CN108837812A - A kind of method of swellable poly ion liquid absorption and recycling coloring agent - Google Patents
A kind of method of swellable poly ion liquid absorption and recycling coloring agent Download PDFInfo
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- CN108837812A CN108837812A CN201810535881.5A CN201810535881A CN108837812A CN 108837812 A CN108837812 A CN 108837812A CN 201810535881 A CN201810535881 A CN 201810535881A CN 108837812 A CN108837812 A CN 108837812A
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- ion liquid
- poly ion
- coloring agent
- absorption
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- 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
- B01J20/26—Synthetic macromolecular compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- 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
- B01J20/30—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
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- 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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- Organic Chemistry (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses the methods of a kind of swellable poly ion liquid absorption and recycling coloring agent, coloring agent is adsorbed using poly ion liquid swelling character, it has three-dimensional space network structure after being swollen, and increases contact of the adsorption activity center with substrate, increases adsorbance；Poly ion liquid can be made from liquid phase separation by simple filtration after absorption, coloring agent can be recycled using with sodium chloride solution ion exchange.Absorption of the invention and the method for recycling coloring agent have many advantages, such as that large amount of adsorption, adsorption efficiency are high, easily separated, the rate of recovery is high, and have good absorption and recovering effect to variety classes coloring agent, have potential application.
Description
Technical field
The invention belongs to chemical, technical field of function materials more particularly to a kind of swellable poly ion liquid absorption
With the method for recycling coloring agent.
Background technique
Waste water containing coloring agent is widely present in the industries such as papermaking, weaving, leather, becomes a very important environment and asks
Topic, effectively adsorbing to pollutant is the key that solve waste water pollution problem containing coloring agent.It is useless using absorption method processing coloring agent
Water tool is at low cost, adsorption efficiency is high, is applicable in the advantages that pollutant is wide, without secondary pollution, thus by the concern of researcher.
The report about adsorbent of early stage is mainly the inorganic material such as active carbon, flyash, however such material is often
Adsorbance is smaller, and using preceding needing to be activated, increases cost and operation difficulty；It typically directly burns up or fills out after use
It buries, coloring agent cannot be reused.And poly ion liquid large amount of adsorption, without pretreatment can direct plunge into it is applicable, have inhale
The advantages that attached high-efficient, without secondary pollution, easily separated and reusable.Document J. Hazard. Mater., 2013,
261, 83、Appl. Surf. Sci., 2015, 326, 276、Poly. J., 2016, 48, 431、ACS
Sustainable Chem. Eng., 2017,5,2829, ChemSusChem, 2018,11,1092 report with poly-
The preparation of adsorbent based on ionic liquid.Although these poly ion liquids have adsorption effect, preparation method mistake
Degree relies on the technologies such as pore-creating, and it is few to adsorb pollutant kind, it is difficult to large scale preparation.
Summary of the invention
The object of the present invention is to provide the method for a kind of swellable poly ion liquid absorption and recycling coloring agent, this method tools
Have that the rate of adsorption is fast, large amount of adsorption, adsorption efficiency are high, without secondary pollution, the rate of recovery is high, easily separated and applicable pollutant is extensively etc. excellent
Point is applicable in methyl blue, sunset yellow, amaranth, gold orange II, Congo red, methylene blue, fluorescein sodium etc..
Realizing the object of the invention specific technical solution is：
A kind of method of swellable poly ion liquid absorption and recycling coloring agent, feature are：Utilize the swellability of poly ion liquid
Coloring agent can be adsorbed, deswelling after absorption is separated through filtering with waste water, by carrying out ion exchange with sodium chloride solution, is reached
To the recycling to poly ion liquid and coloring agent；Specifically include following steps：
Step 1：Poly ion liquid is put into dyeing agent solution, is shaken；Wherein, poly ion liquid input amount is 5 ~ 30 millis
Gram, coloring agent liquor capacity is 35 ~ 210 milliliters, and coloring agent solution concentration is 100 ~ 700 mg/litres, and temperature is 10 ~ 50 DEG C, shake
Swinging the time is 12 ~ 24 hours；
Step 2：After absorption, poly ion liquid deswelling is separated through filtering with dyeing agent solution；Poly ion liquid is put into
Sodium chloride solution is shaken, and poly ion liquid and coloring agent are recycled；Wherein poly ion liquid input amount is 5 ~ 30 milligrams, chlorine
Changing sodium solution volume is 50 ~ 250 milliliters, and concentration is 58 grams per liters ~ saturation, and temperature is 25 ~ 50 DEG C, and the concussion time is 12 ~ 24 small
When；Wherein：
The poly ion liquid is the polymer on polymerized unit with zwitterion, has good swellability in water；Its
Cation is imidazoles, quaternary ammonium salt or quaternary phosphine salt, and anion is chloride ion；It is cationic on the poly ion liquid to take
At least one of Dai Jiwei ethyl, butyl, ethoxy, dihydroxypropyl, hydroxyl and long chain substituents of ehter bond.
Swellable poly ion liquid of the present invention is obtained by following steps：
Step 1：Ionic liquid monomer and crosslinking agent are dissolved in solvent, initiator is added, configuring can poly solution；Wherein, from
The molar ratio of sub- liquid monomer and crosslinking agent is 1:0.1 ~ 1, initiator amount is the 0.5 ~ 20% of ionic liquid monomer quality, molten
The quality of agent is 1 ~ 10 times of ionic liquid monomer quality；It is warming up to 80 DEG C to be polymerize, polymerization time is 12 ~ 24 hours；
Step 2：With the poly ion liquid after the completion of the polymerization of water repeated flushing and dry to get the swellable poly ion liquid,
Wherein；
There is zwitterion, cation is that imidazoles, quaternary ammonium salt or quaternary phosphine salt, anion are on the polymerized unit
Chloride ion；The substituent group of the cation is the long chain substituents of ethyl, butyl, ethoxy, dihydroxypropyl, hydroxyl and ehter bond
At least one of.
The crosslinking agent be N,N methylene bis acrylamide, ethylene glycol dimethacrylate, divinylbenzene or from
Sub- liquid-type crosslinking agent.
The initiator is free radical polymerization azodiisobutyronitrile.
The solvent be N,N-dimethylformamide, methanol, ethyl alcohol, water, dimethyl sulfoxide, acetonitrile, acetone, tetrahydrofuran and
At least one of chloroform.
Poly ion liquid of the present invention is that one kind containing zwitterion group on polymer chain repetitive unit is poly-
Electrolyte can be highly swollen in water, be a kind of unique hydrophilic material, in liquid crystal material, stimuli responsive material, gas
Adsorb with separate, be catalyzed, water process etc. is multi-field is applied.In the swollen state, space three-dimensional net is presented in poly ion liquid
Network structure, can increase the contact of substrate with adsorption activity center, to increase adsorbance.
Compared with prior art, advantage of the invention is that：
（1）The method of the present invention is simple, needs not move through complicated pretreatment process, can direct plunge into use, be easy to extensive
Absorption and recycling coloring agent.
（2）The method for adsorbing and recycling coloring agent with swellable poly ion liquid fast, adsorbance with the rate of adsorption
Greatly, the advantages that adsorption efficiency is high, without secondary pollution, easily separated, the high and applicable pollutant of the rate of recovery is wide, to methyl blue, sunset yellow,
Amaranth, gold orange II, Congo red, methylene blue, fluorescein sodium etc. are applicable in.
（3）The present invention is a kind of to be simple and efficient, be easy to the new method that scale uses.
Detailed description of the invention
Fig. 1 is the electron cryo-microscopy scanning figure of swellable poly ion liquid surface topography prepared by the embodiment of the present invention 1；
Fig. 2 is the electron cryo-microscopy that swellable poly ion liquid prepared by the embodiment of the present invention 1 adsorbs the surface topography after gold orange II
Scanning figure；
Fig. 3 is the thermal gravimetric analysis curve figure of swellable poly ion liquid prepared by the embodiment of the present invention 1；
Fig. 4 is that the prepared swelling poly ion liquid of the embodiment of the present invention 1 adsorbs gold orange II schematic diagram.
Specific embodiment
Below in conjunction with example, present invention is further described in detail.
Embodiment 1
Step 1：By 1.773 grams of ionic liquid monomer 1- vinyl -3- butyl imidazole villaumite, 0.077 gram of crosslinking agent N, N-
Methylene-bisacrylamide and 0.093 gram of initiator azodiisobutyronitrile are dissolved in 10 milliliters of n,N-Dimethylformamide,
It is uniformly mixed；80 degrees Celsius are warming up to, is reacted 24 hours.
Step 2：After the completion of polymerization, polymer is rinsed with deionized water, and in 50 degrees Celsius of drying in oven to get to originally
Invent the swellable poly ion liquid.Refering to fig. 1, it is scanned for the electron cryo-microscopy of the surface topography of the swellable poly ion liquid
Figure, it can be seen that three-dimensional space network structure is presented in it in the swollen state, and aperture is 10-15 microns；Referring to Fig.2, can for this
The electron cryo-microscopy scanning figure of surface topography after being swollen poly ion liquid absorption gold orange II, it can be seen that aperture is bright after it is adsorbed
Aobvious become smaller is 2-5 microns；Refering to Fig. 3, for the thermal gravimetric analysis curve figure of the swellable poly ion liquid, it can be seen that it can be
250 degrees Celsius or less holdings are stablized, and illustrate that this method can adsorb and recycle at a higher temperature coloring agent.
Step 3：By 5 milligrams, the swellable poly ion liquid is placed in conical flask, be added 35 milliliters of concentration be 700 milligrams/
Rise gold orange II aqueous solution, room temperature shake 24 hours, reach adsorption effect, maximal absorptive capacity up to 1192.0 milligrams per grams, refering to
Fig. 4 adsorbs gold orange II schematic diagram for the swellable poly ion liquid, it can be seen that volume expansion after it is swollen, body after absorption
Product reduces.
Step 4：The poly ion liquid after absorption is put into 100 milliliters of saturated sodium chloride solutions, room temperature concussion after filtering
24 hours, reach recovering effect, recycles 22.1 milligrams of gold orange II, the rate of recovery 90%.
Embodiment 2
Step 1：By 1.572 grams of ionic liquid monomer 1- vinyl -3- hydroxyethyl imidazole villaumite, 0.130 gram of crosslinking agent two
Vinyl benzene and 0.085 gram of initiator azodiisobutyronitrile are dissolved in 10 milliliters of methanol, are uniformly mixed；It is Celsius to be warming up to 70
Degree reacts 24 hours.
Step 2：After the completion of polymerization, polymer is rinsed with deionized water, and in 50 degrees Celsius of drying in oven to get to originally
The invention swellable poly ion liquid.
Step 3：By 10 milligrams, the swellable poly ion liquid adsorbent is placed in conical flask, and 80 milliliters of concentration are added and are
The methyl blue aqueous solution of 600 mg/litres, room temperature are shaken 24 hours, reach adsorption effect, maximal absorptive capacity is up to 1909.2 millis
Gram gram.
Step 4：The poly ion liquid after absorption is put into 100 milliliters of saturated sodium chloride solutions, room temperature concussion after filtering
20 hours, reach recovering effect, recycles 45.6 milligrams of methyl blues, the rate of recovery 95%.
Embodiment 3
Step 1：By 1.842 grams of ionic liquid monomer 1- vinyl -3- dihydroxypropyl imidazoles villaumite, 0.198 gram of crosslinking agent
Ethylene glycol dimethacrylate and 0.093 gram of initiator azodiisobutyronitrile are dissolved in 10 milliliters of dimethyl sulfoxide, mixing
Uniformly；80 degrees Celsius are warming up to, is reacted 24 hours.
Step 2：After the completion of polymerization, polymer is rinsed with deionized water, and in 50 degrees Celsius of drying in oven to get to originally
The invention swellable poly ion liquid.
Step 3：The swellable poly ion liquid will be dried to be placed in conical flask, it is 700 mg/litres that 50 milliliters of concentration, which are added,
Amaranth aqueous solution, room temperature are shaken 24 hours, reach adsorption effect, maximal absorptive capacity is up to 1314.1 milligrams per grams.
Step 4：The poly ion liquid after absorption is put into 100 milliliters of saturated sodium chloride solutions, room temperature concussion after filtering
24 hours, reach recovering effect, recycles 32.2 milligrams of amaranths, the rate of recovery 92%.
Claims (1)
1. a kind of method of swellable poly ion liquid absorption and recycling coloring agent, it is characterised in that：Utilize poly ion liquid
Swelling behavior adsorbs coloring agent, and deswelling after absorption is separated through filtering with waste water, by carrying out ion friendship with sodium chloride solution
It changes, reaches the recycling to poly ion liquid and coloring agent；Specifically include following steps：
Step 1：Poly ion liquid is put into dyeing agent solution, carries out concussion to adsorb coloring agent；Wherein, poly ion liquid is thrown
Entering amount is 5 ~ 30 milligrams, and coloring agent liquor capacity is 35 ~ 210 milliliters, and coloring agent solution concentration is 100 ~ 700 mg/litres, temperature
It is 10 ~ 50 DEG C, the concussion time is 12 ~ 24 hours；
Step 2：After absorption, poly ion liquid deswelling is separated through filtering with dyeing agent solution；Poly ion liquid is put into
Sodium chloride solution is shaken, and poly ion liquid and coloring agent are recycled；Wherein poly ion liquid input amount is 5 ~ 30 milligrams, chlorine
Changing sodium solution volume is 50 ~ 250 milliliters, and concentration is 58 grams per liters ~ saturation, and temperature is 25 ~ 50 DEG C, and the concussion time is 12 ~ 24 small
When；Wherein：
The poly ion liquid is the polymer on polymerized unit with zwitterion, has good swellability in water；Its
Cation is imidazoles, quaternary ammonium salt or quaternary phosphine salt, and anion is chloride ion；It is cationic on the poly ion liquid to take
At least one of Dai Jiwei ethyl, butyl, ethoxy, dihydroxypropyl, hydroxyl and long chain substituents of ehter bond.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810535881.5A CN108837812B (en) | 2018-05-30 | 2018-05-30 | Method for adsorbing and recovering coloring agent by swellable polyion liquid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810535881.5A CN108837812B (en) | 2018-05-30 | 2018-05-30 | Method for adsorbing and recovering coloring agent by swellable polyion liquid |
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| Publication Number | Publication Date |
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| CN108837812A true CN108837812A (en) | 2018-11-20 |
| CN108837812B CN108837812B (en) | 2021-05-07 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114276322A (en) * | 2022-01-06 | 2022-04-05 | 惠州市绿色能源与新材料研究院 | Method for preparing cyclic carbonate by photo-initiated polymerization of ionic liquid material |
| CN115518687A (en) * | 2022-09-20 | 2022-12-27 | 江苏大学 | Method for constructing polyacid-based porous polyion liquid by anion exchange method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
-
2018
- 2018-05-30 CN CN201810535881.5A patent/CN108837812B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
|---|
| XIANJING ZHOU等: ""Poly(N-isopropylacrylamide)-based ionic hydrogels: synthesis, swelling properties, interfacial adsorption and release of dyes"", 《POLYMER JOURNAL》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114276322A (en) * | 2022-01-06 | 2022-04-05 | 惠州市绿色能源与新材料研究院 | Method for preparing cyclic carbonate by photo-initiated polymerization of ionic liquid material |
| CN115518687A (en) * | 2022-09-20 | 2022-12-27 | 江苏大学 | Method for constructing polyacid-based porous polyion liquid by anion exchange method and application thereof |
| 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 |
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| CN108837812B (en) | 2021-05-07 |
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