CN113101782B - Functionalized ionic liquid absorption liquid and preparation method and application thereof - Google Patents
Functionalized ionic liquid absorption liquid and preparation method and application thereof Download PDFInfo
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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
- B01D53/1493—Selection of liquid materials for use as absorbents
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- C07D233/58—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring nitrogen atoms
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Abstract
The invention discloses a functionalized ionic liquid absorption liquid and a preparation method and application thereof, and relates to the technical field of ionic liquid application. The method takes 1-butyl-3-methylimidazolium acetate ionic liquid [ BMIMAc ] as an absorption liquid, and prepares the absorption liquid with a certain concentration by matching with a viscosity reducer, an enhancer and an organic solvent, wherein the sulfur adsorption capacity of the functionalized ionic liquid absorption liquid to carbonyl sulfur is 3.092 mol/mol. The ionic liquid prepared by the method has a simple synthesis process, is convenient for large-scale preparation, can realize high-efficiency capture through multi-site action with COS molecules, can analyze the COS by adopting a heating mode, and has good cyclability and industrial prospect.
Description
Technical Field
The invention relates to the technical field of ionic liquid application, in particular to a functionalized ionic liquid absorption liquid, a preparation method thereof and application in the field of carbonyl sulfide purification.
Background
Until now, energy conversion has been mainly based on the combustion of fossil fuels, in the course of which sulfur is expressed as SO 2 And the form of COS is released into the atmosphere. The control and reduction of these emissions is very important because they are a threat to the environment and human health. Compared with SO 2 COS chemistry is more stable and more difficult to remove, and there is a strong need to develop new materials and methods for efficient, reversible and economical capture of COS for environmental protection. Over the past several decades, various Flue Gas Desulfurization (FGD) techniques have been developed, such as limestone scrubbing, ammonia scrubbing, and organic solvent absorption. Absorption in which limestone scrubbing is widely used in industry. However, the inherent disadvantages of these techniques are not negligible, including the fact that only effective removal of SO is possible 2 But the removal of COS is extremely inefficient and produces large amounts of waste water and useless by-products, which is inconsistent with sustainability guidelines.
With the continuous development of ionic liquid research and application, the types of ionic liquids are rapidly increased, and corresponding synthesis methods and means are more diversified. In particular, the rise of green chemistry and the proposal of process economy show that the basic ideas of the synthesis of novel ionic liquids are represented by the aspects of easy availability of synthetic raw materials, cleanness of a synthetic method, high efficiency of the synthetic process, specific functions, compatibility with the environment and the like. Meanwhile, with the continuous deepening of the understanding of the ionic liquid, it is found that the purity of the ionic liquid has a great influence on the performance and the application of the ionic liquid in many cases, and therefore, more attention is paid to how to obtain the high-purity ionic liquid.
The synthesis method of the ionic liquid mainly depends on the structure and the composition of the target ionic liquid, the functionalized ionic liquid is taken as a large class of ionic liquid family, and the synthesis method is similar to the synthesis method of the conventional ionic liquid, namely, the ionic liquid is prepared by selecting raw materials with specific functional groups and carrying out one-step or two-step reaction processes. Mainly divided into cationic functionalization, anionic functionalization and bifunctional functionalization. The functional ionic liquid is introduced into an imidazole skeleton through energy-containing groups such as azide and nitro, and various functional ionic liquids capable of being used for capturing sulfides such as COS are prepared.
In conclusion, it is an object of the present invention to provide an absorbent for removing carbonyl sulfide, which can efficiently and reproducibly remove carbonyl sulfide at low cost, while making full use of ionic liquids.
Chinese patent CN111040804A discloses a method for desulfurizing fuel oil by catalytic oxidation of ionic liquid, which comprises mixing the ionic liquid with the fuel oil, adding an oxidant for reaction, and separating the fuel oil from the ionic liquid after the reaction is finished to obtain clean oil. The disadvantages are too high cost of ionic liquid, limited removal rate and too high later recovery cost.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides the functionalized ionic liquid absorption liquid and the preparation method and the application thereof.
The invention relates to a functionalized ionic liquid absorption liquid which comprises the following raw materials in percentage by weight:
1-butyl-3-methylimidazole acetate: 15-50 percent
Polysiloxane type viscosity reducer: 10 to 50 percent
Enhancer: 10 to 50 percent
Solvent: and (4) the balance.
Further, the polysiloxane-type viscosity reducer is one of polymethylsiloxane, polydimethylsiloxane and polyphenylsiloxane.
Further, the enhancer is one of dimethyl sulfoxide, sulfolane, monomethylphthalein, N-methylpyrrolidone, polyethylene glycol and propylene carbonate.
Further, the solvent of the invention is one of deionized water, absolute ethyl alcohol, acetonitrile solution or cyclohexane.
Furthermore, the invention also defines a preparation method of the functionalized ionic liquid absorption liquid, and the functionalized ionic liquid absorption liquid is obtained by sequentially dripping 1-butyl-3-methylimidazole acetate, a viscosity reducer and an enhancer into a solvent at room temperature through a constant-pressure dropping funnel according to the feeding ratio and ultrasonically stirring.
Furthermore, the invention also defines a preparation method of the 1-butyl-3-methylimidazole acetate ionic liquid, which comprises the following specific steps:
1) N-methylimidazole and bromobutane as raw materials in acetonitrile solvent 2 Reacting for 4-12h at 45-65 ℃ under the atmosphere to obtain acetonitrile solution of a bromo-product intermediate;
2) Adding sodium acetate into the bromination product intermediate acetonitrile solution obtained in the step 1), reacting for 4-12h at 45-65 ℃ under normal pressure, and performing rotary evaporation after the reaction is finished to obtain the product 1-butyl-3-methylimidazole acetate.
The preparation method of the functionalized ionic liquid absorption liquid for efficiently capturing carbonyl sulfide comprises the following specific steps:
1) Taking a three-neck flask as a reaction container, adding 100mL of N-methylimidazole into the three-neck flask containing 100mL of acetonitrile solution, slowly and dropwise adding bromobutane into the acetonitrile solution of N-methylimidazole according to the molar weight of the N-methylimidazole and the bromobutane being 1.2, and introducing N into the reaction container in the preparation process 2 Protection reaction at 65 deg.C and normal pressureCarrying out reflux reaction for 10h to obtain acetonitrile solution of the bromoalkyl imidazole intermediate after the reaction is finished;
2) Taking acetonitrile solution containing bromo-alkyl imidazole intermediate prepared by the above reaction, adding sodium acetate according to 1.2 times of the molar weight of the bromo-alkyl imidazole intermediate, carrying out reflux reaction for 6h at 60 ℃ under normal pressure, and carrying out rotary evaporation and purification after the reaction is finished to obtain the final product 1-butyl-3-methylimidazole acetate;
3) Mixing 1-butyl-3-methylimidazole acetate, a reinforcer, a polysiloxane viscosity reducer and a solvent according to a feeding proportion, and fully stirring to obtain a final product, namely the functionalized ionic liquid absorption liquid.
The reagents used in the preparation process of the desulfurizer are all analytically pure.
Furthermore, the invention also defines the application of the functionalized ionic liquid as a desulfurizing agent in carbonyl sulfur purification.
The activity test of the functionalized ionic liquid absorption liquid is carried out in a circulating fixed bed, and COS standard gas is adopted in the experiment (wherein the concentration of COS is 1%, and the residual gas is N) 2 ) The COS standard gas enters the flowmeter through the pressure reducing valve and then enters the fixed bed adsorption unit at a certain flow rate to capture and adsorb the COS, and the COS standard gas enters the absorption bottle filled with the functional ionic liquid through the pipeline to be tested.
By adopting the technology, compared with the prior art, the functionalized ionic liquid absorption liquid obtained by the invention has the following advantages:
1) The functionalized ionic liquid absorption liquid is composed of four raw materials, and due to the use of a solvent, particularly a water solvent, the overall cost of the absorption liquid is lower than that of liquid-phase desulfurizing agents such as organic amine liquid and the like prepared by the prior art, and the absorption effect is better;
2) The method for regenerating the functional ionic liquid absorption liquid is simple and convenient, has high sulfur capacity recovery rate after regeneration, can be recycled for a long time, and is very suitable for industrial use.
Detailed Description
The present invention is further illustrated by the following examples, which should not be construed as limiting the scope of the invention.
The invention provides a functionalized ionic liquid absorption liquid and a preparation method and application thereof.
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.
The 1-butyl-3-methylimidazole acetate ionic liquid used in the invention has the following preparation process:
1) Adding 100mL of N-methylimidazole into a three-neck flask containing 100mL of acetonitrile solution by using a three-neck flask as a reaction container, slowly and dropwise adding bromobutane into the acetonitrile solution of N-methylimidazole according to the molar weight of 1.2 of N-methylimidazole and bromobutane, and introducing N during the preparation process 2 Protection reaction, wherein the reaction is performed for 10 hours at 65 ℃ under normal pressure by reflux reaction, and after the reaction is finished, acetonitrile solution of the bromoalkyl imidazole intermediate is obtained;
2) Taking the acetonitrile solution containing the bromo-alkyl imidazole intermediate prepared by the previous step, adding sodium acetate which is 1.2 times of the molar weight of the bromo-alkyl imidazole intermediate, carrying out reflux reaction for 6 hours at 60 ℃ under normal pressure, and carrying out rotary evaporation and purification after the reaction is finished to obtain the final product 1-butyl-3-methyl imidazole acetate.
The functionalized ionic liquid absorption liquid is prepared by mixing 1-butyl-3-methylimidazole acetate, a reinforcer, a polysiloxane viscosity reducer and deionized water according to a feeding proportion, and fully stirring to obtain a final product.
Example 1
50mL of deionized water is measured, 30g of 1-butyl-3-methylimidazole acetate, 10g of polymethylsiloxane and 10g of dimethyl sulfoxide are respectively weighed, an ionic liquid, a viscosity reducer and an enhancer are sequentially added into the ionic water dropwise at room temperature through a constant-pressure dropping funnel, and the mixture is ultrasonically stirred for 30 min to obtain the product of example 1.
10mL of the product is taken as absorption liquid and placed in a circulating fixed bed, and after the standard COS gas purified by the ionic liquid absorption liquid is dried by a drying tube, the content of COS in the product is monitored in real time by a gas chromatography. The COS content is detected every 10 min in the test process, the test is stopped when the COS content in the COS standard gas treated by the absorption liquid of the product in the example 1 is increased to 90% of the inlet concentration, and the COS capacity of the absorption liquid of the product in the example 1 is found to be 2.173 mol/mol through experimental calculation.
Example 2
50mL of deionized water is weighed, and then 25g of 1-butyl-3-methylimidazole acetate, 10g of polymethylsiloxane and 15g of dimethyl sulfoxide are respectively weighed. And (3) sequentially dropwise adding the ionic liquid, the viscosity reducer and the reinforcing agent into the ionic water at room temperature through a constant-pressure dropping funnel, and ultrasonically stirring for 30 min to obtain a product of example 2.
10mL of the product is taken as absorption liquid and placed in a circulating fixed bed, and after the standard COS gas purified by the ionic liquid absorption liquid is dried by a drying tube, the content of COS in the product is monitored in real time by a gas chromatography. The COS content is detected every 10 min in the test process, the test is stopped when the COS content in the COS standard gas treated by the absorption liquid of the product in the example 2 rises to 90% of the inlet concentration, and the COS capacity of the absorption liquid of the product in the example 2 is found to be 2.581 mol/mol through experimental calculation.
Example 3
40mL of deionized water is weighed, and then 25g of 1-butyl-3-methylimidazole acetate, 10g of polymethylsiloxane and 15g of dimethyl sulfoxide are respectively weighed. And (3) sequentially dropwise adding the ionic liquid, the viscosity reducer and the reinforcing agent into the ionic water at room temperature through a constant-pressure dropping funnel, and ultrasonically stirring for 30 min to obtain a product of example 3.
10mL of the product is taken as absorption liquid and placed in a circulating fixed bed, and after the standard COS gas purified by the ionic liquid absorption liquid is dried by a drying tube, the content of COS in the product is monitored in real time by a gas chromatography. The COS content is detected every 10 min in the test process, the test is stopped when the COS content in the COS standard gas treated by the absorption liquid of the product in the example 3 is increased to 90% of the inlet concentration, and the COS capacity of the absorption liquid of the product in the example 3 is found to be 2.935 mol/mol through experimental calculation.
Example 4
30mL of deionized water is weighed, and then 25g of 1-butyl-3-methylimidazole acetate, 10g of polymethylsiloxane and 15g of dimethyl sulfoxide are respectively weighed. And (3) sequentially dropwise adding the ionic liquid, the viscosity reducer and the reinforcing agent into the ionic water at room temperature through a constant-pressure dropping funnel, and ultrasonically stirring for 30 min to obtain a product of example 4.
10mL of the product is taken as absorption liquid and placed in a circulating fixed bed, and after the standard COS gas purified by the ionic liquid absorption liquid is dried by a drying tube, the content of COS in the product is monitored in real time by a gas chromatography. In the test process, the content of COS is detected once every 10 min, the test is stopped when the content of COS in the standard COS gas treated by the absorption liquid of the product in the example 4 is increased to 90% of the concentration of the COS at the inlet, and the COS capacity of the absorption liquid of the product in the example 4 is found to be 3.092 mol/mol through experimental calculation.
Example 5
50mL of deionized water is weighed, and then 15g of 1-butyl-3-methylimidazole acetate, 10g of polymethylsiloxane and 25g of dimethyl sulfoxide are respectively weighed. And (3) sequentially dropwise adding the ionic liquid, the viscosity reducer and the reinforcing agent into the ionic water at room temperature through a constant-pressure dropping funnel, and ultrasonically stirring for 30 min to obtain a product of example 5.
10mL of the product is taken as absorption liquid and placed in a circulating fixed bed, and after the standard COS gas purified by the ionic liquid absorption liquid is dried by a drying tube, the content of COS in the product is monitored in real time by a gas chromatography. In the test process, the content of COS is detected once every 10 min, the test is stopped when the content of COS in the standard COS gas treated by the absorption liquid of the product in the example 5 is increased to 90% of the concentration of the COS at the inlet, and the COS capacity of the absorption liquid of the product in the example 5 is found to be 2.351 mol/mol through experimental calculation.
Example 6
40mL of deionized water is weighed, and then 40g of 1-butyl-3-methylimidazole acetate, 10g of polymethylsiloxane and 10g of dimethyl sulfoxide are respectively weighed. And (3) sequentially dropwise adding the ionic liquid, the viscosity reducer and the reinforcing agent into the ionic water at room temperature through a constant-pressure dropping funnel, and ultrasonically stirring for 30 min to obtain a product of example 6.
10mL of the product is taken as absorption liquid and placed in a circulating fixed bed, and after the standard COS gas purified by the ionic liquid absorption liquid is dried by a drying tube, the content of COS in the product is monitored in real time by a gas chromatography. In the test process, the content of COS is detected once every 10 min, the test is stopped when the content of COS in the standard COS gas treated by the absorption liquid of the product in the example 6 is increased to 90% of the concentration of the inlet, and the COS capacity of the absorption liquid of the product in the example 6 is found to be 2.104 mol/mol through experimental calculation.
Example 7
30mL of deionized water is weighed, and then 40g of 1-butyl-3-methylimidazole acetate, 10g of polymethylsiloxane and 10g of dimethyl sulfoxide are respectively weighed. And (3) sequentially dropwise adding the ionic liquid, the viscosity reducer and the reinforcing agent into the ionic water at room temperature through a constant-pressure dropping funnel, and ultrasonically stirring for 30 min to obtain a product of example 7.
10mL of the product is taken as absorption liquid and placed in a circulating fixed bed, and after the standard COS gas purified by the ionic liquid absorption liquid is dried by a drying tube, the content of COS in the product is monitored in real time by a gas chromatography. The COS content is detected every 10 min in the test process, the test is stopped when the COS content in the COS standard gas treated by the absorption liquid of the product in the example 7 is increased to 90% of the concentration of the inlet, and the COS capacity of the absorption liquid of the product in the example 7 is found to be 2.008 mol/mol through experimental calculation.
Example 8
The prepared functionalized ionic liquid absorption liquid obtained by experimental proportioning of example 4 is repeatedly saturated after absorbing COS, and is subjected to N bubbling at 85 ℃ for 90 min 2 And (4) regenerating. And after regeneration, placing the regenerated COS standard gas in a circulating fixed bed, and performing gas chromatography to monitor the content of COS in the purified COS standard gas in real time after the purified COS standard gas is dried by a drying tube. Detecting the content of COS once every 10 min in the test process, stopping the test when the content of COS in the COS standard gas treated by the absorption liquid is increased to 90% of the concentration of an inlet, and finding out that N with the bubbling temperature of 85 ℃ is blown in through the test 2 The functional ionic liquid absorption liquid obtained by the experimental proportion of the example 4 can be effectively regenerated, andand the sulfur capacity can recover more than 95 percent of the original sulfur capacity.
Example 9
The prepared functionalized ionic liquid absorption liquid obtained by experimental proportioning of example 4 is repeatedly heated to 85 ℃ in water bath and stirred for regeneration after absorbing COS saturation. And after regeneration, placing the regenerated COS standard gas in a circulating fixed bed, and performing gas chromatography to monitor the content of COS in the purified COS standard gas in real time after the purified COS standard gas is dried by a drying tube. The COS content is detected once every 10 min in the test process, the experiment is stopped when the COS content in the COS standard gas to be treated by the absorption liquid rises to 90% of the concentration of the inlet, the experiment shows that the functionalized ionic liquid absorption liquid obtained by the experiment proportioning of the embodiment 4 can be effectively regenerated in a heating and stirring mode, and the sulfur capacity can be recovered to be more than 93% of the initial sulfur capacity.
Table 1: different proportions of the functionalized ionic liquid absorption liquid and sulfur capacity thereof in examples 1-7
Example 10
30g of absolute ethyl alcohol is weighed, and then 25g of 1-butyl-3-methylimidazole acetate, 10g of polymethylsiloxane and 15g of sulfolane are respectively weighed. And (3) sequentially dropwise adding the ionic liquid, the viscosity reducer and the reinforcing agent into the ionic water at room temperature through a constant-pressure dropping funnel, and ultrasonically stirring for 30 min to obtain a product of example 10.
10mL of the product is taken as absorption liquid and placed in a circulating fixed bed, and after the standard COS gas purified by the ionic liquid absorption liquid is dried by a drying tube, the content of COS in the product is monitored in real time by a gas chromatography. In the test process, the content of the COS is detected once every 10 min, the test is stopped when the content of the COS in the standard COS gas treated by the absorption liquid of the product No. 10 in the example rises to 90% of the concentration of the COS at the entrance, and the COS capacity of the absorption liquid of the product No. 10 in the example is found to be 2.693 mol/mol through experimental calculation.
Example 11
30g of cyclohexane was weighed out, and then 25g of 1-butyl-3-methylimidazolium acetate, 10g of polydimethylsiloxane and 15g of N-methylpyrrolidone were weighed out, respectively. And (3) sequentially dropwise adding the ionic liquid, the viscosity reducer and the reinforcing agent into the ionic water at room temperature through a constant-pressure dropping funnel, and ultrasonically stirring for 30 min to obtain a product of example 11.
10mL of the product is taken as absorption liquid and placed in a circulating fixed bed, and after the standard COS gas purified by the ionic liquid absorption liquid is dried by a drying tube, the content of COS in the product is monitored in real time by a gas chromatography. The COS content is detected every 10 min in the test process, the test is stopped when the COS content in the COS standard gas treated by the absorption liquid of the product in the example 11 is increased to 90% of the inlet concentration, and the COS capacity of the absorption liquid of the product in the example 11 is found to be 2.925 mol/mol through experimental calculation.
Example 12
30g of acetonitrile solution is weighed, and then 25g of 1-butyl-3-methylimidazole acetate, 10g of polyphenylsiloxane and 15g of polyethylene glycol are respectively weighed. And (3) sequentially dropwise adding the ionic liquid, the viscosity reducer and the reinforcing agent into the ionic water at room temperature through a constant-pressure dropping funnel, and ultrasonically stirring for 30 min to obtain a product of example 12.
10mL of the product is taken as absorption liquid and placed in a circulating fixed bed, and after the standard COS gas purified by the ionic liquid absorption liquid is dried by a drying tube, the content of COS in the product is monitored in real time by a gas chromatography. In the test process, the content of COS is detected once every 10 min, the test is stopped when the content of COS in the standard COS gas treated by the absorption liquid of the product No. 12 is increased to 90% of the concentration of the inlet, and the COS capacity of the absorption liquid of the product No. 12 in the example is found to be 2.351 mol/mol through experimental calculation.
Table 2: examples 10-12 different ratios of functionalized ionic liquid absorbents and sulfur capacities
The comparison example shows that when deionized water or an organic solvent is used as the solvent of the ionic liquid absorption liquid, the difference of the sulfur capacities is not large, the organic solvent is expensive, so that the overall cost is too high, and the organic solvent is volatile, so that the viscosity of the ionic liquid is gradually increased, the fluidity of carbonyl sulfide is weakened, and the sulfur capacity is gradually reduced. Deionized water is relatively more suitable as a solvent for the ionic liquid absorbent.
Claims (4)
1. A functional ionic liquid absorption liquid is characterized in that raw materials comprise the following components in percentage by weight:
1-butyl-3-methylimidazole acetate: 15-30%
Polysiloxane type viscosity reducer: 10 to 50 percent
Enhancer: 10 to 15 percent of
Deionized water: the balance;
according to the feeding ratio, sequentially dripping 1-butyl-3-methylimidazole acetate, a viscosity reducer and an enhancer into the ionic water at room temperature through a constant-pressure dropping funnel, and ultrasonically stirring to obtain the functionalized ionic liquid absorption liquid;
the preparation method of the 1-butyl-3-methylimidazole acetate comprises the following steps:
1) N-methylimidazole and bromobutane as raw materials in acetonitrile solvent 2 Reacting for 4-12h at 45-65 ℃ under the atmosphere to obtain acetonitrile solution of a bromo-product intermediate;
2) Adding sodium acetate into the bromination product intermediate acetonitrile solution obtained in the step 1), reacting for 4-12h at 45-65 ℃ under normal pressure, and performing rotary evaporation after the reaction is finished to obtain the product 1-butyl-3-methylimidazole acetate.
2. The functionalized ionic liquid absorption liquid according to claim 1, wherein the polysiloxane-based viscosity reducer is one of polymethylsiloxane, polydimethylsiloxane and polyphenylsiloxane.
3. The functionalized ionic liquid absorbent solution according to claim 1, wherein the enhancer is one of dimethylsulfoxide, sulfolane, N-methylpyrrolidone, polyethylene glycol, and propylene carbonate.
4. The functionalized ionic liquid absorption liquid as claimed in claim 1 is applied to carbonyl sulfur purification as a desulfurizing agent.
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