CN111514865A - Preparation of resin microspheres and application of resin microspheres in printing and dyeing wastewater treatment - Google Patents

Preparation of resin microspheres and application of resin microspheres in printing and dyeing wastewater treatment Download PDF

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CN111514865A
CN111514865A CN202010388537.5A CN202010388537A CN111514865A CN 111514865 A CN111514865 A CN 111514865A CN 202010388537 A CN202010388537 A CN 202010388537A CN 111514865 A CN111514865 A CN 111514865A
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resin microspheres
resin
wastewater
printing
dyeing wastewater
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闫娟
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    • 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
    • B01J20/261—Synthetic macromolecular compounds obtained by reactions only involving carbon to carbon unsaturated bonds
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    • 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
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    • B01J20/28021—Hollow particles, e.g. hollow spheres, microspheres or cenospheres
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    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F9/00—Multistage treatment of water, waste water or sewage
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    • C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
    • 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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    • 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
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2305/00—Use of specific compounds during water treatment
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    • C02F2305/023—Reactive oxygen species, singlet oxygen, OH radical
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2305/00—Use of specific compounds during water treatment
    • C02F2305/02—Specific form of oxidant
    • C02F2305/026—Fenton's reagent

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Abstract

The invention provides a preparation method of resin microspheres, which comprises the steps of preparing 5-chloromethyl-8-hydroxyquinoline by using 8-hydroxyquinoline as a raw material, then obtaining an alkylated monomer with N, N' -methylene bisacrylamide, and carrying out cross-linking polymerization reaction with hydroxyethyl methacrylate, ferulic acid and ethylene glycol dimethacrylate to obtain the resin microspheres; the invention also provides a method for treating printing and dyeing wastewater by using the resin microspheres, which comprises the steps of rough filtration, pH adjustment, coagulating sedimentation, sand filtration, oxidative degradation, heavy metal adsorption, activated carbon decoloration, secondary pH adjustment and discharge or recycling. The resin microsphere has a three-dimensional space three-dimensional net structure and strong oxidation resistance, can efficiently degrade organic matters when being applied to printing and dyeing wastewater treatment, cannot cause secondary pollution, has large heavy metal ion adsorption capacity, is easy to desorb and recycle, and can be better applied to industrial wastewater treatment.

Description

Preparation of resin microspheres and application of resin microspheres in printing and dyeing wastewater treatment
Technical Field
The invention belongs to the technical field of wastewater treatment, and particularly relates to preparation of resin microspheres and application of the resin microspheres in printing and dyeing wastewater treatment.
Background
At present, people face the problems of water resource shortage and increasingly serious water pollution, so that the water treatment technology becomes more and more important, especially printing and dyeing wastewater consumes 100-, 80-90% of the dye becomes wastewater, 10-20% of the dye is discharged as wastewater in the processing process, and with the development of the dye industry, the varieties and the quantity of the dyes are increased day by day, a large number of chemical fiber products appear, and the adoption of new chemical pulp, dye and finishing agent greatly changes the property of the printing and dyeing wastewater and increases the treatment difficulty of the printing and dyeing wastewater, the COD concentration is also increased from the original hundreds of mg/L to 2000-3000mg/L, therefore, the COD removal rate of the prior biological treatment device is reduced from 70 percent to about 50 percent or even lower, so how to treat the printing and dyeing wastewater with high efficiency is a problem which needs to be solved urgently.
The printing and dyeing wastewater contains a large amount of heavy metal ions, such as copper ions, chromium ions, lead ions and the like, which can exist in the natural environment for a long time if directly discharged and endanger human health through a food chain, for example, water pollution, pain disease and other public hazards caused by heavy metal mercury and cadmium pollution, the heavy metal chromium is relatively more used in the printing and dyeing process, potassium dichromate is commonly used as an oxidant and a mordant in the dyeing process, and the chromium as a mutagenic substance can induce lung cancer and nasopharyngeal carcinoma. Therefore, the efficient removal of heavy metal ions in printing and dyeing wastewater is an urgent problem to be solved, the common method is to add an adsorbent to chelate heavy metals in water to remove the heavy metal ions, whether the adsorbent can chelate the heavy metals in the water depends on whether functional groups on the surface of the adsorbent can be combined with the heavy metals, and the traditional material has low absorption efficiency because of small specific surface area, few active sites and poor selectivity, so that the resin microspheres prepared by the invention can efficiently adsorb the heavy metal ions, and the Fenton-like reagent prepared by the resin microspheres can effectively degrade organic pollutants.
Disclosure of Invention
The invention aims to provide a preparation method of resin microspheres and application thereof in printing and dyeing wastewater treatment aiming at overcoming the defects of the prior art, so as to solve the problems of reduced COD removal rate and low heavy metal ion adsorption removal efficiency in wastewater.
In order to solve the technical problems, the invention adopts the technical scheme that:
a preparation method of resin microspheres specifically comprises the following steps:
1) reacting 8-hydroxyquinoline as a raw material with concentrated hydrochloric acid and formaldehyde solution to prepare 5-chloromethyl-8-hydroxyquinoline;
2) dissolving the prepared 5-chloromethyl-8-hydroxyquinoline in acetonitrile, adding N, N' -methylene bisacrylamide and potassium carbonate, stirring and reacting for 20 hours at 50-60 ℃, filtering while hot, filtering crystals precipitated in the filtrate again, washing with distilled water to obtain an alkylation reaction product, and drying for later use;
3) stirring and mixing hydroxyethyl methacrylate, ferulic acid, ethylene glycol dimethacrylate and deionized water, adding an alkylation product, heating to 60-70 ℃, reacting for 20-30min under the protection of nitrogen, adding ammonium persulfate, continuing to react for 15-20h, filtering and washing the product, and drying in vacuum at 50 ℃ to obtain the crosslinked resin microsphere.
Preferably, the mass volume ratio of the 8-hydroxyquinoline to the formaldehyde to the concentrated hydrochloric acid in the step 1) is 1g:3-5mL:5-8mL, hydrogen chloride gas is introduced in the reaction process, and the reaction temperature is controlled to be 10-20 ℃;
preferably, the molar mass ratio of the 5-chloromethyl-8-hydroxyquinoline, the N, N' -methylene bisacrylamide and the potassium carbonate in the step 2) is 3-4:1.2-1.5: 1.5-2.0;
preferably, the mass ratio of the alkylation product, the hydroxyethyl methacrylate, the ferulic acid, the ethylene glycol dimethacrylate, the ammonium persulfate and the deionized water in the step 3) is 30-40:10-20:3-5:5-8:0.2-0.5: 40-50.
A method for treating printing and dyeing wastewater by using resin microspheres specifically comprises the following steps:
firstly, primary filtration: roughly filtering the printing and dyeing wastewater through a grating, and then adjusting the pH value to 6.0-8.0;
secondly, introducing the printing and dyeing wastewater with the adjusted pH into a coagulating sedimentation tank, adding a coagulant and a coagulant aid, carrying out primary sedimentation and decoloration, carrying out sand filtration on supernatant liquor, wherein the sand filtration adopts quartz sand, and the particle size of the particles is 0.8-1.2mm, and then introducing into a degradation tank;
adding a Fenton-like reagent into the wastewater in the degradation tank, stirring for 2-3h, and carrying out oxidation treatment, wherein the resin microspheres can be filtered, recycled and reused;
fourthly, introducing the wastewater treated in the third step into an adsorption tank, grafting resin microspheres on the surface of the adsorption tank through a silane coupling agent, mechanically stirring for 1-1.5h to remove heavy metal ions in the printing and dyeing wastewater and the resin microspheres through coordination and electrostatic interaction, and then introducing the wastewater into a chromaticity adjusting tank;
fifthly, the chroma adjusting tank takes activated carbon as a medium filter, the wastewater is subjected to deep decolorization treatment through the activated carbon and is filtered again to remove impurities, then the pH value is adjusted to 6.5-7.5, and then the wastewater is discharged or recycled.
Preferably, the coagulant and coagulant aid in the step two are industrial aluminum sulfate and sodium silicate respectively; the adding amount of the coagulant and the coagulant aid is 70mg/L and 20mg/L respectively, and solutions with mass fractions of 20 percent and 0.4 percent are prepared respectively and then are added into the wastewater when the coagulant and the coagulant aid are added;
preferably, the Fenton-like reagent in the third step is adsorbing Fe2+The composition of the resin microspheres and hydrogen peroxide can adsorb Fe2+The mass volume ratio of the resin microspheres to hydrogen peroxide is 1g:45-60mL, the concentration of the hydrogen peroxide is 0.1-0.2mmol/L, and the adsorbed Fe2+The preparation method of the resin microsphere comprises the following steps: soaking the prepared resin microspheres in FeCl with the concentration of 100-150mmol/L in the mass-volume ratio of 1g:150-200mL2Shaking in a shaker at 140r/min at room temperature to perform coordination reaction for 5-7 hr to ensure adsorption balance, filtering, washing with deionized water for 2-3 times, and oven drying in a vacuum drying oven at 40 deg.C to obtain Fe adsorbent2+The resin microsphere of (1).
Preferably, in the fourth step, the silane coupling agent is vinyl trialkoxysilane, and the specific method for grafting the resin microspheres with the silane coupling agent comprises the following steps: firstly, reacting and modifying the prepared resin microspheres with 2-methacryloyl chloride, and then grafting the resin microspheres with a silane coupling agent under the action of an initiator ammonium persulfate; the mass ratio of the resin microspheres to the 2-methacryloyl chloride to the ammonium persulfate is 5-8:2-3: 0.1-0.2.
The resin microsphere provided by the invention takes 8-hydroxyquinoline as a raw material, 5-chloromethyl-8-hydroxyquinoline is obtained under the action of formaldehyde and concentrated hydrochloric acid, then the obtained product reacts with N, N' -methylene bisacrylamide to obtain an alkylation product, the alkylation product, hydroxyethyl methacrylate and ferulic acid are taken as monomers, ethylene glycol dimethacrylate is taken as a cross-linking agent to prepare the cross-linked resin microsphere, the resin microsphere has a three-dimensional space three-dimensional network structure, the surface of the microsphere contains a large amount of hydroxyl groups, modification and modification are easy, and the 8-hydroxyquinoline group contains hydroxyl groups and lone pair electrons on nitrogen and are easy to complex metal ions, and meanwhile, the resin microsphere has certain oxidation resistance, can prevent self oxidative degradation and can be recycled.
The printing and dyeing wastewater treatment method comprises the steps of filtering the printing and dyeing wastewater, adjusting pH, coagulating and precipitating, filtering fine or suspended impurities by sand filtration, adding a Fenton-like reagent into the wastewater, oxidizing and degrading organic pollutants difficult to biodegrade by generated hydroxyl free radicals, removing heavy metal ions from the wastewater by an adsorption tank modified by resin microsphere grafting, decoloring and filtering the impurities by activated carbon, and finally adjusting the pH to reach the discharge standard. The Fenton-like reagent is composed of resin microspheres complexed with ferrous ions and hydrogen peroxide, wherein the resin microspheres are complexed with the ferrous ions to form a stable compound, hydroxyl radicals generated by the action of the resin microspheres and the hydrogen peroxide can oxidize and degrade organic pollutants, and the resin cannot be oxidized and degraded; the resin microspheres grafted by the silane coupling agent in the adsorption tank contain carboxyl, hydroxyl and nitrogen containing lone pair electrons, so that heavy metal ions can be effectively adsorbed.
The resin microspheres in the printing and dyeing wastewater treatment method are modified and grafted on the surface of the adsorption tank through the silane coupling agent, heavy metal ions are removed by combining with the resin microspheres, the resin microspheres have large aperture and small ion diffusion resistance, the adsorption of the metal ions is easy, and the metal ions can be desorbed, namely the resin microspheres can be recycled.
Compared with the prior art, the invention has the following advantages:
1. the 8-hydroxyquinoline group in the resin microsphere can well complex metal ions, the ethylene glycol dimethacrylate cross-linking agent enables the resin to form a three-dimensional space three-dimensional network structure, the ferulic acid enhances the oxidation resistance of the resin, and the hydroxyethyl methacrylate enables the surface of the resin to contain a large amount of hydroxyl groups to facilitate the grafting modification of the resin.
2. The resin microsphere prepared by the invention has the advantages of high mechanical strength, good chemical stability, excellent pollution resistance and oxidation resistance, large aperture, high metal ion passing rate, high complexing efficiency and high regeneration efficiency of the resin microsphere.
3. The Fenton-like reagent prepared from the resin microspheres is used for treating printing and dyeing wastewater, can efficiently degrade organic matters, cannot cause secondary pollution, and is easy to regenerate and recycle.
4. The resin microspheres are modified on the surface of the adsorption tank by the grafted silane coupling agent, so that the adsorption capacity of the resin microspheres to heavy metal ions is large, the adsorption is easy to remove, the adsorption and the cyclic utilization are realized, and the resin microspheres can be better applied to industrial wastewater treatment.
Drawings
FIG. 1 is a process flow diagram of the treatment of printing and dyeing wastewater according to the present invention.
Detailed Description
The following detailed description of the embodiments of the present invention is provided in connection with the accompanying drawings for the purpose of better understanding and enabling those skilled in the art to practice the invention, and the embodiments are not intended to limit the invention.
Example 1
A preparation method of resin microspheres specifically comprises the following steps:
1) reacting 8-hydroxyquinoline as a raw material with a formaldehyde solution and concentrated hydrochloric acid to prepare 5-chloromethyl-8-hydroxyquinoline;
2) dissolving the prepared 5-chloromethyl-8-hydroxyquinoline in acetonitrile, adding N, N '-methylene bisacrylamide and potassium carbonate, wherein the molar mass ratio of the 5-chloromethyl-8-hydroxyquinoline to the N, N' -methylene bisacrylamide to the potassium carbonate is 4:1.5:2.0, stirring and reacting for 20 hours at 50 ℃, filtering while hot, filtering crystals precipitated in the filtrate again, washing with distilled water, and drying the obtained alkylation reaction product for later use;
3) stirring and mixing hydroxyethyl methacrylate, ferulic acid, ethylene glycol dimethacrylate and deionized water, adding an alkylation product, heating to 60 ℃, reacting for 20-30min under the protection of nitrogen, adding ammonium persulfate, continuing to react for 20h, filtering and washing the product, and drying in vacuum at 50 ℃ to obtain the crosslinked resin microsphere.
Wherein the mass volume ratio of the 8-hydroxyquinoline to the formaldehyde to the concentrated hydrochloric acid in the step 1) is 1g to 3mL to 5mL, hydrogen chloride gas is introduced in the reaction process, and the reaction temperature is controlled at 10 ℃;
the mass ratio of the alkylation product, hydroxyethyl methacrylate, ferulic acid, ethylene glycol dimethacrylate, ammonium persulfate and deionized water in the step 3) is 30:10:3:5:0.2: 40.
A method for treating printing and dyeing wastewater by using resin microspheres specifically comprises the following steps:
firstly, primary filtration: roughly filtering the printing and dyeing wastewater through a grating, and then adjusting the pH value to 6.0-8.0;
secondly, introducing the printing and dyeing wastewater with the adjusted pH into a coagulating sedimentation tank, adding 20% of industrial aluminum sulfate and 0.4% of sodium silicate, wherein the adding amount is 70mg/L and 20mg/L respectively, carrying out primary sedimentation and decoloration, carrying out sand filtration on supernatant, wherein quartz sand is adopted in the sand filtration, the particle size of the particles is 0.8-1.2mm, and then introducing into a degradation tank;
adding a Fenton-like reagent into the wastewater in the degradation tank, stirring for 2 hours, and carrying out oxidation treatment, wherein the resin microspheres can be filtered, recycled and reused;
fourthly, introducing the wastewater treated in the third step into an adsorption tank, grafting resin microspheres on the surface of the adsorption tank through a silane coupling agent, mechanically stirring for 1.5 hours to remove heavy metal ions in the printing and dyeing wastewater and the resin microspheres through coordination and electrostatic interaction, and then introducing the wastewater into a chromaticity adjusting tank;
fifthly, the chroma adjusting tank takes activated carbon as a medium filter, the wastewater is subjected to deep decolorization treatment through the activated carbon and is filtered again to remove impurities, then the pH value is adjusted to 6.5-7.5, and then the wastewater is discharged or recycled.
Wherein, the Fenton-like reagent in the third step is used for adsorbing Fe2+The composition of the resin microspheres and hydrogen peroxide can adsorb Fe2+The mass volume ratio of the resin microspheres to hydrogen peroxide is 1g:45mL, the concentration of the hydrogen peroxide is 0.2mmol/L, and the adsorbed Fe is2+The preparation method of the resin microsphere comprises the following steps: soaking the prepared resin microspheres in FeCl of 100mmol/L in a mass-volume ratio of 1g to 200mL2Shaking in a shaking table at 140r/min at room temperature to perform coordination reaction for 7h to ensure that adsorption balance is achieved, filtering, washing with deionized water for 2-3 times, and drying in a vacuum drying oven at 40 deg.C to obtain Fe adsorbed2+The resin microsphere of (1).
The silane coupling agent is vinyl trialkoxysilane, and the specific method for grafting the silane coupling agent to the resin microspheres comprises the following steps: firstly, reacting and modifying the prepared resin microspheres with 2-methacryloyl chloride, and then grafting the resin microspheres with a silane coupling agent under the action of an initiator ammonium persulfate; the mass ratio of the resin microspheres to the 2-methacryloyl chloride to the ammonium persulfate is 8:3: 0.2.
Example 2
A preparation method of resin microspheres specifically comprises the following steps:
1) reacting 8-hydroxyquinoline as a raw material with a formaldehyde solution and concentrated hydrochloric acid to prepare 5-chloromethyl-8-hydroxyquinoline;
2) dissolving the prepared 5-chloromethyl-8-hydroxyquinoline in acetonitrile, adding N, N '-methylene bisacrylamide and potassium carbonate, wherein the molar mass ratio of the 5-chloromethyl-8-hydroxyquinoline to the N, N' -methylene bisacrylamide to the potassium carbonate is 3:1.5:2.0, stirring and reacting for 20 hours at 50 ℃, filtering while hot, filtering crystals precipitated in the filtrate again, washing with distilled water, and drying the obtained alkylation reaction product for later use;
3) stirring and mixing hydroxyethyl methacrylate, ferulic acid, ethylene glycol dimethacrylate and deionized water, adding an alkylation product, heating to 60 ℃, reacting for 20-30min under the protection of nitrogen, adding ammonium persulfate, continuing to react for 20h, filtering and washing the product, and drying in vacuum at 50 ℃ to obtain the crosslinked resin microsphere.
Wherein the mass volume ratio of the 8-hydroxyquinoline to the formaldehyde to the concentrated hydrochloric acid in the step 1) is 1g:4mL:6mL, hydrogen chloride gas is introduced in the reaction process, and the reaction temperature is controlled at 10 ℃;
the mass ratio of the alkylation product, hydroxyethyl methacrylate, ferulic acid, ethylene glycol dimethacrylate, ammonium persulfate and deionized water in the step 3) is 35:15:4:6:0.3: 45.
A method for treating printing and dyeing wastewater by using resin microspheres specifically comprises the following steps:
firstly, primary filtration: roughly filtering the printing and dyeing wastewater through a grating, and then adjusting the pH value to 6.0-8.0;
secondly, introducing the printing and dyeing wastewater with the adjusted pH into a coagulating sedimentation tank, adding 20% of industrial aluminum sulfate and 0.4% of sodium silicate, wherein the adding amount is 70mg/L and 20mg/L respectively, carrying out primary sedimentation and decoloration, carrying out sand filtration on supernatant, wherein quartz sand is adopted in the sand filtration, the particle size of the particles is 0.8-1.2mm, and then introducing into a degradation tank;
adding a Fenton-like reagent into the wastewater in the degradation tank, stirring for 3 hours, and carrying out oxidation treatment, wherein the resin microspheres can be filtered, recycled and reused;
fourthly, introducing the wastewater treated in the third step into an adsorption tank, grafting resin microspheres on the surface of the adsorption tank through a silane coupling agent, mechanically stirring for 1h to remove heavy metal ions in the printing and dyeing wastewater and the resin microspheres through coordination and electrostatic interaction, and then introducing the wastewater into a chromaticity adjusting tank;
fifthly, the chroma adjusting tank takes activated carbon as a medium filter, the wastewater is subjected to deep decolorization treatment through the activated carbon and is filtered again to remove impurities, then the pH value is adjusted to 6.5-7.5, and then the wastewater is discharged or recycled.
Wherein, the Fenton-like reagent in the third step is used for adsorbing Fe2+The composition of the resin microspheres and hydrogen peroxide can adsorb Fe2+The mass volume ratio of the resin microspheres to hydrogen peroxide is 1g:50mL, the concentration of the hydrogen peroxide is 0.15mmol/L, and the adsorbed Fe is2+The preparation method of the resin microsphere comprises the following steps: the prepared resinThe microspheres are soaked in 130mmol/L FeCl in a mass-to-volume ratio of 1g to 180mL2Shaking in a shaking table at 140r/min at room temperature to perform coordination reaction for 5h to ensure adsorption balance, filtering, washing with deionized water for 2-3 times, and oven drying in a vacuum drying oven at 40 deg.C to obtain Fe adsorbent2+The resin microsphere of (1).
The silane coupling agent is vinyl trialkoxysilane, and the specific method for grafting the silane coupling agent to the resin microspheres comprises the following steps: firstly, reacting and modifying the prepared resin microspheres with 2-methacryloyl chloride, and then grafting the resin microspheres with a silane coupling agent under the action of an initiator ammonium persulfate; the mass ratio of the resin microspheres to the 2-methacryloyl chloride to the ammonium persulfate is 7:3: 0.1.
Example 3
A preparation method of resin microspheres specifically comprises the following steps:
1) reacting 8-hydroxyquinoline as a raw material with a formaldehyde solution and concentrated hydrochloric acid to prepare 5-chloromethyl-8-hydroxyquinoline;
2) dissolving the prepared 5-chloromethyl-8-hydroxyquinoline in acetonitrile, adding N, N '-methylene bisacrylamide and potassium carbonate, wherein the molar mass ratio of the 5-chloromethyl-8-hydroxyquinoline to the N, N' -methylene bisacrylamide to the potassium carbonate is 3:1.2:1.5, stirring and reacting for 20 hours at 50 ℃, filtering while hot, filtering crystals precipitated in the filtrate again, washing with distilled water, and drying the obtained alkylation reaction product for later use;
3) stirring and mixing hydroxyethyl methacrylate, ferulic acid, ethylene glycol dimethacrylate and deionized water, adding an alkylation product, heating to 70 ℃, reacting for 20-30min under the protection of nitrogen, adding ammonium persulfate, continuing to react for 15h, filtering and washing the product, and drying in vacuum at 50 ℃ to obtain the crosslinked resin microsphere.
Wherein the mass volume ratio of the 8-hydroxyquinoline to the formaldehyde to the concentrated hydrochloric acid in the step 1) is 1g:5mL:8mL, hydrogen chloride gas is introduced in the reaction process, and the reaction temperature is controlled at 20 ℃;
the mass ratio of the alkylation product, hydroxyethyl methacrylate, ferulic acid, ethylene glycol dimethacrylate, ammonium persulfate and deionized water in the step 3) is 40:20:5:8:0.5: 50.
A method for treating printing and dyeing wastewater by using resin microspheres specifically comprises the following steps:
firstly, primary filtration: roughly filtering the printing and dyeing wastewater through a grating, and then adjusting the pH value to 6.0-8.0;
secondly, introducing the printing and dyeing wastewater with the adjusted pH into a coagulating sedimentation tank, adding 20% of industrial aluminum sulfate and 0.4% of sodium silicate, wherein the adding amount is 70mg/L and 20mg/L respectively, carrying out primary sedimentation and decoloration, carrying out sand filtration on supernatant, wherein quartz sand is adopted in the sand filtration, the particle size of the particles is 0.8-1.2mm, and then introducing into a degradation tank;
adding a Fenton-like reagent into the wastewater in the degradation tank, stirring for 3 hours, and carrying out oxidation treatment, wherein the resin microspheres can be filtered, recycled and reused;
fourthly, introducing the wastewater treated in the third step into an adsorption tank, grafting resin microspheres on the surface of the adsorption tank through a silane coupling agent, mechanically stirring for 1h to remove heavy metal ions in the printing and dyeing wastewater and the resin microspheres through coordination and electrostatic interaction, and then introducing the wastewater into a chromaticity adjusting tank;
fifthly, the chroma adjusting tank takes activated carbon as a medium filter, the wastewater is subjected to deep decolorization treatment through the activated carbon and is filtered again to remove impurities, then the pH value is adjusted to 6.5-7.5, and then the wastewater is discharged or recycled.
Wherein, the Fenton-like reagent in the third step is used for adsorbing Fe2+The composition of the resin microspheres and hydrogen peroxide can adsorb Fe2+The mass volume ratio of the resin microspheres to hydrogen peroxide is 1g:60mL, the concentration of the hydrogen peroxide is 0.1mmol/L, and the adsorbed Fe is2+The preparation method of the resin microsphere comprises the following steps: soaking the prepared resin microspheres in 150mmol/L FeCl in a mass-to-volume ratio of 1g:150mL2Shaking in a shaking table at 140r/min at room temperature to perform coordination reaction for 5h to ensure adsorption balance, filtering, washing with deionized water for 2-3 times, and oven drying in a vacuum drying oven at 40 deg.C to obtain Fe adsorbent2+The resin microsphere of (1).
The silane coupling agent is vinyl trialkoxysilane, and the specific method for grafting the silane coupling agent to the resin microspheres comprises the following steps: firstly, reacting and modifying the prepared resin microspheres with 2-methacryloyl chloride, and then grafting the resin microspheres with a silane coupling agent under the action of an initiator ammonium persulfate; the mass ratio of the resin microspheres to the 2-methacryloyl chloride to the ammonium persulfate is 6:2: 0.1.
Example 4
Compared with the embodiment 1, the preparation method of the resin microspheres is completely the same as that of the embodiment 1, and the specific application method of the resin microspheres in the treatment of printing and dyeing wastewater is as follows:
a method for treating printing and dyeing wastewater by using resin microspheres specifically comprises the following steps:
firstly, primary filtration: roughly filtering the printing and dyeing wastewater through a grating, and then adjusting the pH value to 6.0-8.0;
secondly, introducing the printing and dyeing wastewater with the adjusted pH into a coagulating sedimentation tank, adding 20% of industrial aluminum sulfate and 0.4% of sodium silicate, wherein the adding amount is 70mg/L and 20mg/L respectively, carrying out primary sedimentation and decoloration, carrying out sand filtration on supernatant, wherein quartz sand is adopted in the sand filtration, the particle size of the particles is 0.8-1.2mm, and then introducing into a degradation tank;
thirdly, adding a Fenton-like reagent into the wastewater in the degradation pool, and stirring for 2 hours to carry out oxidation treatment;
fourthly, introducing the wastewater treated in the third step into an adsorption tank, grafting resin microspheres on the surface of the adsorption tank through a silane coupling agent, mechanically stirring for 1.5 hours to remove heavy metal ions in the printing and dyeing wastewater and the resin microspheres through coordination and electrostatic interaction, and then introducing the wastewater into a chromaticity adjusting tank;
fifthly, the chroma adjusting tank takes activated carbon as a medium filter, the wastewater is subjected to deep decolorization treatment through the activated carbon and is filtered again to remove impurities, then the pH value is adjusted to 6.5-7.5, and then the wastewater is discharged or recycled.
Wherein, the Fenton-like reagent in the third step is used for adsorbing Fe2+The composition of the Y-type zeolite molecular sieve and hydrogen peroxide is used for adsorbing Fe2+The mass volume ratio of the Y-type zeolite molecular sieve to hydrogen peroxide is 1g:45mL, the concentration of the hydrogen peroxide is 0.2mmol/L, and the adsorbed Fe2+Y shape ofThe preparation method of the zeolite molecular sieve comprises the following steps: soaking a Y-type zeolite molecular sieve in FeCl of 100mmol/L at the mass-volume ratio of 1g to 200mL2Shaking in a shaking table at 140r/min at room temperature to perform coordination reaction for 7h to ensure that adsorption balance is achieved, filtering, washing with deionized water for 2-3 times, and drying in a vacuum drying oven at 40 deg.C to obtain Fe adsorbed2+The Y-type zeolite molecular sieve of (1).
The silane coupling agent is vinyl trialkoxysilane, and the specific method for grafting the silane coupling agent to the resin microspheres comprises the following steps: firstly, reacting and modifying the prepared resin microspheres with 2-methacryloyl chloride, and then grafting the resin microspheres with a silane coupling agent under the action of an initiator ammonium persulfate; the mass ratio of the resin microspheres to the 2-methacryloyl chloride to the ammonium persulfate is 8:3: 0.2.
Example 5
Compared with the embodiment 1, the preparation method of the resin microsphere is changed to a certain extent, and the specific application method of the resin microsphere in the printing and dyeing wastewater treatment is not changed:
a preparation method of resin microspheres specifically comprises the following steps:
1) reacting 8-hydroxyquinoline serving as a raw material with formaldehyde solution and concentrated hydrochloric acid to prepare 5-chloromethyl-8-hydroxyquinoline;
2) dissolving the prepared 5-chloromethyl-8-hydroxyquinoline in acetonitrile, adding N, N '-methylene bisacrylamide and potassium carbonate, wherein the molar mass ratio of the 5-chloromethyl-8-hydroxyquinoline to the N, N' -methylene bisacrylamide to the potassium carbonate is 4:1.5:2.0, stirring and reacting for 20 hours at 50 ℃, filtering while hot, filtering crystals precipitated in the filtrate again, washing with distilled water, and drying the obtained alkylation reaction product for later use;
3) dissolving ethylene glycol dimethacrylate in deionized water, stirring and mixing, adding an alkylation product, heating to 60 ℃, reacting for 20-30min under the protection of nitrogen, adding ammonium persulfate, continuing to react for 20h, filtering and washing the product, and drying in vacuum at 50 ℃ to obtain the crosslinked resin microsphere.
Wherein the mass volume ratio of the 8-hydroxyquinoline to the formaldehyde to the concentrated hydrochloric acid in the step 1) is 1g to 3mL to 5mL, hydrogen chloride gas is introduced in the reaction process, and the reaction temperature is controlled at 10 ℃;
the mass ratio of the alkylation product, the ethylene glycol dimethacrylate, the ammonium persulfate and the deionized water in the step 3) is 30:5:0.2: 40.
A method for treating printing and dyeing wastewater by using resin microspheres specifically comprises the following steps:
firstly, primary filtration: roughly filtering the printing and dyeing wastewater through a grating, and then adjusting the pH value to 6.0-8.0;
secondly, introducing the printing and dyeing wastewater with the adjusted pH into a coagulating sedimentation tank, adding 20% of industrial aluminum sulfate and 0.4% of sodium silicate, wherein the adding amount is 70mg/L and 20mg/L respectively, carrying out primary sedimentation and decoloration, carrying out sand filtration on supernatant, wherein quartz sand is adopted in the sand filtration, the particle size of the particles is 0.8-1.2mm, and then introducing into a degradation tank;
adding a Fenton-like reagent into the wastewater in the degradation tank, stirring for 2 hours, and carrying out oxidation treatment, wherein the resin microspheres can be filtered, recycled and reused;
fourthly, introducing the wastewater treated in the third step into an adsorption tank, grafting resin microspheres on the surface of the adsorption tank through a silane coupling agent, mechanically stirring for 1.5 hours to remove heavy metal ions in the printing and dyeing wastewater and the resin microspheres through coordination and electrostatic interaction, and then introducing the wastewater into a chromaticity adjusting tank;
fifthly, the chroma adjusting tank takes activated carbon as a medium filter, the wastewater is subjected to deep decolorization treatment through the activated carbon and is filtered again to remove impurities, then the pH value is adjusted to 6.5-7.5, and then the wastewater is discharged or recycled.
Wherein, the Fenton-like reagent in the third step is used for adsorbing Fe2+The composition of the resin microspheres and hydrogen peroxide can adsorb Fe2+The mass volume ratio of the resin microspheres to hydrogen peroxide is 1g:45mL, the concentration of the hydrogen peroxide is 0.2mmol/L, and the adsorbed Fe is2+The preparation method of the resin microsphere comprises the following steps: soaking the prepared resin microspheres in FeCl of 100mmol/L in a mass-volume ratio of 1g to 200mL2Shaking in a shaker at 140r/min at room temperature to perform coordination reaction for 7 hr to ensure adsorption balance, filtering, washing with deionized water for 2-3 times, and vacuum drying at 40 deg.CDrying to obtain the Fe-adsorbing material2+The resin microsphere of (1).
The silane coupling agent is vinyl trialkoxysilane, and the specific method for grafting the silane coupling agent to the resin microspheres comprises the following steps: firstly, reacting and modifying the prepared resin microspheres with 2-methacryloyl chloride, and then grafting the resin microspheres with a silane coupling agent under the action of an initiator ammonium persulfate; the mass ratio of the resin microspheres to the 2-methacryloyl chloride to the ammonium persulfate is 8:3: 0.2.
Example 6
Compared with the embodiment 1, the preparation method of the resin microsphere is changed to a certain extent, and the specific application method of the resin microsphere in the printing and dyeing wastewater treatment is not changed:
a preparation method of resin microspheres specifically comprises the following steps:
stirring and mixing hydroxyethyl methacrylate, ferulic acid, ethylene glycol dimethacrylate and deionized water, heating to 60 ℃, reacting for 20-30min under the protection of nitrogen, adding ammonium persulfate, continuing to react for 20h, filtering and washing the product, and drying in vacuum at 50 ℃ to obtain the crosslinked resin microsphere.
Wherein the mass ratio of the N, N' -methylene bisacrylamide, the hydroxyethyl methacrylate, the ferulic acid, the ethylene glycol dimethacrylate, the ammonium persulfate and the deionized water is 30:10:3:5:0.2: 40.
A method for treating printing and dyeing wastewater by using resin microspheres specifically comprises the following steps:
firstly, primary filtration: roughly filtering the printing and dyeing wastewater through a grating, and then adjusting the pH value to 6.0-8.0;
secondly, introducing the printing and dyeing wastewater with the adjusted pH into a coagulating sedimentation tank, adding 20% of industrial aluminum sulfate and 0.4% of sodium silicate, wherein the adding amount is 70mg/L and 20mg/L respectively, carrying out primary sedimentation and decoloration, carrying out sand filtration on supernatant, wherein quartz sand is adopted in the sand filtration, the particle size of the particles is 0.8-1.2mm, and then introducing into a degradation tank;
adding a Fenton-like reagent into the wastewater in the degradation tank, stirring for 2 hours, and carrying out oxidation treatment, wherein the resin microspheres can be filtered, recycled and reused;
fourthly, introducing the wastewater treated in the third step into an adsorption tank, grafting resin microspheres on the surface of the adsorption tank through a silane coupling agent, mechanically stirring for 1.5 hours to remove heavy metal ions in the printing and dyeing wastewater and the resin microspheres through coordination and electrostatic interaction, and then introducing the wastewater into a chromaticity adjusting tank;
fifthly, the chroma adjusting tank takes activated carbon as a medium filter, the wastewater is subjected to deep decolorization treatment through the activated carbon and is filtered again to remove impurities, then the pH value is adjusted to 6.5-7.5, and then the wastewater is discharged or recycled.
Wherein, the Fenton-like reagent in the third step is used for adsorbing Fe2+The composition of the resin microspheres and hydrogen peroxide can adsorb Fe2+The mass volume ratio of the resin microspheres to hydrogen peroxide is 1g:45mL, the concentration of the hydrogen peroxide is 0.2mmol/L, and the adsorbed Fe is2+The preparation method of the resin microsphere comprises the following steps: soaking the prepared resin microspheres in FeCl of 100mmol/L in a mass-volume ratio of 1g to 200mL2Shaking in a shaking table at 140r/min at room temperature to perform coordination reaction for 7h to ensure that adsorption balance is achieved, filtering, washing with deionized water for 2-3 times, and drying in a vacuum drying oven at 40 deg.C to obtain Fe adsorbed2+The resin microsphere of (1).
The silane coupling agent is vinyl trialkoxysilane, and the specific method for grafting the silane coupling agent to the resin microspheres comprises the following steps: firstly, reacting and modifying the prepared resin microspheres with 2-methacryloyl chloride, and then grafting the resin microspheres with a silane coupling agent under the action of an initiator ammonium persulfate; the mass ratio of the resin microspheres to the 2-methacryloyl chloride to the ammonium persulfate is 8:3: 0.2.
The water quality parameters before and after the treatment of the printing and dyeing wastewater in examples 1 to 6 were measured, and the results are shown in Table 1.
TABLE 1
Figure BDA0002484764080000101
Figure BDA0002484764080000111
(except for pH and chroma, the rest units are mg/L)
As can be seen from the data in Table 1, when the resin microspheres prepared in examples 1 to 3 are used for treating printing and dyeing wastewater, the wastewater does not meet the discharge standard before treatment until the wastewater finally reaches the discharge standard GB 4287-.
As is clear from the data of example 4 in Table 1, the COD of the treated dyeing wastewater was determinedCr、BOD5The value of (A) is increased more than that of example 1, that is, COD is higher than that of example 1CrThe removal rate is reduced from 97 percent to 88 percent, BOD5The removal rate is reduced from 94% to 82%, the contents of ammonia nitrogen, total nitrogen and total phosphorus are increased and exceed the discharge standard GB 4287-2+The Fenton-like reagent consisting of the Y-type zeolite molecular sieve and the hydrogen peroxide has no effect on degrading organic pollutants in the wastewater as compared with the Fe adsorption in example 12+The Fenton-like reagent consisting of the resin microspheres and hydrogen peroxide improves the oxidative degradation performance due to the ligand synergistic effect generated by ferulic acid and 8-hydroxyquinoline ligands in the resin microspheres.
As is obvious from the data of the example 5 in the table 1, the water quality parameters of the printing and dyeing wastewater treated in the example 5 are all higher than the parameters of the wastewater treated in the example 1, and the indexes of the parameters cannot reach the discharge standard GB 4287-.
As can be seen from the data of example 6 in Table 1, the parameters except pH and chromaticity are greatly increased compared with example 1, which also reflects that the removal rate of organic pollutants and heavy metal ions in the wastewater is greatly reduced, and the fact that the performance of the resin microspheres which do not contain 8-hydroxyquinoline groups and are prepared in example 6 is obviously weakened when the resin microspheres are applied to printing and dyeing wastewater treatment is shown because the 8-hydroxyquinoline groups not only adsorb Fe2+The Fenton-like reagent is prepared from only structural components, and is an important structural component for removing heavy metal ions by complexing adsorption.
The above description is only a preferred embodiment of the present invention, and not intended to limit the scope of the present invention, and all modifications of equivalent structures and equivalent processes, which are made by the present specification, or directly or indirectly applied to other related technical fields, are included in the scope of the present invention.

Claims (8)

1. The preparation method of the resin microspheres is characterized by comprising the following steps:
1) reacting 8-hydroxyquinoline as a raw material with concentrated hydrochloric acid and formaldehyde solution to prepare 5-chloromethyl-8-hydroxyquinoline;
2) dissolving the prepared 5-chloromethyl-8-hydroxyquinoline in acetonitrile, adding N, N' -methylene bisacrylamide and potassium carbonate, stirring and reacting for 20 hours at 50-60 ℃, filtering while hot, filtering crystals precipitated in the filtrate again, washing with distilled water to obtain an alkylation reaction product, and drying for later use;
3) stirring and mixing hydroxyethyl methacrylate, ferulic acid, ethylene glycol dimethacrylate and deionized water, adding an alkylation product, heating to 60-70 ℃, reacting for 20-30min under the protection of nitrogen, adding ammonium persulfate, continuing to react for 15-20h, filtering and washing the product, and drying in vacuum at 50 ℃ to obtain the crosslinked resin microsphere.
2. The method for preparing resin microspheres according to claim 1, wherein the mass-to-volume ratio of the 8-hydroxyquinoline to the formaldehyde to the concentrated hydrochloric acid in step 1) is 1g:3-5mL:5-8mL, hydrogen chloride gas is introduced during the reaction, and the reaction temperature is controlled to be 10-20 ℃.
3. The method for preparing resin microspheres according to claim 1, wherein the molar mass ratio of the 5-chloromethyl-8-hydroxyquinoline, the N, N' -methylenebisacrylamide, and the potassium carbonate in step 2) is 3-4:1.2-1.5: 1.5-2.0.
4. The method for preparing resin microspheres according to claim 1, wherein the mass ratio of the alkylation product, hydroxyethyl methacrylate, ferulic acid, ethylene glycol dimethacrylate, ammonium persulfate and deionized water in the step 3) is 30-40:10-20:3-5:5-8:0.2-0.5: 40-50.
5. The method for treating printing and dyeing wastewater by using the resin microspheres as claimed in claims 1 to 4 is characterized by comprising the following steps:
firstly, primary filtration: roughly filtering the printing and dyeing wastewater through a grating, and then adjusting the pH value to 6.0-8.0;
secondly, introducing the printing and dyeing wastewater with the adjusted pH into a coagulating sedimentation tank, adding a coagulant and a coagulant aid, carrying out primary sedimentation and decoloration, carrying out sand filtration on supernatant liquor, wherein the sand filtration adopts quartz sand, and the particle size of the particles is 0.8-1.2mm, and then introducing into a degradation tank;
thirdly, adding adsorbed Fe into the wastewater of the degradation tank2+The Fenton-like reagent consisting of the resin microspheres and hydrogen peroxide is stirred for 2-3 hours for oxidation treatment, and the resin microspheres can be filtered, recovered and recycled;
fourthly, introducing the wastewater treated in the third step into an adsorption tank, grafting resin microspheres on the surface of the adsorption tank through a silane coupling agent, mechanically stirring for 1-1.5h to remove heavy metal ions in the printing and dyeing wastewater and the resin microspheres through coordination and electrostatic interaction, and then introducing the wastewater into a chromaticity adjusting tank;
fifthly, the chroma adjusting tank takes activated carbon as a medium filter, the wastewater is subjected to deep decolorization treatment through the activated carbon and is filtered again to remove impurities, then the pH value is adjusted to 6.5-7.5, and then the wastewater is discharged or recycled.
6. The method for treating printing and dyeing wastewater according to claim 5, wherein in the second step, the coagulant and coagulant aid are industrial aluminum sulfate and sodium silicate; the adding amount of the coagulant and the coagulant aid is 70mg/L and 20mg/L respectively, and solutions with mass fractions of 20 percent and 0.4 percent are prepared respectively and then are added into the wastewater.
7. The method of treating printing and dyeing wastewater according to claim 5, characterized in that Fe is adsorbed by said Fenton-like reagent in step three2+The mass volume ratio of the resin microspheres to hydrogen peroxide is 1g:45-60mL, the concentration of the hydrogen peroxide is 0.1-0.2mmol/L, and the adsorbed Fe2+The preparation method of the resin microsphere comprises the following steps: soaking the prepared resin microspheres in FeCl with the concentration of 100-150mmol/L in the mass-volume ratio of 1g:150-200mL2Shaking in a shaker at 140r/min at room temperature to perform coordination reaction for 5-7 hr to ensure adsorption balance, filtering, washing with deionized water for 2-3 times, and oven drying in a vacuum drying oven at 40 deg.C to obtain Fe adsorbent2+The resin microsphere of (1).
8. The method for treating printing and dyeing wastewater according to claim 5, characterized in that in step four, the silane coupling agent is vinyl trialkoxysilane, and the specific method for grafting the resin microspheres with the silane coupling agent is as follows: firstly, reacting and modifying the prepared resin microspheres with 2-methacryloyl chloride, and then grafting the resin microspheres with a silane coupling agent under the action of an initiator ammonium persulfate; the mass ratio of the resin microspheres to the 2-methacryloyl chloride to the ammonium persulfate is 5-8:2-3: 0.1-0.2.
CN202010388537.5A 2020-05-09 2020-05-09 Preparation of resin microspheres and application of resin microspheres in printing and dyeing wastewater treatment Withdrawn CN111514865A (en)

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