CN108837812B - Method for adsorbing and recovering coloring agent by swellable polyion liquid - Google Patents
Method for adsorbing and recovering coloring agent by swellable polyion liquid Download PDFInfo
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- CN108837812B CN108837812B CN201810535881.5A CN201810535881A CN108837812B CN 108837812 B CN108837812 B CN 108837812B CN 201810535881 A CN201810535881 A CN 201810535881A CN 108837812 B CN108837812 B CN 108837812B
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/26—Nature of the water, waste water, sewage or sludge to be treated from the processing of plants or parts thereof
- C02F2103/28—Nature of the water, waste water, sewage or sludge to be treated from the processing of plants or parts thereof from the paper or cellulose industry
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/30—Nature of the water, waste water, sewage or sludge to be treated from the textile industry
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Abstract
The invention discloses a method for adsorbing and recovering a coloring agent by a swellable polyionic liquid, which is characterized in that the coloring agent is adsorbed by utilizing the swelling characteristic of the polyionic liquid, and the swollen coloring agent has a three-dimensional space network structure, so that the contact between an adsorption active center and a substrate is increased, and the adsorption capacity is increased; after adsorption, the polyion liquid can be separated from the liquid phase by simple filtration, and the coloring agent can be recovered by ion exchange with a sodium chloride solution. The method for adsorbing and recovering the coloring agent has the advantages of large adsorption capacity, high adsorption efficiency, easiness in separation, high recovery rate and the like, has good adsorption and recovery effects on different coloring agents, and has potential application value.
Description
Technical Field
The invention belongs to the technical field of chemical engineering and functional materials, and particularly relates to a method for adsorbing and recovering a coloring agent by a swellable polyion liquid.
Background
The wastewater containing the coloring agent widely exists in industries such as papermaking, textile, leather and the like, becomes a non-negligible environmental problem, and the effective adsorption of pollutants is the key to solve the pollution problem of the wastewater containing the coloring agent. The adsorption method for treating the dyeing agent wastewater has the advantages of low cost, high adsorption efficiency, wide application range of pollutants, no secondary pollution and the like, thereby being attracted by researchers.
Early reports about adsorbents mainly include inorganic materials such as activated carbon, fly ash and the like, but the materials are usually small in adsorption capacity and need activation treatment before use, so that the cost and the operation difficulty are increased; the dye is generally directly burnt off or buried after use, and cannot be recycled. The polyion liquid has large adsorption capacity, can be directly put into practice without pretreatment, and has the advantages of high adsorption efficiency, no secondary pollution, easy separation, reusability and the like. Documents j, hazard. mater, 2013, 261, 83, appl. surf. sci, 2015, 326, 276, poly. j., 2016, 48, 431, ACS susteable chem. eng, 2017, 5, 2829, ChemSusChem, 2018, 11, 1092 all report the preparation of adsorbents based on polyionic liquids. Although the polyion liquid has an adsorption effect, the preparation method of the polyion liquid excessively depends on the technologies such as pore-forming and the like, and the preparation method is difficult to prepare on a large scale due to few adsorbed pollutant types.
Disclosure of Invention
The invention aims to provide a method for adsorbing and recovering a coloring agent by using a swellable polyionic liquid, which has the advantages of high adsorption rate, large adsorption capacity, high adsorption efficiency, no secondary pollution, high recovery rate, easiness in separation, wide application range of pollutants and the like, and is suitable for methyl blue, sunset yellow, amaranth, golden orange II, congo red, methylene blue, fluorescein sodium and the like.
The specific technical scheme for realizing the aim of the invention is as follows:
a method for absorbing and recovering coloring agent by swellable polyion liquid is characterized in that: adsorbing the coloring agent by using the swelling property of the polyion liquid, eliminating swelling after adsorption, separating the coloring agent from the wastewater by filtering, and performing ion exchange with a sodium chloride solution to recover the polyion liquid and the coloring agent; the method specifically comprises the following steps:
step 1: putting the polyion liquid into the coloring agent solution, and oscillating; wherein the input amount of the polyion liquid is 5-30 mg, the volume of the coloring agent solution is 35-210 ml, the concentration of the coloring agent solution is 100-700 mg/L, the temperature is 10-50 ℃, and the oscillation time is 12-24 hours;
step 2: after adsorption, the polyion liquid is deswelled and separated from the coloring agent solution through filtration; putting the polyion liquid into a sodium chloride solution, oscillating, and recovering the polyion liquid and a coloring agent; wherein the input amount of the polyion liquid is 5-30 mg, the volume of the sodium chloride solution is 50-250 ml, the concentration is 58 g/L-saturation, the temperature is 25-50 ℃, and the oscillation time is 12-24 hours; wherein:
the polyion liquid is a polymer with anions and cations on a polymerization unit, and has good swelling property in water; the cation is imidazolium, quaternary ammonium salt or quaternary phosphonium salt, and the anion is chloride; the cationic substituent on the polyionic liquid is at least one of ethyl, butyl, hydroxyethyl, dihydroxypropyl and long-chain substituent containing hydroxyl and ether bond.
The swellable polyion liquid disclosed by the invention is obtained by the following steps:
step 1: dissolving an ionic liquid monomer and a cross-linking agent in a solvent, adding an initiator, and preparing a polymerizable solution; wherein the molar ratio of the ionic liquid monomer to the cross-linking agent is 1: 0.1-1, the dosage of the initiator is 0.5-20% of the mass of the ionic liquid monomer, and the mass of the solvent is 1-10 times of the mass of the ionic liquid monomer; heating to 80 ℃ for polymerization, wherein the polymerization time is 12-24 hours;
step 2: repeatedly washing the polymerized polyion liquid with water and drying to obtain the swellable polyion liquid, wherein the water is used for washing the polymerized polyion liquid;
the polymerization unit is provided with anions and cations, wherein the cations are imidazolium, quaternary ammonium salts or quaternary phosphonium salts, and the anions are chloride ions; the substituent of the cation is at least one of ethyl, butyl, hydroxyethyl, dihydroxypropyl and long-chain substituent containing hydroxyl and ether bond.
The cross-linking agent is N, N-methylene bisacrylamide, ethylene glycol dimethacrylate, divinylbenzene or an ionic liquid type cross-linking agent.
The initiator is free radical initiated azobisisobutyronitrile.
The solvent is at least one of N, N-dimethylformamide, methanol, ethanol, water, dimethyl sulfoxide, acetonitrile, acetone, tetrahydrofuran and chloroform.
The polyion liquid is polyelectrolyte containing anionic and cationic groups on a polymer chain repeating unit, can be highly swelled in water, is a unique hydrophilic material, and is applied to various fields of liquid crystal materials, stimulus response materials, gas adsorption and separation, catalysis, water treatment and the like. In a swelling state, the polyion liquid presents a spatial three-dimensional network structure, so that the contact of a substrate and an adsorption active center can be increased, and the adsorption quantity is increased.
Compared with the prior art, the invention has the advantages that:
(1) the method is simple, can be directly put into use without a complex pretreatment flow, and is easy for large-scale adsorption and recovery of the coloring agent.
(2) The method for adsorbing and recovering the coloring agent by using the swellable polyion liquid has the advantages of high adsorption rate, large adsorption capacity, high adsorption efficiency, no secondary pollution, easiness in separation, high recovery rate, wide application range of pollutants and the like, and is suitable for methyl blue, sunset yellow, amaranth, golden orange II, congo red, methylene blue, fluorescein sodium and the like.
(3) The invention is a novel method which is simple, efficient and easy to use in scale.
Drawings
FIG. 1 is a scanning electron microscope scan of the surface topography of the swellable polyion liquid prepared in example 1 of the present invention;
FIG. 2 is a scanning electron microscope image of the surface morphology of the swellable polymeric ionic liquid prepared in example 1 of the present invention after adsorbing orange II;
FIG. 3 is a thermogravimetric analysis plot of a swellable polyionic liquid prepared in example 1 of the present invention;
FIG. 4 is a schematic view of the swollen polyion liquid adsorption of golden orange II prepared in example 1 of the present invention.
Detailed Description
The present invention is described in further detail below with reference to examples.
Example 1
Step 1: dissolving 1.773 g of ionic liquid monomer 1-vinyl-3-butylimidazolium chloride, 0.077 g of cross-linking agent N, N-methylene bisacrylamide and 0.093 g of initiator azobisisobutyronitrile into 10 ml of N, N-dimethylformamide, and uniformly mixing; the temperature is increased to 80 ℃ and the reaction is carried out for 24 hours.
Step 2: and after the polymerization is finished, washing the polymer by using deionized water, and drying in a 50 ℃ oven to obtain the swellable polyion liquid. Referring to fig. 1, a scanning electron microscope image of the surface topography of the swellable polyion liquid shows that the swellable polyion liquid presents a three-dimensional space network structure in a swelling state, and the pore size is 10-15 micrometers; referring to fig. 2, a scanning image of a cryoelectron microscope of the surface morphology of the swellable polyionic liquid after adsorbing the golden orange II shows that the pore diameter is obviously reduced to 2 to 5 micrometers after the swellable polyionic liquid adsorbs the golden orange II; referring to fig. 3, a thermogravimetric analysis graph of the swellable polyionic liquid can be seen that it can remain stable below 250 degrees celsius, indicating that the method can adsorb and recover colorants at higher temperatures.
And step 3: placing 5 mg of the swellable polyionic liquid in a conical flask, adding 35 ml of 700 mg/l aqueous solution of aurantium II, shaking at room temperature for 24 hours to achieve an adsorption effect, wherein the maximum adsorption capacity can reach 1192.0 mg/g, referring to fig. 4, which is a schematic diagram of the swellable polyionic liquid adsorbing aurantium II, it can be seen that the volume of the swellable polyionic liquid expands after swelling, and the volume of the swellable polyionic liquid reduces after adsorption.
And 4, step 4: and after filtering, putting the adsorbed polyion liquid into 100 ml of saturated sodium chloride solution, oscillating at room temperature for 24 hours to achieve a recovery effect, and recovering 22.1 mg of orange II with a recovery rate of 90%.
Example 2
Step 1: 1.572 g of ionic liquid monomer 1-vinyl-3-hydroxyethyl imidazolium chloride, 0.130 g of cross-linking agent divinylbenzene and 0.085 g of initiator azobisisobutyronitrile are dissolved in 10 ml of methanol and mixed evenly; the temperature is raised to 70 ℃ and the reaction is carried out for 24 hours.
Step 2: and after the polymerization is finished, washing the polymer by using deionized water, and drying in a 50 ℃ oven to obtain the swellable polyion liquid.
And step 3: 10 mg of the swellable polyion liquid adsorbent is placed in a conical flask, 80 ml of methyl blue aqueous solution with the concentration of 600 mg/L is added, and the mixture is shaken at room temperature for 24 hours to achieve the adsorption effect, wherein the maximum adsorption capacity can reach 1909.2 mg/g.
And 4, step 4: and after filtration, putting the adsorbed polyion liquid into 100 ml of saturated sodium chloride solution, and oscillating at room temperature for 20 hours to achieve the recovery effect, wherein 45.6 mg of methyl blue is recovered, and the recovery rate is 95%.
Example 3
Step 1: 1.842 g of ionic liquid monomer 1-vinyl-3-dihydroxypropyl imidazolium chloride, 0.198 g of cross-linking agent ethylene glycol dimethacrylate and 0.093 g of initiator azobisisobutyronitrile are dissolved in 10 ml of dimethyl sulfoxide and mixed evenly; the temperature is increased to 80 ℃ and the reaction is carried out for 24 hours.
Step 2: and after the polymerization is finished, washing the polymer by using deionized water, and drying in a 50 ℃ oven to obtain the swellable polyion liquid.
And step 3: placing the swellable polyion liquid in a conical flask, adding 50 ml of amaranth water solution with the concentration of 700 mg/L, and shaking at room temperature for 24 hours to achieve the adsorption effect, wherein the maximum adsorption capacity can reach 1314.1 mg/g.
And 4, step 4: and after filtering, putting the adsorbed polyion liquid into 100 ml of saturated sodium chloride solution, shaking at room temperature for 24 hours to achieve a recovery effect, and recovering 32.2 mg of amaranth, wherein the recovery rate is 92%.
Claims (1)
1. A method for absorbing and recovering coloring agent by swellable polyion liquid, which is characterized in that: adsorbing the coloring agent by using the swelling property of the polyion liquid, eliminating swelling after adsorption, separating from a coloring agent solution by filtering, and performing ion exchange with a sodium chloride solution to recover the polyion liquid and the coloring agent; the method specifically comprises the following steps:
step 1: putting the polyion liquid into the coloring agent solution, and oscillating to adsorb the coloring agent; wherein the input amount of the polyion liquid is 5-30 mg, the volume of the coloring agent solution is 35-210 ml, the concentration of the coloring agent solution is 100-700 mg/L, the temperature is 10-50 ℃, and the oscillation time is 12-24 hours;
step 2: after adsorption, the polyion liquid is deswelled and separated from the coloring agent solution through filtration; putting the polyion liquid into a sodium chloride solution, oscillating, and recovering the polyion liquid and a coloring agent; wherein the input amount of the polyion liquid is 5-30 mg, the volume of the sodium chloride solution is 50-250 ml, the concentration is 58 g/L-saturation, the temperature is 25-50 ℃, and the oscillation time is 12-24 hours; wherein:
the polyion liquid is a polymer with anions and cations on a polymerization unit, and has good swelling property in water;
the polyion liquid is obtained through the following steps:
step 1: dissolving ionic liquid monomer and cross-linking agent in solvent, adding initiator to prepare polymerizable solution; wherein the molar ratio of the ionic liquid monomer to the cross-linking agent is 1: 0.1-1, the dosage of the initiator is 0.5-20% of the mass of the ionic liquid monomer, and the mass of the solvent is 1-10 times of the mass of the ionic liquid monomer; heating to 80 ℃ for polymerization, wherein the polymerization time is 12-24 hours;
step 2: repeatedly washing the polymerized polyion liquid with water and drying to obtain the polyion liquid, wherein the polyion liquid is obtained;
the polymerization unit is provided with anions and cations, wherein the cations are imidazolium, quaternary ammonium salts or quaternary phosphonium salts, and the anions are chloride ions; the substituent of the cation is at least one of ethyl, butyl, hydroxyethyl, dihydroxypropyl and long-chain substituent containing hydroxyl and ether bond;
the cross-linking agent is N, N-methylene bisacrylamide, ethylene glycol dimethacrylate, divinylbenzene or an ionic liquid cross-linking agent;
the initiator is azobisisobutyronitrile;
the solvent is at least one of N, N-dimethylformamide, methanol, ethanol, water, dimethyl sulfoxide, acetonitrile, acetone, tetrahydrofuran and chloroform.
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| CN115518687B (en) * | 2022-09-20 | 2024-01-05 | 江苏大学 | Method for constructing multi-acid-base porous polyion liquid by anion exchange method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106732436A (en) * | 2017-02-15 | 2017-05-31 | 西华师范大学 | A kind of magnetic starch compound adsorbent preparation method and application |
| CN107098426A (en) * | 2017-05-18 | 2017-08-29 | 付主枝 | A kind of method of low-carbon environment-friendly degradation of dye waste water |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106732436A (en) * | 2017-02-15 | 2017-05-31 | 西华师范大学 | A kind of magnetic starch compound adsorbent preparation method and application |
| CN107098426A (en) * | 2017-05-18 | 2017-08-29 | 付主枝 | A kind of method of low-carbon environment-friendly degradation of dye waste water |
Non-Patent Citations (1)
| Title |
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| "Poly(N-isopropylacrylamide)-based ionic hydrogels: synthesis, swelling properties, interfacial adsorption and release of dyes";Xianjing Zhou等;《Polymer Journal》;20160120;第48卷;第432页右栏第1段、第433页左栏第2-3段、Figure 4 * |
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