
Example 4
This example provides a sulfur dioxide absorbent, which is prepared from N, N-dimethylethanolamine formic acid ionic liquid and tetrabutylphosphonium furoate ([ P ]4444][FA]) The functional ionic liquid comprises a functional ionic liquid aqueous solution, the mixing molar ratio of the alcohol amine ionic liquid to the furoic acid type functional ionic liquid is 1:8, and the total concentration of the N, N-dimethylethanolamine formic acid ionic liquid and the furoic acid type functional ionic liquid is 0.1-0.5 mol/L.
The absorption effect of the mixed ionic liquid of the N, N-dimethylethanolamine formic acid ionic liquid and the furoic acid type functionalized ionic liquid with different total concentrations on sulfur dioxide is shown in the following table 5, and the absorption effect takes the time required for researching the absorption of the sulfur dioxide in the tail gas to 100ppm after absorption as the reference.
TABLE 5 summary of the sulfur dioxide absorption time of mixed ionic liquids of different total concentrations
| Total concentration/mol/L | Mixed ILs absorption time/min |
| 0.1 | 470 |
| 0.25 | 480 |
| 0.5 | 468 |
| 0.6 | 420 |
| 0.05 | 290 |
From the results in Table 5, it is found that N, N-dimethylethanolamine carboxylic acid ionic liquid and tetrabutyl phosphonium furoate ([ P ]4444][FA]) The total concentration of the mixed ionic liquid formed after the functionalized ionic liquid is mixed is 0.25mol/L, the sulfur dioxide is absorbed, and longer absorption time is needed when the sulfur dioxide in tail gas reaches 100ppm, which shows that the N, N-dimethyl ethanolamine formic acid ionic liquid and the tetrabutyl ammonium are mixedPhosphine furoate ([ P ]4444][FA]) The mixed total concentration of the functionalized ionic liquid is 0.25mol/L, the absorption effect on sulfur dioxide is optimal, and the change of the mixed total concentration of the functionalized ionic liquid and the functionalized ionic liquid is not beneficial to the exertion of the optimal sulfur dioxide absorption effect.
Example 5
This example provides a sulfur dioxide absorbent, which is prepared from N, N-dimethylethanolamine formic acid ionic liquid and tetrabutylphosphonium furoate ([ P ]4444][FA]) The functional ionic liquid aqueous solution is composed of the alcohol amine type ionic liquid and the furoic acid type functional ionic liquid, the mixing molar ratio of the alcohol amine type ionic liquid to the furoic acid type functional ionic liquid is 1:8, the total concentration of the N, N-dimethyl ethanolamine formic acid ionic liquid and the furoic acid type functional ionic liquid is 0.25mol/L, the influences of temperature and pressure on the sulfur dioxide absorption performance of the mixed ionic liquid are discussed, and the results are respectively shown in figures 1 and 2, wherein the absorption amount in the figures is g SO2IL is expressed in units of/g.
From the results in FIG. 1, it is understood that the absorption amount is increased from 0.850g SO when the absorption temperature is increased from 293.15K to 333.15K2IL/g decreased to 0.352g SO2/g IL。
FIG. 2 is a graph showing the relationship between the absorption amount and the partial pressure at 303.15K, and it is understood from the results of the graph that the absorption amount sharply increases with an increase in pressure, and when the pressure is increased from 0.096 bar to 1.0bar, the absorption amount is from 0.259g of SO2IL/g is raised to 0.625g SO2/g IL。
The above results indicate that low temperature is favorable for absorption, high temperature is favorable for desorption and regeneration of the absorbent, and depressurization is also a method for regeneration of the absorbent.
Example 6
In practice, gas absorption is usually associated with gas separation, and gas separation techniques usually involve gas mixtures; for example, in real flue gas, SO2And CO2Are two main acid gas components, therefore, the selectivity of a specific gas absorbent to different gases is one of important indexes in the evaluation process of the specific gas absorbent; SO must be removed before carbon in the flue gas can be captured2This is because of SO2Compared with CO2More acidic, and more importantly, in CO2Regenerating the absorbentIn the process, SO previously absorbed2The ionic liquid is difficult to desorb, and in order to examine the potential application performance of the ionic liquid used in the invention, the ionic liquid prepared from N, N-dimethylethanolamine formic acid and tetrabutyl phosphonium furoate ([ P ] at 293.15K and 1.0bar is measured4444][FA]) The concentration of the functionalized ionic liquid mixed with the ionic liquid in a molar ratio of 1:8 is 0.25mol/L to CO2And N2The results of the test are shown in FIG. 3.
As can be seen from the figure, N, N-dimethylethanolamine carboxylic acid ionic liquid and tetrabutylphosphonium furoate ([ P ]4444][FA]) SO of mixed ionic liquids2The absorption capacity is obviously higher than that of CO2And N2Therefore, the mixed ionic liquid can be applied to SO in flue gas2Capture of, or removal of CO from, flue gases2And (4) pretreatment.
Example 7
In practical application, the regenerability of the ionic liquid as a gas absorbent is an important property because the ionic liquid directly relates to operation, cost and economic benefit, thereby determining the replacement frequency of the ionic liquid4444][FA]) The functionalized ionic liquid is mixed according to the molar ratio of 1:8, the mixed ionic liquid with the ionic liquid concentration of 0.25mol/L is subjected to five times of continuous absorption-desorption cycle experiments, the change rule of the absorption amount along with time is shown in figure 4, and the experimental conditions of the absorption process are 303.15K, 1atm and SO2Flow rate of 30 cm3The experimental conditions of the desorption process are 343.15K, 1atm and N2Flow rate of 60 cm3/mim。
From the results of fig. 4, it can be seen that the desorption process can be completed within 30min, and the absorption capacity of the mixed ionic liquid is not significantly reduced after five absorption-desorption cycles, which means that the ionic liquid of N, N-dimethylethanolamine formic acid and tetrabutyl phosphonium furoate ([ P ] P)4444][FA]) The functionalized ionic liquid mixed with the ionic liquid can realize SO2And (4) absorption/desorption recycling.
While the invention has been described with respect to specific embodiments thereof, it will be understood by those skilled in the art that the foregoing and other changes, omissions and deviations in the form and detail thereof may be made without departing from the scope of this invention; those skilled in the art should appreciate that they can readily use the disclosed conception and specific embodiments as a basis for designing or modifying other structures for carrying out the same purposes of the present invention without departing from the spirit and scope of the invention; meanwhile, any equivalent changes, modifications and alterations of the above embodiments according to the spirit and techniques of the present invention are also within the scope of the present invention.
Claims (4)
1. The sulfur dioxide gas absorbent is characterized by comprising an aqueous solution of an alcohol amine ionic liquid and a furoic acid type functional ionic liquid, wherein the mixing molar ratio of the alcohol amine ionic liquid to the furoic acid type functional ionic liquid is 1:5-10, the alcohol amine ionic liquid is any one of N, N-dimethylethanolamine acetic acid, N-dimethylethanolamine lactic acid, ethanolamine formic acid or diethanolamine formic acid, and the furoic acid type functional ionic liquid is tributyl ethyl furoic phosphine ([ P ] ethyl furoic acid4442][FA]) Tetrabutylfuroylphosphine ([ P ])4444][FA]) Or trihexyltetradecylphosphine furoate ([ P ]66614][FA]) Any one of them.
2. The sulfur dioxide gas absorbent as defined in claim 1, wherein the furoic acid type functionalized ionic liquid is prepared by anion exchange of tetraalkyl quaternary phosphine halide used as raw material to obtain tetraalkyl quaternary phosphine hydroxide solution, and then neutralization reaction of tetraalkyl quaternary phosphine hydroxide solution with equimolar furoic acid to obtain furoic acid anion functionalized non-protonic ionic liquid.
3. The sulfur dioxide gas absorbent as claimed in claim 2, wherein the neutralization reaction temperature is 35-40 ℃ and the reaction time is 1-2 h.
4. The sulfur dioxide gas absorbent as claimed in claim 1, wherein the total concentration of the alcohol amine type ionic liquid and the furoic acid type functionalized ionic liquid is 0.1-0.5 mol/L.
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