CN110614081A - Method for treating printing and dyeing wastewater by using magnetic microcapsules - Google Patents
Method for treating printing and dyeing wastewater by using magnetic microcapsules Download PDFInfo
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- CN110614081A CN110614081A CN201910960797.2A CN201910960797A CN110614081A CN 110614081 A CN110614081 A CN 110614081A CN 201910960797 A CN201910960797 A CN 201910960797A CN 110614081 A CN110614081 A CN 110614081A
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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
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
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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
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
- B01J20/28009—Magnetic properties
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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
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
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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
- C02F1/48—Treatment of water, waste water, or sewage with magnetic or electric fields
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
Abstract
The invention relates to a method for treating printing and dyeing wastewater by using magnetic microcapsules, belonging to the field of composite materials. The method comprises the following steps: coating polyacrylamide hydrochloride (PAH) and ferromagnetic graphene oxide layer by layer on a template under the action of electrostatic force, and removing template particles to obtain a hollow-structure microcapsule formed by self-assembling the ferromagnetic graphene oxide and polyelectrolyte layer by layer; putting the prepared microcapsule into a methylene blue dye solution for adsorption research; washing and desorbing the microcapsules adsorbing the methylene blue dye by using a certain amount of acetic acid methanol solution; the ferromagnetic graphene oxide microcapsule prepared by the invention has the capability of embedding various medicines, has a good release control function, can realize the separation of certain dyes in printing and dyeing wastewater under the action of an external magnetic field by using the hybrid magnetic microcapsule as a carrier, provides practical experience for sewage treatment and environmental protection in dyeing and finishing industry, and has a very wide development space in the aspect of environmental protection.
Description
Technical Field
The invention relates to a method for treating printing and dyeing wastewater by using magnetic microcapsules, belonging to the field of composite materials.
Background
The composite material prepared by the graphene oxide can be used as a photocatalyst for organic pollutants such as Methylene Blue (MB), rhodamine B (RhB) and other dyes, and can realize high removal rate of the dyes. In engineering applications, ferromagnetic graphene oxide (Fe)3O4@ GO) and the hybridized microcapsule taking the @ GO as a capsule wall material have the advantages of easy desorption, good recycling performance, certain magnetism and obvious advantage in the process of removing pollutants due to the fact that the methylene blue dye can be efficiently and massively adsorbed.
The graphene oxide with the ferromagnetic particles has the characteristics of easy separation, recycling, magnetic response and the like. In order to explore the adsorption performance of the ferromagnetic graphene oxide and the hybrid microcapsule thereof on the printing and dyeing wastewater, a cationic dye methylene blue is used as a simulation object, and the aim of treating the printing and dyeing wastewater is fulfilled by adsorbing the cationic dye by utilizing the electrostatic interaction between the ferromagnetic graphene oxide and the hybrid microcapsule thereof and the cationic dye.
Disclosure of Invention
The invention improves the method, and prepares ferromagnetic graphene oxide/polyelectrolyte composite microcapsules with certain response performance; using a certain concentration of sodium polystyrene sulfosulfonate (PSS) solution and Na2CO3Solution and Ca (NO)3)2·4H2Preparation of CaCO from O solution3The template adopts a layer-by-layer self-assembly technology, and Polypropylene Amine Hydrochloride (PAH) solution and ferromagnetic graphene oxide solution are alternately assembled on the CaCO of the template3Removing cores by using a sodium ethylene diamine tetracetate solution with a certain concentration to prepare a novel microcapsule which can be used for embedding various medicines; putting the prepared ferromagnetic graphene oxide/polyelectrolyte composite microcapsule into a methylene blue dye solution for adsorption research; adsorbing methylene blue dye with a certain amount of methanol acetate solutionAnd washing and desorbing the microcapsules.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a method for treating printing and dyeing wastewater by using magnetic microcapsules comprises the following steps:
(1) preparing a template of the microcapsule: mixing Na2CO3Solution and Ca (NO) containing sodium salt of polystyrene sulfonic acid (PSS)3)2·4H2Mixing the O solutions, standing until the solution is layered, and removing the supernatant to obtain CaCO with negative charges3Microparticles;
(2) coating of wall material of the microcapsule: mixing CaCO3Uniformly dispersing the particle powder in a polyacrylamide hydrochloride (PAH) solution, oscillating in a water bath oscillator, and then carrying out centrifugal washing to finish the assembly of the first layer; and dispersing the particle powder assembled with a layer of polyacrylamide hydrochloride (PAH) in a ferromagnetic graphene oxide solution, oscillating the particle powder in a water bath under the same conditions, and performing centrifugal washing, so that the assembly is a double-layer assembly. Repeating the above operations to prepare ferromagnetic graphene oxide/polyelectrolyte-calcium carbonate microspheres with different assembly layers;
(3) removing the template of the microcapsule: CaCO to be coated3Dispersing the particles in EDTA solution, oscillating in water bath, centrifuging, removing supernatant, washing with deionized water, and repeating the above steps to completely remove CaCO3Obtaining ferromagnetic graphene oxide/polyelectrolyte composite hollow microcapsules by using template particles;
(4) adsorption of the microcapsules to the methylene blue dye: adding the ferromagnetic graphene oxide microcapsules into a methylene blue solution, carrying out magnetic separation on the mixture under the action of an external magnetic field, and measuring the absorbance of supernatant liquid after different time. Adjusting the pH value of the solution by using hydrochloric acid and sodium hydroxide solution, and exploring the adsorption effect of the ferromagnetic graphene oxide microcapsule mixed solution on methylene blue dye under different pH values;
(5) desorption of the microcapsules for methylene blue dye: adding a certain amount of acetic acid methanol solution into the ferromagnetic graphene oxide microcapsule mixed solution adsorbed with methylene blue for elution;
na as described in the above step (1)2CO3The concentration of the solution is 0.1-1mol/L, Ca (NO)3)2·4H2The concentration of O solution is 0.1-1mol/L, Ca (NO)3)2·4H2The concentration of PSS in the O solution is 1-8g/L, and the standing time is 15-40 min.
CaCO as described in the above step (2)3The concentration of the microparticle solution is 1-5g/mL, the concentration of the polyacrylamide hydrochloride (PAH) solution is 0.5-5g/L, the times of centrifugal washing are 1-5 times, the concentration of the ferromagnetic graphene oxide solution is 0.01-0.05g/L, and the dosage of the solution is 5-15 mL. .
The concentration of the ethylenediaminetetraacetic acid sodium (EDTA) solution in the step (3) is 0.1-0.5mol/L, the dosage of the solution is 15-50mL, and CaCO is added3The water bath oscillation time of the particles in the sodium ethylene diamine tetracetate solution is 15-45 min.
The volume of the ferromagnetic graphene oxide solution in the step (4) is 1-10mL, the concentration of the adopted hydrochloric acid and sodium hydroxide solution is 0.1-1mol/L, and the pH value of the solution is adjusted to be 2-14.
The volume percentage of the acetic acid-methanol solution in the step (5) is 0-15%.
The invention has the advantages that:
in the field of textile printing and dyeing, the ferromagnetic graphene oxide/polyelectrolyte composite microcapsule can be used for coating and controllable release of dye, can effectively improve the utilization rate of the dye, can realize treatment of printing and dyeing wastewater in dyeing and finishing processing due to the electrostatic effect between the microcapsule and cationic dye, and has very positive influence on environmental protection; and the ferromagnetic graphene oxide/polyelectrolyte composite microcapsule can coat some medicines with health care or treatment functions, is arranged on the surface of the fabric, and has good treatment effect on some diseases (such as rheumatism and the like) by controlling the release of the medicines. Meanwhile, the hybrid magnetic graphene oxide/polyacrylamide hydrochloride microcapsule has the advantages of easy desorption, good recycling performance and certain magnetism, has remarkable advantages in the process of removing pollutants, and provides an effective method for purifying printing and dyeing wastewater.
Drawings
The drawings are only for purposes of illustrating and explaining the present invention and are not to be construed as limiting the scope of the present invention. Wherein:
FIG. 1 is a photograph showing the results of example 1 of the present invention;
FIG. 2 is a photograph showing the results of example 2 of the present invention;
FIG. 3 is a photograph showing the results of example 3 of the present invention.
Detailed Description
The invention is described below in connection with specific embodiments with the attached figures. Unless otherwise specified, the technical means used in the present invention are well known to those skilled in the art. In addition, the embodiments should be considered illustrative, and not restrictive, of the scope of the invention, which is defined solely by the claims. It will be apparent to those skilled in the art that various changes or modifications in the components and amounts of the materials used in these embodiments can be made without departing from the spirit and scope of the invention.
Example 1:
mixing PAH and Fe3O4@ GO is alternately assembled on the template particles, and the template is removed by EDTA to obtain (PAH/Fe)3O4@GO)nPAH, as a carrier for absorbing dye in printing and dyeing wastewater, is prepared by the photo as shown in figure 1.
Example 2:
150. mu.L, 200. mu.L, 250. mu.L, 300. mu.L, 350. mu.L and 400. mu.L of the dye solution are respectively taken by a pipette gun, added into 25mL centrifuge tubes, respectively added with distilled water to make the volume of the solution be 10mL, and respectively measured with 4mL of methylene blue dye solution from each centrifuge tube by the pipette gun to measure the absorbance. The photographs shown in FIG. 2 were obtained as the absorbance standard curve of methylene blue dye.
Example 3:
the pH of the solution was adjusted to a range of 2-14 using NaOH and HCl hydrochloric acid. And testing the adsorption amount of the ferromagnetic graphene oxide microcapsules on the methylene blue dye under different pH values. A picture as shown in fig. 3 is obtained.
Claims (6)
1. A method for treating printing and dyeing wastewater by using magnetic microcapsules comprises the following steps:
(1) preparing a template of the microcapsule: mixing Na2CO3Solution and Ca (NO) containing sodium salt of polystyrene sulfonic acid (PSS)3)2·4H2Mixing the O solutions, standing until the solution is layered, and removing the supernatant to obtain CaCO with negative charges3Microparticles;
(2) coating of wall material of the microcapsule: mixing CaCO3Uniformly dispersing the particle powder in a polyacrylamide hydrochloride (PAH) solution, oscillating in a water bath oscillator, and then carrying out centrifugal washing to finish the assembly of the first layer; then, the particle powder assembled with a layer of polyacrylamide hydrochloride (PAH) is dispersed in ferromagnetic graphene oxide solution, and the water bath is oscillated and centrifugally washed under the same conditions, so that a two-layer assembly is formed. Repeating the above operations to prepare ferromagnetic graphene oxide/polyelectrolyte-calcium carbonate microspheres with different assembly layers;
(3) removing the template of the microcapsule: CaCO to be coated3Dispersing the particles in EDTA solution, oscillating in water bath, centrifuging, removing supernatant, washing with deionized water, and repeating the above steps to completely remove CaCO3Obtaining ferromagnetic graphene oxide/polyelectrolyte composite hollow microcapsules by using template particles;
(4) adsorption of the microcapsules to the methylene blue dye: adding the ferromagnetic graphene oxide microcapsules into a methylene blue solution, carrying out magnetic separation on the mixture under the action of an external magnetic field, and measuring the absorbance of supernatant liquid after different time. Adjusting the pH value of the solution by using hydrochloric acid and sodium hydroxide solution, and exploring the adsorption effect of the ferromagnetic graphene oxide microcapsule mixed solution on methylene blue dye under different pH values;
(5) desorption of the microcapsules for methylene blue dye: and adding a certain amount of acetic acid methanol solution into the ferromagnetic graphene oxide microcapsule mixed solution adsorbed with the methylene blue for desorption.
2. The method for treating printing and dyeing wastewater with magnetic microcapsules as claimed in claim 1, wherein Na is used in the step (1)2CO3The concentration of the solution is 0.1-1mol/L, Ca (NO)3)2·4H2The concentration of O solution is 0.1-1mol/L, Ca (NO)3)2·4H2The concentration of PSS in the O solution is 1-8g/L, and the standing time is 15-40 min.
3. The method for treating printing and dyeing wastewater with magnetic microcapsules as claimed in claim 1, wherein the CaCO used in the step (2) is CaCO3The concentration of the microparticle solution is 1-5g/mL, the concentration of the polyacrylamide hydrochloride (PAH) solution is 0.5-5g/L, the times of centrifugal washing are 1-5 times, the concentration of the ferromagnetic graphene oxide solution is 0.01-0.05g/L, and the dosage of the solution is 5-15 mL.
4. The method for treating printing and dyeing wastewater by using magnetic microcapsules as claimed in claim 1, wherein the concentration of the solution of sodium Ethylenediaminetetraacetate (EDTA) in the step (3) is 0.1-0.5mol/L, the amount of the solution is 15-50mL, CaCO3The water bath oscillation time of the particles in the sodium ethylene diamine tetracetate solution is 15-45 min.
5. The method for treating printing and dyeing wastewater by using magnetic microcapsules as claimed in claim 1, wherein the volume of the ferromagnetic graphene oxide solution in the step (4) is 1-10mL, the concentration of the hydrochloric acid and sodium hydroxide solution is 0.1-1mol/L, and the pH value of the solution is adjusted to be 2-14.
6. The method for treating printing and dyeing wastewater by using magnetic microcapsules as claimed in claim 1, wherein the volume percentage of the acetic acid-methanol solution in the step (5) is 0% -15%.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201910960797.2A CN110614081A (en) | 2019-10-09 | 2019-10-09 | Method for treating printing and dyeing wastewater by using magnetic microcapsules |
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| CN201910960797.2A CN110614081A (en) | 2019-10-09 | 2019-10-09 | Method for treating printing and dyeing wastewater by using magnetic microcapsules |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104056597A (en) * | 2014-06-30 | 2014-09-24 | 大连理工大学 | Application of recyclable magnetic nanocapsule to dye adsorption |
| CN104098729A (en) * | 2014-07-02 | 2014-10-15 | 同济大学 | Preparing method and application of MGO-MIP (Magnetic Graphene Oxide-Molecular Imprinting) composite material |
| CN107837792A (en) * | 2017-12-20 | 2018-03-27 | 中国海洋大学 | A kind of preparation method of cyclodextrin modified magnetic hollow microcapsules sorbing material |
| CN109126651A (en) * | 2018-09-19 | 2019-01-04 | 天津工业大学 | A kind of preparation method of ferromagnetic graphene oxide/polyelectrolyte composite micro-capsule |
| CN110639442A (en) * | 2019-10-09 | 2020-01-03 | 天津工业大学 | Preparation method of diclofenac sodium-loaded natural polysaccharide microcapsule |
-
2019
- 2019-10-09 CN CN201910960797.2A patent/CN110614081A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104056597A (en) * | 2014-06-30 | 2014-09-24 | 大连理工大学 | Application of recyclable magnetic nanocapsule to dye adsorption |
| CN104098729A (en) * | 2014-07-02 | 2014-10-15 | 同济大学 | Preparing method and application of MGO-MIP (Magnetic Graphene Oxide-Molecular Imprinting) composite material |
| CN107837792A (en) * | 2017-12-20 | 2018-03-27 | 中国海洋大学 | A kind of preparation method of cyclodextrin modified magnetic hollow microcapsules sorbing material |
| CN109126651A (en) * | 2018-09-19 | 2019-01-04 | 天津工业大学 | A kind of preparation method of ferromagnetic graphene oxide/polyelectrolyte composite micro-capsule |
| CN110639442A (en) * | 2019-10-09 | 2020-01-03 | 天津工业大学 | Preparation method of diclofenac sodium-loaded natural polysaccharide microcapsule |
Non-Patent Citations (1)
| Title |
|---|
| 赵芷芪: "氧化石墨烯/聚电解质微胶囊的制备与应用研究", 《中国优秀硕士学位论文全文数据库工程科技1辑》 * |
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Application publication date: 20191227 |