CN112191237A - Preparation and application of porous polyion liquid compound and method for adsorbing carbon dioxide by using porous polyion liquid compound - Google Patents
Preparation and application of porous polyion liquid compound and method for adsorbing carbon dioxide by using porous polyion liquid compound Download PDFInfo
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Abstract
The invention discloses a preparation method of a porous polyion liquid compound, which is formed by compounding polyion liquid serving as a matrix and ionic liquid and a surfactant serving as a reinforcement. The porous polyion liquid composite has the effect of increasing the pore channel structure of the material by using the surfactant, and the ionic liquid reinforcement has the characteristic of reacting with carbon dioxide, so that the polyion liquid composite achieves the aim of adsorbing the carbon dioxide with high selectivity. The invention discloses a method for adsorbing carbon dioxide by using a porous polyion liquid compound, which can realize the cyclic utilization of the compound.
Description
Technical Field
The invention relates to the field of gas adsorption, in particular to preparation and application of a porous polyion liquid compound and a method for adsorbing carbon dioxide by using the porous polyion liquid compound.
Background
The greenhouse effect caused by the continuous increase of the concentration of carbon dioxide in the atmosphere is widely concerned globally, wherein the emission of coal-fired flue gas is closely related to the increase of the greenhouse effect. The method for leaching the flue gas by industrially utilizing the alcohol amine aqueous solution achieves the aim of reducing the emission of carbon dioxide, but has the defects of high carbon dioxide desorption energy consumption, easy corrosion of equipment and the like.
Solid adsorbents are favored for ease of handling, and ionization of solid adsorbents reportedly increases the carbon dioxide adsorption capacity. Thomas et al [ J.Mater.chem.A., 2014,2(30),11825-11829]A cationic microporous polymer CPN-1-Br was reported at 273K and 1bar CO2The adsorption capacity under pressure was 11.0 wt%. Plum army et al [ j.mater.chem.a.,2018,6(15),6660-6666]By supercritical CO2The porous ionized cross-linked polymer PVIm-6-SCD is prepared in CO by a drying technology2At 273K and 1bar CO215.8 wt.% under pressure. Despite extensive research on carbon dioxide adsorbent materials, the inventors have found that the ionized polymer has a high CO2Capacity for trapping and potential for selective adsorption of gases, e.g. Wangjun et al Green chem, 2017,19(11),2675-2686]Report preparation of imidazolyl-bearing porous hypercrosslinked ionomer HIP-Cl-1 by Friedel-crafts alkylation at 273K and 1bar CO2CO under pressure2An adsorption capacity of 13.7 wt% and has a capacity relative to N2Is a selectivity of 90, but its adsorption effect on carbon dioxide at low pressure has not been satisfactory. Patent CN 106492758A proposes a carbon-based carbon dioxide adsorbent material capable of adsorbing CO at low pressure (0.15bar)2However, the adsorption performance is not ideal.
Disclosure of Invention
In view of the above, the present invention aims to provide a method for preparing a porous polyion liquid composite with high selectivity (especially low pressure) for adsorbing carbon dioxide.
The invention also aims to provide application of the porous polyion liquid composite.
The invention further aims to provide a method for adsorbing carbon dioxide with high selectivity by using the porous polyion liquid composite.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a preparation method of a porous polyion liquid compound is characterized in that polyion liquid is used as a matrix, and ionic liquid capable of chemically absorbing carbon dioxide and a surfactant with the effect of increasing the pore structure of a material are used as reinforcement bodies to be compounded to form the porous polyion liquid compound.
Further, the ionic liquid is an ionic liquid with 2-hydroxypyridine as an anion.
Further, the surfactants were Span60, Span80, tween60 and tween 80.
Further, the polyion liquid is polyion liquid BzIm, and the preparation of the polyion liquid BzIm comprises the following steps: adding halide, imidazole substitute with equal reaction equivalent and acetonitrile into a hydrothermal kettle, stirring until uniform mixing and sealing, placing the hydrothermal kettle at a constant temperature of 60-120 ℃ for 24-96 hours, putting the obtained solid product into water for soaking, filtering to obtain a solid, adding a sodium hydroxide aqueous solution into the obtained solid, soaking, filtering to obtain a solid, putting the solid into the sodium hydroxide aqueous solution again for soaking, washing the obtained solid with water until the washing liquid is neutral, putting the washed solid into a 10 wt% 2-hydroxypyridine aqueous solution, stirring for 4 hours, and freeze-drying the obtained solid to obtain the polyion liquid matrix BzIm.
Further, the halide includes at least one of 1,3, 5-tris (bromomethyl) benzene, 1, 4-dichlorobenzyl, and 4, 4' -biphenyldichlorobenzyl; the imidazole substituent is at least one of 1,3, 5-tri (1-imidazole) benzene, 1, 4-di (1-imidazole benzyl), 4' -biphenyl di (1-imidazole) benzyl and 1, 4-di (1-imidazole) benzene.
Further, 2.5g of the ionic liquid is dissolved in 2.5g of surfactant to prepare ionic liquid mixed liquor, 20-30 g of water is added into 20.0 g of polyionic liquid, the ionic liquid mixed liquor is added after 30 minutes of soaking, the polyionic liquid mixed liquor is frozen for 4 hours at the temperature of-20 ℃ after ultrasonic oscillation for one hour, and the polyionic liquid compound enhanced by the ionic liquid is obtained after the polyionic liquid mixed liquor is placed in a freeze dryer to remove water.
Further, the specific surface area of the polyion liquid composite is 17-250m2The inner pore canal is micropore and mesopore with the pore diameter distribution of 1-15 nm.
After the scheme is adopted, the invention has the beneficial effects that: aiming at the technical problem of low selectivity commonly existing in the separation of carbon dioxide in industrial flue gas at present, the porous polyion liquid composite material is prepared, a surfactant is used as one of the reinforcements to enable polyion liquid to form a porous structure, and ionic liquid capable of reacting with carbon dioxide is used as the other reinforcement to achieve the purpose of selectively adsorbing carbon dioxide by the polyion liquid composite; meanwhile, the polyion liquid is used as the matrix, so that the reinforced phase is always dispersed in the matrix in the carbon dioxide adsorption and desorption process of the compound, the energy consumption and equipment requirements caused by the fact that a liquid absorbent needs to be circulated by a pump are avoided, and the operation is convenient.
The application of the porous polyion liquid compound prepared by the preparation method is used for adsorbing carbon dioxide.
A method for adsorbing carbon dioxide by the porous polyion liquid composite prepared by the preparation method comprises the steps of carrying out vacuum treatment on the porous polyion liquid composite for 2 hours at 80-120 ℃ on an adsorption instrument, and carrying out isothermal adsorption on carbon dioxide at 0-50 ℃, wherein the adsorption pressure range of the carbon dioxide is 0-102 kPa.
Further, when the isothermal adsorption of the carbon dioxide is finished, carrying out isothermal desorption of the carbon dioxide at the carbon dioxide adsorption temperature, heating the temperature to 80-120 ℃ for 2 hours after the isothermal desorption is finished, and carrying out the next isothermal adsorption of the carbon dioxide on the recovered porous polyion liquid compound.
Drawings
FIG. 1 is a graph showing isothermal adsorption curves of nitrogen (■) and carbon dioxide (●) under 25 ℃ conditions of a porous polyionic liquid composite BzIm-Mix of the invention.
Detailed Description
In order to further explain the technical solution of the present invention, the present invention is explained in detail by the following specific examples.
Example 1
Preparation of porous polyion liquid compound
1. Preparation of ionic liquids
The ionic liquid of the present invention is an ionic liquid having 2-hydroxypyridine as an anion, and the following ionic liquid is 2-hydroxypyridinated N-hexane-N-methylimidazolium salt ([ C ]6Mim][2-Op]) The description is given for the sake of example.
Ionic liquid 2-hydroxypyridinated N-hexane-N-methylimidazolium salt ([ C ]6Mim][2-Op]) The preparation method comprises the following steps: in a 250 three-neck flask, 8.2 g of methylimidazole and 50 ml of acetonitrile were added, and the methylimidazole and acetonitrile were uniformly mixed by magnetic stirring. The mixed solution of the methylimidazole and the acetonitrile is heated to be kept at the constant temperature of 80 ℃, 16.5 g of bromohexane is added dropwise under the protection of nitrogen, and the solution is kept at the temperature of 80 ℃ and stirred magnetically for 24 hours. The obtained reaction solution was subjected to rotary evaporation at 60 ℃ to remove most of the acetonitrile solvent, followed by extraction with ethyl acetate to remove the ethyl acetate solvent phase and unreacted methylimidazole and bromohexane dissolved in ethyl acetate, and the ethyl acetate extraction operation was repeated three times. The remaining phase was rotary-evaporated at 50 ℃ to remove most of the ethyl acetate solvent, and then placed in a vacuum oven at 80 ℃ for 6 hours to obtain N-methyl-N-hexylimidazole bromide ([ C ]6Mim][Br]). Taking 5.0 g of [ C ]6Mim][Br]Dissolved in 5.0 ml of water to give [ C ]6Mim][Br]The aqueous solution is subjected to anion exchange by 717 type basic anion exchange resin to obtain N-methyl-N-hexyl imidazole hydroxide ([ C)6Mim][OH]) An aqueous solution. [ C ]6Mim][OH]The water solution reacts with 2-hydroxypyridine according to the solute equimolar for 4 hours, and the solution is subject to rotary evaporation at 70 ℃ to remove water, so as to obtain the ionic liquid [ C6Mim][2-Op]。
2. Preparation of polyionic liquids
The preparation method of the polyion liquid BzIm comprises the following steps: 5.0 g of 1,3, 5-tri (bromomethyl) benzene, 5.0 g of 1, 4-diimidazole benzyl and 20 ml of acetonitrile are added into a 100 ml stainless steel hydrothermal kettle, the mixture is stirred by a glass rod until the mixture is uniformly mixed and then sealed, and the hydrothermal kettle is kept at the constant temperature of 80 ℃ for 24 hours. The resulting solid product was immersed in 100 ml of water for 24 hours and filtered to obtain an elastic gel. Adding 30 ml of 1.0mol/L sodium hydroxide aqueous solution into the obtained elastic colloid, soaking for 24 hours, filtering to obtain a solid, adding the solid into 30 ml of 1.0mol/L sodium hydroxide aqueous solution again, soaking for 24 hours, washing the filtered solid with water until the washing liquid is neutral, adding the washed solid into 15 ml of 10 wt% 2-hydroxypyridine aqueous solution, magnetically stirring for 4 hours at normal temperature, and freeze-drying the filtered solid to obtain the polyion liquid matrix BzIm.
In addition, the halide used is not only the above-mentioned 1,3, 5-tris (bromomethyl) benzene; 1, 4-dichlorobenzyl can also be adopted; 4, 4' -Biphenyldichlorobenzyl.
The imidazole substitute is prepared by adopting the 1, 4-diimidazole benzyl; 1,3, 5-tris (1-imidazole) benzene may also be used; 1, 4-bis (1-imidazole) benzene; 4, 4' -Biphenyldiimidazole benzyl.
3. Preparation of porous polyion liquid compound
The preparation method of the porous polyion liquid compound comprises the following steps: 2.5g of ionic liquid [ C ]6Mim][2-Op]Dissolved in 2.5g of surfactant Span80 to prepare ionic liquid Span80 mixed solution. And adding 20.00 g of water into 20.0 g of polyion liquid BzIm matrix, soaking for 30 minutes, adding the mixed solution of the prepared ionic liquid Span80, performing ultrasonic oscillation for one hour, freezing for 4 hours at the temperature of-20 ℃, and putting into a freeze dryer to remove water to obtain the polyion liquid compound BzIm-Mix enhanced by the ionic liquid. The specific surface area of BzIm-Mix is 17-250m by characterization2(preferably 31.5 m/g)2And/g), the inner pore canal is a micropore and a mesopore with the pore diameter distribution of 1-15 nm.
In addition to the above-mentioned Span80, the surfactant of the present invention may also be Span60, Tween60, Tween80, or the like.
Aiming at the technical problem of low selectivity commonly existing in the separation of carbon dioxide in industrial flue gas at present, the preparation method of the porous polyion liquid composite material has the advantages that the polyion liquid is made to form a porous structure by taking Span80 as one of the reinforcements, and the ionic liquid capable of reacting with carbon dioxide is taken as the other reinforcement, so that the aim of selectively adsorbing the carbon dioxide by the polyion liquid composite is fulfilled; meanwhile, the polyion liquid is used as the matrix, so that the reinforcing phase of the composite material is always dispersed in the matrix in the carbon dioxide adsorption and desorption process, the energy consumption and equipment requirements caused by the fact that a liquid absorbent needs to be circulated by a pump are avoided, and the operation is convenient.
Second, adsorption of carbon dioxide
0.2 g of porous polyion liquid compound is taken and treated for 2 hours in vacuum at 100 ℃ on a microscopic JW-DEL 200 physical adsorption instrument, and isothermal adsorption of carbon dioxide is carried out at 25 ℃. And when the isothermal adsorption of the carbon dioxide is finished, carrying out isothermal desorption of the carbon dioxide at the temperature of 25 ℃. The adsorption capacities of the porous polyionic liquid composites at different carbon dioxide pressures are listed in table 1 below.
TABLE 1.25 deg.C carbon dioxide Capacity comparison Table for porous polyion liquid composite
As can be seen from the data in Table 1, the porous polyionic liquid composite can adsorb 2.4 wt% of CO at a relatively low pressure, such as 0.5kPa2In CO2Pressure of 10-15kPa (CO in flue gas)2Equivalent pressure), CO2The adsorption capacity of the material can reach 2.9-3.0 wt%, which shows that the material is low in CO2Has carbon dioxide adsorption capacity under pressure. And with CO2The pressure is increased and the adsorption capacity is increased when CO is added2The adsorption capacity reached 7.6 wt% at a pressure of 100.2 kPa.
Example 2
The invention discloses a method for selectively adsorbing carbon dioxide by a porous polyion liquid compound, which comprises the following steps:
1. 0.2 g of porous polyion liquid compound is taken and treated for 2 hours in vacuum at 100 ℃ on a microscopic JW-DEL 200 physical adsorption instrument, and isothermal adsorption of carbon dioxide is carried out at 25 ℃.
2. 0.2 g of porous polyion liquid compound is taken and treated for 2 hours in vacuum at 100 ℃ on a precise JW-DEL 200 physical adsorption instrument, and nitrogen isothermal adsorption is carried out at 25 ℃. The carbon dioxide adsorption selectivity was calculated by the ideal solvent adsorption theory represented by equation (1), and the calculation results are shown in table 2.
TABLE 2 Selectivity of polyionic liquid complexes for adsorption of carbon dioxide.
| Carbon dioxide pressure/KPa | Carbon dioxide adsorption selectivity |
| 3.0 | 1481 |
| 4.7 | 965 |
| 8.0 | 591 |
| 15.2 | 330 |
| 24.1 | 219 |
| 34.4 | 161 |
| 45.8 | 126 |
| 58.0 | 104 |
| 70.9 | 89 |
| 84.2 | 78 |
| 97.8 | 70 |
From the results in Table 2, it can be seen that the porous polyion liquid composite can adsorb carbon dioxide with high selectivity, especially in low CO2The selectivity of the material for adsorbing carbon dioxide under pressure can reach as high as 330(15.2KPa CO)2Under pressure) and 1000 or more (3.0KPa CO)2Under pressure).
3. The porous polyion liquid compound prepared by the embodiment is applied to carbon dioxide adsorption, and the polyion liquid disperses the ionic liquid capable of reacting with carbon dioxide, so that the adsorbent has the characteristic of high-selectivity adsorption of carbon dioxide.
4. The determination method of the carbon dioxide adsorption selectivity comprises the following steps of taking 0.2 g of the porous polyion liquid composite, carrying out vacuum treatment for 2 hours at 100 ℃ on a microscopic JW-DEL 200 physical adsorption instrument, and carrying out nitrogen isothermal adsorption under the condition of carbon dioxide adsorption temperature. CO 22/N2The adsorption selectivity of (a) is calculated according to the ideal solvent adsorption theory reported by Myers and Prausnitz, and the equation is calculated as equation (1):
S＝(q1/q2)/(p1/p2) (1)
wherein S represents the adsorption selectivity of gas 1, q1And q is2Is the adsorption quantity, p, of Components 1 and 21And p2Is the partial pressure of components 1 and 2. In Table 2According to the data shown in FIG. 1, N at 25 deg.C2And CO2The isothermal adsorption data of (a) were calculated.
As a preferred embodiment, the porous polyion liquid composite of the present invention is used for recycling carbon dioxide selective adsorption, and comprises the following steps:
step 1. adsorption and desorption of carbon dioxide
0.2 g of porous polyion liquid compound is taken and treated for 2 hours in vacuum at 100 ℃ on a microscopic JW-DEL 200 physical adsorption instrument, and isothermal adsorption of carbon dioxide is carried out at 25 ℃. And when the isothermal adsorption of the carbon dioxide is finished, carrying out isothermal desorption of the carbon dioxide at the carbon dioxide adsorption temperature, namely finishing the first cycle.
Step 2, recycling of porous polyion liquid compound
And (3) finishing the isothermal desorption in the step (1), heating to 100 ℃, performing vacuum treatment for 2 hours, and performing isothermal adsorption of carbon dioxide at 25 ℃. And when the isothermal adsorption of the carbon dioxide is finished, carrying out isothermal desorption of the carbon dioxide at the carbon dioxide adsorption temperature, namely finishing the second cycle.
And 3, repeating the step 2 to obtain the capture capacity of the porous polyion liquid composite listed in the table 4 for adsorbing the carbon dioxide for 10 times of cycles.
Table 3 carbon dioxide adsorption capacity of porous polyion liquid composite at different times of use.
| Number of cycles | Adsorption Capacity (wt%) | Number of cycles | Adsorption Capacity (wt%) |
| 1 | 7.6 | 6 | 7.9 |
| 2 | 7.5 | 7 | 7.6 |
| 3 | 7.9 | 8 | 7.7 |
| 4 | 7.8 | 9 | 7.5 |
| 5 | 7.9 | 10 | 7.8 |
From the data in table 3, it can be seen that the porous polyion liquid composite can be recycled, and the carbon dioxide capture capacity is not reduced in 10 cycles.
Example 3
The invention discloses a method for adsorbing carbon dioxide by a porous polyion liquid compound under different temperature conditions, which comprises the following steps:
0.2 g of porous polyion liquid compound is taken and treated for 2 hours in vacuum at 100 ℃ on a microscopic JW-DEL 200 physical adsorption instrument, and isothermal adsorption of carbon dioxide is carried out at 0 ℃, 10 ℃,20 ℃, 25 ℃, 30 ℃ and 40 ℃ respectively, wherein the adsorption capacity of carbon dioxide at different temperatures is shown in Table 4.
Table 4. carbon dioxide adsorption capacity of polyionic liquid complexes at different temperatures.
As the polyion liquid compound can react with carbon dioxide, the data in the table 4 show that the adsorption capacity of the carbon dioxide is not obviously changed in the range of 0-40 ℃.
The above examples are not intended to limit the preparation process of the present invention, and any suitable changes or modifications made by those skilled in the art should be construed as not departing from the scope of the present invention.
Claims (10)
1. A preparation method of a porous polyion liquid compound is characterized by comprising the following steps: the composite material is formed by compounding polyion liquid serving as a matrix, and ionic liquid capable of chemically absorbing carbon dioxide and a surfactant capable of increasing the pore structure of the material serving as a reinforcement.
2. The method of claim 1, wherein the porous polyionic liquid composite is prepared by: the ionic liquid is the ionic liquid taking 2-hydroxypyridine as anions.
3. The method of claim 1, wherein the porous polyionic liquid composite is prepared by: the surfactant is Span60, Span80, Tween60 or Tween 80.
4. The method for preparing the porous polyion liquid composite according to claim 1 or 3, wherein the polyion liquid is polyion liquid BzIm, and the preparation of the polyion liquid BzIm comprises the following steps: adding halide, imidazole substitute with equal reaction equivalent and acetonitrile into a hydrothermal kettle, stirring until uniform mixing and sealing, placing the hydrothermal kettle at a constant temperature of 60-120 ℃ for 24-96 hours, putting the obtained solid product into water for soaking, filtering to obtain a solid, adding a sodium hydroxide aqueous solution into the obtained solid, soaking, filtering to obtain a solid, putting the solid into the sodium hydroxide aqueous solution again for soaking, washing the obtained solid with water until the washing liquid is neutral, putting the washed solid into a 10 wt% 2-hydroxypyridine aqueous solution, stirring for 4 hours, and freeze-drying the obtained solid to obtain the polyion liquid matrix BzIm.
5. The method of claim 4, wherein the porous polyionic liquid composite is prepared by the following steps: the halide comprises at least one of 1,3, 5-tris (bromomethyl) benzene, 1, 4-dichlorobenzyl, and 4, 4' -biphenyl dichlorobenzyl; the imidazole substituent is at least one of 1,3, 5-tri (1-imidazole) benzene, 1, 4-di (1-imidazole benzyl), 4' -biphenyl di (1-imidazole) benzyl and 1, 4-di (1-imidazole) benzene.
6. The method of claim 1, wherein the porous polyionic liquid composite is prepared by: dissolving 2.5g of the ionic liquid in 2.5g of surfactant to prepare ionic liquid mixed liquid, adding 20-30 g of water into 20.0 g of polyionic liquid, soaking for 30 minutes, adding the prepared ionic liquid mixed liquid, freezing for 4 hours at-20 ℃ after ultrasonic oscillation for one hour, and removing water in a freeze dryer to obtain the ionic liquid enhanced polyionic liquid compound.
7. The method of claim 1 or 6, wherein the porous polyionic liquid composite is prepared by: the specific surface area of the polyion liquid composite is 17-250m2The inner pore canal is micropore and mesopore with the pore diameter distribution of 1-15 nm.
8. Use of the porous polyionic liquid composite prepared by the preparation method of claim 1, wherein: for adsorbing carbon dioxide.
9. A method for adsorbing carbon dioxide by the porous polyion liquid composite prepared by the preparation method of claim 1, which is characterized in that: and (3) carrying out vacuum treatment on the porous polyion liquid compound for 2 hours at the temperature of 80-120 ℃ on an adsorption instrument, and carrying out carbon dioxide isothermal adsorption at the temperature of 0-50 ℃, wherein the adsorption pressure range of carbon dioxide is 0-102 kPa.
10. The method for adsorbing carbon dioxide by a porous polyionic liquid composite according to claim 9, wherein: and when the isothermal adsorption of the carbon dioxide is finished, carrying out isothermal desorption of the carbon dioxide at the carbon dioxide adsorption temperature, heating the temperature to 80-120 ℃ for 2 hours after the desorption is finished, and carrying out the next isothermal adsorption of the carbon dioxide on the recovered porous polyion liquid compound.
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| CN113144816A (en) * | 2021-03-12 | 2021-07-23 | 华侨大学 | Metal complex ion functionalized polyion liquid and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105418843A (en) * | 2015-12-23 | 2016-03-23 | 北京化工大学 | Preparation method of porous polymerized ionic liquid used for capture/absorption of CO2 |
| CN105597706A (en) * | 2015-12-23 | 2016-05-25 | 北京化工大学 | Preparation method for porous polymeric ionic liquid for carbon dioxide adsorption |
| CN108273477A (en) * | 2018-02-07 | 2018-07-13 | 厦门大学 | A kind of porous poly ion liquid adsorbent and its application |
| CN109456489A (en) * | 2018-09-30 | 2019-03-12 | 南京工业大学 | A kind of ordered porous poly ion liquid material, preparation method and applications |
-
2020
- 2020-09-27 CN CN202011033002.2A patent/CN112191237B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105418843A (en) * | 2015-12-23 | 2016-03-23 | 北京化工大学 | Preparation method of porous polymerized ionic liquid used for capture/absorption of CO2 |
| CN105597706A (en) * | 2015-12-23 | 2016-05-25 | 北京化工大学 | Preparation method for porous polymeric ionic liquid for carbon dioxide adsorption |
| CN108273477A (en) * | 2018-02-07 | 2018-07-13 | 厦门大学 | A kind of porous poly ion liquid adsorbent and its application |
| CN109456489A (en) * | 2018-09-30 | 2019-03-12 | 南京工业大学 | A kind of ordered porous poly ion liquid material, preparation method and applications |
Non-Patent Citations (2)
| Title |
|---|
| 郭辰辰: ""离子液体聚合物CO2吸附性能研究"", 《洁净煤技术》 * |
| 骆静宜,等: ""功能化聚合离子液体的合成及其在CO2 吸附中的应用"", 《高校化学工程学报》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113144816A (en) * | 2021-03-12 | 2021-07-23 | 华侨大学 | Metal complex ion functionalized polyion liquid and preparation method and application thereof |
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