CN113620393A - Method for removing impurity ions in ionic liquid aqueous solution system - Google Patents

Method for removing impurity ions in ionic liquid aqueous solution system Download PDF

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CN113620393A
CN113620393A CN202110901195.7A CN202110901195A CN113620393A CN 113620393 A CN113620393 A CN 113620393A CN 202110901195 A CN202110901195 A CN 202110901195A CN 113620393 A CN113620393 A CN 113620393A
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ionic liquid
ions
impurity ions
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aqueous solution
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CN113620393B (en
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王均凤
张珊珊
王道广
聂毅
张锁江
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Institute of Process Engineering of CAS
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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/469—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis
    • C02F1/4693—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis electrodialysis
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract

The invention provides a method for removing impurity ions in an ionic liquid system, which comprises the following steps: and sequentially treating the ionic liquid aqueous solution containing the impurity ions by a first-stage electrodialysis device, a second-stage electrodialysis device and a third-stage electrodialysis device to remove high-valence impurity ions, low-charge-to-mass-ratio monovalent impurity ions and high-charge-to-mass-ratio monovalent impurity ions in the ionic liquid aqueous solution to obtain the purified ionic liquid aqueous solution. And the effective separation rate of the ionic liquid and the impurity ions is improved by adopting a three-stage electrodialysis combination mode. The removal method provided by the invention effectively separates the ionic liquid and impurity ions to obtain the purified ionic liquid, does not generate industrial three wastes, and is an efficient and environment-friendly removal process; the method is simple to operate, low in energy consumption and high in efficiency, can remove impurity ions in different ionic liquid aqueous solution systems, is a removal method with strong universality, and is easy for large-scale industrial popularization.

Description

Method for removing impurity ions in ionic liquid aqueous solution system
Technical Field
The invention belongs to the technical field of ionic liquid recovery treatment, and particularly relates to a method for removing impurity ions in an ionic liquid aqueous solution system.
Background
The ionic liquid has a series of excellent characteristics, such as strong polarity, non-volatility, designable structure and the like, has wide application prospects in industry by taking the ionic liquid as a green solvent, and comprises the steps of extracting and separating heavy metals, recycling n-butyl alcohol, purifying taurine and the like by taking the ionic liquid as a solvent. The ionic liquid has good application in the process of dissolving cellulose, and various products can be obtained by dissolving natural high molecular compounds in the ionic liquid and carrying out regeneration, processing and other treatments, so that the ionic liquid is widely applied to various fields. However, in the process of dissolving cellulose with ionic liquid, there is a phenomenon that a small amount of cellulose is degraded, and since cellulose contains some impurity ions, impurity ions (Na) are contained in an ionic liquid aqueous solution obtained in the drawing and washing steps of the ionic liquid dissolving spinning process+、K+、Fe3+、Zn2+、Ca2+And Cu2+Etc.). Impurity ions are continuously accumulated in a coagulating bath and a water washing bath, and part of the impurity ions enter regenerated fibers, so that the strength and dyeing property of the regenerated fibers are seriously influenced, and the problem of removing the impurity ions in an ionic liquid aqueous solution is urgently solved for realizing the reutilization of the ionic liquid.
CN101503866 discloses a method for recovering a solvent in the preparation of regenerated cellulose fibers by using an ionic liquid as the solvent, wherein a reverse osmosis membrane is used for membrane concentration. And then carrying out reduced pressure distillation on the concentrated ionic liquid aqueous solution to obtain the ionic liquid with the water content of less than 2%. CN1944357B discloses that hydrophilic ionic liquid can be recycled after solvent extraction, water washing and dehydration treatment. CN202011324962.4 discloses a method for removing impurity ions in an ionic liquid system. The prepared cellulose-chitosan microspheres adsorb impurity ions, so that the ionic liquid is effectively recovered.
In summary, few processes for removing impurity ions from an aqueous ionic liquid solution have been reported. Based on the current situation, a method with low energy consumption, high efficiency and simple process is developed to efficiently separate impurity ions in an ionic liquid aqueous solution system, so that the ionic liquid is recycled, and the premise of large-scale industrial application of the ionic liquid is solved.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a method for removing impurity ions in an ionic liquid aqueous solution system. The ionic liquid and the impurity ions are separated through the electrodialysis treatment process, the purified ionic liquid is obtained, meanwhile, the ionic liquid is purified and concentrated fast and efficiently, and technical support is provided for resource recycling of the ionic liquid. Through three-stage electrodialysis tandem work, different substances are removed according to different electrodialysis function separation mechanisms, so that the separation efficiency of ionic liquid and impurity ions is effectively improved, and the method has the advantages of low energy consumption, high efficiency, simple process and the like.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a method for removing impurity ions in an ionic liquid aqueous solution system, which comprises the following steps: treating an ionic liquid aqueous solution to be purified by a first-stage electrodialysis device, obtaining a concentrated solution I containing low-charge-mass-ratio monovalent impurity ions and high-charge-mass-ratio monovalent impurity ions in a concentration chamber, treating the concentrated solution I as a desalting solution of a second-stage electrodialysis device, obtaining a concentrated solution II containing high-charge-mass-ratio monovalent impurity ions in the concentration chamber, treating the concentrated solution II as a desalting solution of a third-stage electrodialysis device, obtaining a desalting solution III from which high-charge-mass-ratio monovalent impurity ions, low-charge-mass-ratio monovalent impurity ions and high-charge-mass-ratio monovalent impurity ions are removed at an outlet of a desalting chamber of the third-stage electrodialysis, and obtaining a concentrated solution III containing high-charge-mass-ratio monovalent impurity ions at an outlet of the concentration chamber of the third-stage electrodialysis.
The method for removing impurity ions in the ionic liquid aqueous solution system is realized by an electrodialysis device. The removal of various impurity ions in various ionic liquids and the purification of the impurity ions are realized by utilizing the migration behavior difference and the size effect of the ionic liquids and the impurity ions in the presence of an electric field. The removal method is carried out under the drive of an electric field, has higher efficiency and small occupied area of equipment, and is more favorable for realizing large-scale industrialized application.
Preferably, the electrodialysis treatment apparatus comprises the steps of:
(1) leading the ionic liquid aqueous solution to be purified to a desalting chamber of first-stage electrodialysis, obtaining a desalting solution I containing high-valence impurity ions at an outlet of the desalting chamber of the first-stage electrodialysis, and obtaining a concentrated solution I without the high-valence impurity ions at an outlet of a concentrating chamber of the first-stage electrodialysis;
(2) conveying the concentrated solution I obtained in the step (1) to a desalting chamber of second-stage electrodialysis, obtaining a desalted solution II containing low-charge-mass-ratio monovalent impurity ions at an outlet of the desalting chamber of the second-stage electrodialysis, and obtaining a concentrated solution II without high-valence impurity ions and low-charge-mass-ratio monovalent impurity ions at an outlet of the concentrating chamber of the second-stage electrodialysis;
(3) and (3) conveying the concentrated solution II obtained in the step (2) to a desalting chamber of third electrodialysis, obtaining a desalted solution III from which high-valence impurity ions, low-charge-mass-ratio monovalent impurity ions and high-charge-mass-ratio monovalent impurity ions are removed at an outlet of the desalting chamber of the third electrodialysis, and obtaining a concentrated solution III containing high-charge-mass-ratio monovalent impurity ions at an outlet of the concentrating chamber of the third electrodialysis.
Preferably, the ionic liquid in the concentrated solution in the steps (1), (2) and (3) is the same as the ionic liquid in the ionic liquid aqueous solution to be purified.
Preferably, the concentration of the ionic liquid in the ionic liquid aqueous solution to be purified in the step (1) is 5-50 g/L, such as 5g/L, 10g/L, 15g/L, 20g/L, 25g/L, 30g/L, 35g/L, 40g/L, 45g/L and 49g/L, and specific values therebetween, which are limited by space and for the sake of brevity, the invention does not exhaustively enumerate the specific values included in the range.
Preferably, the concentration of the impurity ions in the ionic liquid aqueous solution to be purified in the step (1) is 0-5 g/L, such as 0.5g/L, 1g/L, 1.5g/L, 2g/L, 2.5g/L, 3g/L, 3.5g/L, 4.0g/L, 4.5g/L and 5.0g/L, and the specific values therebetween are limited by space and for the sake of brevity, and the invention is not exhaustive.
Preferably, step (1)The first-stage electrodialysis comprises 3 groups of electrodialysis units, wherein the electrodialysis units adopt a positive membrane of a selective sulfonic acid type cation exchange membrane CIMS and a negative membrane of a selective quaternary amine type anion exchange membrane AGU, and the feeding rate of a desalting chamber of the first-stage electrodialysis is 25-35L/(min m & lt/m & gt)2)。
Preferably, the second-stage electrodialysis in the step (2) comprises 4-6 groups of electrodialysis units, the electrodialysis units adopt a positive membrane of a selective sulfonic acid type cation exchange membrane CIMS and a negative membrane of a selective quaternary amine type anion exchange membrane AGU, and the feeding rate of a desalting chamber of the second-stage electrodialysis is 10-20L/(min m & lt/m & gt)2)。
Preferably, the third-stage electrodialysis in the step (3) comprises 4-6 groups of electrodialysis units, the electrodialysis units adopt a positive membrane of a selective sulfonic acid type cation exchange membrane CIMS and a negative membrane of a selective quaternary amine type anion exchange membrane AGU, and the feeding rate of a desalting chamber of the third-stage electrodialysis is 5-15L/(min m & lt/m & gt)2)。
Preferably, the polar liquid in the steps (1), (2) and (3) is an aqueous solution of an ionic liquid.
Preferably, the concentration of the ionic liquid in the polar liquid in the steps (1), (2) and (3) is 10-40 g/L, such as 10g/L, 13g/L, 15g/L, 18g/L, 20g/L, 23g/L, 25g/L, 27g/L, 30g/L, 32g/L, 35g/L, 37g/L or 39g/L, and the specific values therebetween are limited by space and for the sake of brevity, and the invention is not exhaustive.
Preferably, the ionic liquid in the polar liquid in the steps (1), (2) and (3) is the same as the ionic liquid in the sample to be treated.
Preferably, the operation voltage of the electrified voltage first-stage electrodialysis device in the steps (1), (2) and (3) is 60-100V. For example 60V, 70V, 80V, 90V or 100V, the operating voltages of the second and third electrodialysis units are between 40V and 80V, for example 40V, 50V, 60V, 70V or 80V, and the specific values between the above values, limited to space and for the sake of brevity, are not exhaustive of the invention to include the specific values within the stated ranges.
As a preferable technical scheme of the invention, when the electrified voltage in the steps (1), (2) and (3) is 40-100V, the process is carried out under the measured limiting current density, and the ionic liquid and the impurity ions can be efficiently separated and simultaneously the energy consumption is proper; if the voltage is set to be too high, the energy consumption is too high, and the large-scale industrial popularization is not facilitated.
Preferably, the sample to be treated, the concentrated solution and the polar solution in the steps (1), (2) and (3) are circulated at the same flow rate.
Preferably, the impurity ions in the ionic liquid aqueous solution to be treated are any 1 or at least 2 of potassium ions, sodium ions, magnesium ions, calcium ions, zinc ions, copper ions, iron ions, aluminum ions, hexyl imidazolium salts or ethyl pyridinium salts.
Preferably, the high-valence impurity ions in the ionic liquid aqueous solution to be purified are any 1 or at least 2 combinations of magnesium ions, calcium ions, zinc ions, copper ions, iron ions and aluminum ions.
Preferably, the monovalent impurity ions with small charge-mass ratio in the ionic liquid aqueous solution to be treated are any 1 or 2 of hexyl imidazolium salt or ethyl pyridinium salt.
Preferably, the monovalent impurity ions with large charge-mass ratio in the ionic liquid aqueous solution to be treated are any 1 or 2 combination of potassium ions and sodium ions.
Preferably, the desalted liquid III is a purified ionic liquid aqueous solution, wherein the content of the ionic liquid is 10-100g/L, and the content of impurity ions is less than 50 mg/L.
Compared with the prior art, the invention has the following beneficial effects:
(1) the invention relates to a method for removing impurity ions in an ionic liquid system, which adopts a three-stage electrodialysis device to realize the separation of ionic liquid and impurity ions and efficiently recover the ionic liquid.
(2) The invention has the advantages of high ionic liquid recovery rate, low energy consumption, small equipment floor area and simple process.
(3) The method for removing the impurity ions in the ionic liquid system can remove different types of ionic liquid aqueous solution systems and various impurity ions, is a widely applicable removing method, and has good application prospect.
(4) The invention adopts the combination of three-stage electrodialysis, thereby improving the effective separation efficiency of the ionic liquid and the impurity ions.
Drawings
Fig. 1 is a process flow diagram of the method for removing impurity ions in the ionic liquid aqueous solution system according to the present invention.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
The embodiment provides a method for removing impurity ions in an ionic liquid aqueous solution system, wherein the ionic liquid in the ionic liquid aqueous solution to be purified is alkyl imidazolium salt 1-ethyl-3-methylimidazolium diethyl phosphate, the impurity ions are potassium ions, and a mixture of sodium ions, calcium ions, magnesium ions and copper ions, and a positive membrane is a sulfonic acid type cation exchange membrane CIMS and a negative membrane is a quaternary amine type anion exchange membrane AGU;
the method comprises the following specific steps:
(1) 500mL of ionic liquid aqueous solution to be purified with the ionic liquid concentration of 20g/L and the impurity ion concentration of 0.5g/L are respectively led into a desalting chamber of an electrodialysis device at the flow rate of 30L/(min m.m)2) Circulating;
(2) 500mL of water (i.e., an ionic liquid having a concentration of 0g/L) was introduced as a concentrated solution into a concentration chamber of an electrodialysis device at a flow rate of 30L/(min. m)2) Circulating;
(3) introducing polar liquid with the ionic liquid concentration of 40g/L into a polar chamber of an electrodialysis device for circulation;
(4) the electrodialysis device was powered on, the first stage voltage was 70V, and the power was turned off until the current was 0.03A.
(5) Putting the solution obtained in the first stage into a desalting chamber of a second electrodialysis device, and putting the concentration chamber of the second electrodialysis device into an equal bodyThe flow rate of the accumulated water in the two chambers is 15L/(min m)2) The cycle is carried out, the operating voltage is 40V, and the power supply is turned off when the current is 0.03A.
(6) Placing the sample obtained from the second stage concentration chamber into a desalting chamber of a third electrodialysis device, placing equal volume of water into the concentration chamber of the third electrodialysis device, and placing the two chambers at a flow rate of 10L/(min m.m)2) And circulating until the current is 0.03A, and turning off the power supply.
Example 2
The embodiment provides a method for removing impurity ions in an ionic liquid aqueous solution system, wherein an ionic liquid in a sample to be treated is alkyl imidazolium salt 1-ethyl-3-methylimidazolium diethyl phosphate, the impurity ions are potassium ions, a mixture of sodium ions, calcium ions and magnesium ions, a positive membrane is a sulfonic acid type cation exchange membrane CIMS, and a negative membrane is a quaternary amine type anion exchange membrane AGU;
the method comprises the following specific steps:
(1) 500mL of ionic liquid aqueous solution to be purified with the ionic liquid concentration of 20g/L and the impurity ion concentration of 0.5g/L are respectively led into a desalting chamber of an electrodialysis device at the flow rate of 30L/(min m.m)2) Circulating;
(2) 500mL of water (i.e., an ionic liquid having a concentration of 0g/L) was introduced as a concentrated solution into a concentration chamber of an electrodialysis device at a flow rate of 30L/(min. m)2) Circulating;
(3) introducing polar liquid with the ionic liquid concentration of 40g/L into a polar chamber of an electrodialysis device for circulation;
(4) the electrodialysis device was powered on, the first stage voltage was 70V, and the power was turned off until the current was 0.03A.
(5) Putting the solution obtained in the first stage into a desalting chamber of a second electrodialysis device, putting equal volume of water into the concentrating chamber of the second electrodialysis device, and controlling the flow rate of the two chambers to be 15L/(min m & m)2) The cycle is carried out, the operating voltage is 40V, and the power supply is turned off when the current is 0.03A.
(6) Placing the sample obtained from the second stage concentration chamber into a desalting chamber of a third electrodialysis device, placing equal volume of water into the concentration chamber of the third electrodialysis device, and placing the two chambers at a flow rate of 10L/(min m.m)2) Is circulated until the current flowsThe power supply was turned off at 0.03A.
Example 3
The embodiment provides a method for removing impurity ions in an ionic liquid system, wherein the ionic liquid in an ionic liquid aqueous solution to be purified is alkyl imidazolium salt 1-ethyl-3-methylimidazolium diethyl phosphate, the impurity ions are a mixture of sodium ions and magnesium ions, a positive membrane is a sulfonic acid type cation exchange membrane CIMS, and a negative membrane is a quaternary amine type anion exchange membrane AGU;
the method comprises the following specific steps:
(1) 500mL of ionic liquid aqueous solution to be purified with the ionic liquid concentration of 20g/L and the impurity ion concentration of 0.5g/L are respectively led into a desalting chamber of an electrodialysis device at the flow rate of 30L/(min m.m)2) Circulating;
(2) 500mL of water (i.e., an ionic liquid having a concentration of 0g/L) was introduced as a concentrated solution into a concentration chamber of an electrodialysis device at a flow rate of 30L/(min. m)2) Circulating;
(3) introducing polar liquid with the ionic liquid concentration of 40g/L into a polar chamber of an electrodialysis device for circulation;
(4) the electrodialysis device was powered on, the first stage voltage was 70V, and the power was turned off until the current was 0.03A.
(5) Putting the solution obtained in the first stage into a desalting chamber of a second electrodialysis device, putting equal volume of water into the concentrating chamber of the second electrodialysis device, and controlling the flow rate of the two chambers to be 15L/(min m & m)2) The cycle is carried out, the operating voltage is 40V, and the power supply is turned off when the current is 0.03A.
(6) Placing the sample obtained from the second stage concentration chamber into a desalting chamber of a third electrodialysis device, placing equal volume of water into the concentration chamber of the third electrodialysis device, and placing the two chambers at a flow rate of 10L/(min m.m)2) And circulating until the current is 0.03A, and turning off the power supply.
Example 4
The embodiment provides a method for removing impurity ions in an ionic liquid system, wherein an ionic liquid in an ionic liquid aqueous solution to be purified is alkyl imidazolium salt 1-ethyl-3-methylimidazolium diethyl phosphate, the impurity ions are a mixture of magnesium ions, a positive membrane is a sulfonic acid type cation exchange membrane CIMS, and a negative membrane is a quaternary amine type anion exchange membrane AGU;
the method comprises the following specific steps:
(1) 500mL of ionic liquid aqueous solution to be purified with the ionic liquid concentration of 20g/L and the impurity ion concentration of 0.5g/L are respectively led into a desalting chamber of an electrodialysis device at the flow rate of 25L/(min m.m)2) Circulating;
(2) 500mL of water (i.e., an ionic liquid having a concentration of 0g/L) was introduced as a concentrated solution into a concentration chamber of an electrodialysis device at a flow rate of 25L/(min. m)2) Circulating;
(3) introducing polar liquid with the ionic liquid concentration of 40g/L into a polar chamber of an electrodialysis device for circulation;
(4) the electrodialysis device was powered on, the first stage voltage was 70V, and the power was turned off until the current was 0.03A.
(5) Putting the solution obtained in the first stage into a desalting chamber of a second electrodialysis device, putting equal volume of water into the concentrating chamber of the second electrodialysis device, and allowing the flow rate of the two chambers to be 10L/(min m.m)2) The cycle is carried out, the operating voltage is 40V, and the power supply is turned off when the current is 0.03A.
(6) Placing the sample obtained from the second stage concentration chamber into a desalting chamber of a third electrodialysis device, placing equal volume of water into the concentration chamber of the third electrodialysis device, and placing the two chambers at a flow rate of 5L/(min m.m)2) And circulating until the current is 0.03A, and turning off the power supply.
Example 5
The embodiment provides a method for removing impurity ions in an ionic liquid aqueous solution system, wherein the ionic liquid in the ionic liquid aqueous solution to be purified is alkyl imidazolium salt 1-ethyl-3-methyl imidazole diethyl phosphate, the impurity ions are a mixture of magnesium ions, a positive membrane is a sulfonic acid type cation exchange membrane CIMS, and a negative membrane is a quaternary amine type anion exchange membrane AGU;
the method comprises the following specific steps:
(1) 500mL of ionic liquid aqueous solution to be purified with the ionic liquid concentration of 20g/L and the impurity ion concentration of 0.5g/L are respectively led into a desalting chamber of an electrodialysis device at the flow rate of 25L/(min m.m)2) Circulating;
(2) 500mL of water (i.e., water)The concentration of the ionic liquid is 0g/L) is taken as a concentrated solution to enter a concentration chamber of the electrodialysis device at the flow rate of 25L/(min m.m)2) Circulating;
(3) introducing polar liquid with the ionic liquid concentration of 40g/L into a polar chamber of an electrodialysis device for circulation;
(4) and electrifying the electrodialysis device, wherein the voltage of the first stage is 80V, and turning off the power supply when the current is 0.03A.
(5) Putting the solution obtained in the first stage into a desalting chamber of a second electrodialysis device, putting equal volume of water into the concentrating chamber of the second electrodialysis device, and allowing the flow rate of the two chambers to be 10L/(min m.m)2) The cycle is carried out, the operating voltage is 50V, and the power supply is turned off when the current is 0.03A.
(6) Placing the sample obtained from the second stage concentration chamber into a desalting chamber of a third electrodialysis device, placing equal volume of water into the concentration chamber of the third electrodialysis device, and placing the two chambers at a flow rate of 5L/(min m.m)2) And circulating until the current is 0.03A, and turning off the power supply.
Example 6
The embodiment provides a method for removing impurity ions in an ionic liquid aqueous solution system, wherein the ionic liquid in the ionic liquid aqueous solution to be purified is alkyl imidazolium salt 1-ethyl-3-methyl imidazole diethyl phosphate, the impurity ions are a mixture of magnesium ions, a positive membrane is a sulfonic acid type cation exchange membrane CIMS, and a negative membrane is a quaternary amine type anion exchange membrane AGU;
the method comprises the following specific steps:
(1) 500mL of ionic liquid aqueous solution to be purified with the ionic liquid concentration of 20g/L and the impurity ion concentration of 0.5g/L are respectively led into a desalting chamber of an electrodialysis device at the flow rate of 25L/(min m.m)2) Circulating;
(2) 500mL of water (i.e., an ionic liquid having a concentration of 0g/L) was introduced as a concentrated solution into a concentration chamber of an electrodialysis device at a flow rate of 25L/(min. m)2) Circulating;
(3) introducing polar liquid with the ionic liquid concentration of 40g/L into a polar chamber of an electrodialysis device for circulation;
(4) and electrifying the electrodialysis device, wherein the voltage of the first stage is 90V, and turning off the power supply when the current is 0.03A.
(5) Putting the solution obtained in the first stage into a desalting chamber of a second electrodialysis device, putting equal volume of water into the concentrating chamber of the second electrodialysis device, and allowing the flow rate of the two chambers to be 10L/(min m.m)2) The cycle is carried out, the operating voltage is 60V, and the power supply is turned off when the current is 0.03A.
(6) Placing the sample obtained from the second stage concentration chamber into a desalting chamber of a third electrodialysis device, placing equal volume of water into the concentration chamber of the third electrodialysis device, and placing the two chambers at a flow rate of 5L/(min m.m)2) And circulating until the current is 0.03A, and turning off the power supply.
Example 7
The embodiment provides a method for removing impurity ions in an ionic liquid aqueous solution system, wherein the ionic liquid in the ionic liquid aqueous solution to be purified is alkyl imidazolium salt 1-ethyl-3-methyl imidazole diethyl phosphate, the impurity ions are a mixture of magnesium ions, a positive membrane is a sulfonic acid type cation exchange membrane CIMS, and a negative membrane is a quaternary amine type anion exchange membrane AGU;
the method comprises the following specific steps:
(1) 500mL of ionic liquid aqueous solution to be purified with the ionic liquid concentration of 20g/L and the impurity ion concentration of 0.5g/L are respectively led into a desalting chamber of an electrodialysis device at the flow rate of 25L/(min m.m)2) Circulating;
(2) 500mL of water (i.e., an ionic liquid having a concentration of 0g/L) was introduced as a concentrated solution into a concentration chamber of an electrodialysis device at a flow rate of 25L/(min. m)2) Circulating;
(3) introducing polar liquid with the ionic liquid concentration of 40g/L into a polar chamber of an electrodialysis device for circulation;
(4) and electrifying the electrodialysis device, wherein the voltage of the first stage is 100V, and turning off the power supply when the current is 0.03A.
(5) Putting the solution obtained in the first stage into a desalting chamber of a second electrodialysis device, putting equal volume of water into the concentrating chamber of the second electrodialysis device, and controlling the flow rate of the two chambers to be 15L/(min m & m)2) The cycle is carried out, the operating voltage is 70V, and the power supply is turned off when the current is 0.03A.
(6) Putting the sample obtained from the second-stage concentration chamber into a third-stage electrodialysis device for dilutionThe concentration chamber of the third electrodialysis device is filled with water with the same volume, and the flow rate of the two chambers is 10L/(min m)2) And circulating until the current is 0.03A, and turning off the power supply.
Figure BDA0003199905170000121
And (4) testing results:
(1) permeability of ionic liquid
And diluting the sample by a certain multiple, determining the absorbance of the sample at 211.40nm by using an ultraviolet spectrophotometer, and finally drawing a standard curve to obtain the concentration of the ionic liquid in the sample to be detected.
(2) Transmittance of impurity ions
And diluting the sample by a certain multiple, and measuring the content of impurity ions in the sample to be measured by an inductively coupled plasma spectrometer (ICP).
The applicant states that the present invention is illustrated by the above examples to the removal method of impurity ions in the ionic liquid system of the present invention, but the present invention is not limited to the above process steps, i.e. it does not mean that the present invention must rely on the above process steps to be carried out. It will be apparent to those skilled in the art that any modification of the present invention, equivalent substitutions of selected materials and additions of auxiliary components, selection of specific modes and the like, which are within the scope and disclosure of the present invention, are contemplated by the present invention.

Claims (7)

1. A method for removing impurity ions in an ionic liquid system is characterized in that the method for removing impurity ions is to treat an ionic liquid aqueous solution containing impurity ions to be purified through a three-stage electrodialysis device so as to efficiently separate the ionic liquid from the impurity ions, and specifically comprises the following steps:
(1) leading the ionic liquid aqueous solution to be purified with the ionic liquid concentration of 5-50 g/L and the impurity ion concentration of 0-5 g/L to a desalting chamber of first-stage electrodialysis, wherein the first-stage electrodialysis comprises 3 groups of electrodialysis units, and the electrodialysis units adopt positive membranes of selective sulfonic acid typesThe cation exchange membrane CIMS and the anion exchange membrane AGU are selective quaternary ammonium anion exchange membranes, and the feeding rate of a desalting chamber of the first-stage electrodialysis is 25-35L/(min m.m)2) Obtaining a desalted liquid I containing high-valence impurity ions at an outlet of a desalting chamber of the first-stage electrodialysis, and obtaining a concentrated liquid I without the high-valence impurity ions at an outlet of a concentrating chamber of the first-stage electrodialysis;
(2) conveying the concentrated solution I obtained in the step (1) to a desalting chamber of second-stage electrodialysis, wherein the second-stage electrodialysis comprises 4-6 groups of electrodialysis units, positive membranes adopted by the electrodialysis units are sulfonic acid type cation exchange membranes CIMS, negative membranes are quaternary ammonium type anion exchange membranes AGU, and the feeding rate of the desalting chamber of the second-stage electrodialysis is 10-20L/(min m & m)2) Obtaining a desalted solution II containing low-charge-mass-ratio monovalent impurity ions at an outlet of a desalting chamber of the second-stage electrodialysis, and obtaining a concentrated solution II without the low-charge-mass-ratio monovalent impurity ions at an outlet of a concentrating chamber of the second-stage electrodialysis;
(3) conveying the concentrated solution II obtained in the step (2) to a desalting chamber of third-stage electrodialysis, wherein the third-stage electrodialysis comprises 4-6 groups of electrodialysis units, positive membranes adopted by the electrodialysis units are sulfonic acid type cation exchange membranes CIMS, negative membranes are quaternary ammonium type anion exchange membranes AGU, and the feeding rate of the desalting chamber of the third-stage electrodialysis is 5-15L/(min m & m)2) Obtaining a desalted solution III without monovalent impurity ions with large charge-mass ratio at an outlet of a desalting chamber of the third electrodialysis, and obtaining a concentrated solution III containing monovalent impurity ions with large charge-mass ratio at an outlet of a concentrating chamber of the third electrodialysis;
the first-stage electrodialysis, the second-stage electrodialysis and the third-stage electrodialysis adopt solutions with ionic liquid concentration of 10-40 g/L as polar liquids of polar chambers, and the ionic liquids in the polar liquids are the same as the ionic liquids in the ionic liquid aqueous solution to be purified;
the operating voltage of the first-stage electrodialysis is 60-100V, and the operating voltage of the second-stage electrodialysis and the third-stage electrodialysis is 40-80V.
2. The removal method according to claim 1, wherein the ionic liquid in the ionic liquid aqueous solution to be purified in step (1) is any one of ethylimidazole salt, butylimidazole salt, ethylpyridine salt or butylpyridine salt.
3. The removal method according to claim 1, wherein the impurity ions in the ionic liquid aqueous solution to be purified in step (1) are any 1 or at least 2 of potassium ions, sodium ions, magnesium ions, calcium ions, zinc ions, copper ions, iron ions, aluminum ions, hexyl imidazolium salts or ethyl pyridinium salts.
4. The removal method of claim 1, wherein the high-valence impurity ions in the ionic liquid aqueous solution to be purified in the step (1) are any 1 or at least 2 of magnesium ions, calcium ions, zinc ions, copper ions, iron ions and aluminum ions.
5. The removal method of claim 1, wherein the monovalent impurity ions with small charge-to-mass ratio in the ionic liquid aqueous solution to be purified in step (1) are any 1 or 2 of hexyl imidazolium salt or ethyl pyridinium salt.
6. The removing method of claim 1, wherein the monovalent impurity ions with large charge-to-mass ratio in the ionic liquid aqueous solution to be purified in the step (1) are any 1 or 2 combination of potassium ions and sodium ions.
7. The removal method of claim 1, wherein the desalted liquid III is a purified ionic liquid aqueous solution, wherein the content of ionic liquid is 10-100g/L, and the content of impurity ions is less than 50 mg/L.
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