CN113104947A - Preparation method of flocculation decolorizing agent - Google Patents

Preparation method of flocculation decolorizing agent Download PDF

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CN113104947A
CN113104947A CN202110325213.1A CN202110325213A CN113104947A CN 113104947 A CN113104947 A CN 113104947A CN 202110325213 A CN202110325213 A CN 202110325213A CN 113104947 A CN113104947 A CN 113104947A
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flocculation
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silane coupling
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不公告发明人
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Jinhua Jingqi Technology Co ltd
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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
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
    • C02F1/56—Macromolecular compounds
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
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    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract

The invention discloses a preparation method of a flocculation decolorizing agent, belonging to the technical field of flocculating agents and comprising the following procedures: step 1, preparing magnetic Fe by adopting a solvothermal method3O4Nanoparticles; step 2, adopting alliin and silane coupling agent to obtain modified silane coupling agent; worker's tool3, adopting modified silane coupling agent to react magnetic Fe3O4Modifying the nano particles to obtain modified magnetic Fe3O4Nanoparticles; step 4, modified magnetic Fe is adopted3O4The chitosan is subjected to graft copolymerization reaction by the nano particles and the L-allyl glycine to obtain the flocculation decolorizing agent. The preparation method takes chitosan as a grafting main chain, and takes L-allyl glycine and modified magnetic Fe3O4The nano particles are graft comonomer to prepare the flocculation decolorizing agent, and a large amount of carboxyl, amino active groups and magnetic particles are introduced to chitosan to prepare the chitosan-based flocculation decolorizing agent with multiple functions of decolorization, flocculation, sterilization, salt resistance, magnetic response performance and the like.

Description

Preparation method of flocculation decolorizing agent
Technical Field
The invention belongs to the technical field of flocculating agents, and particularly relates to a preparation method of a flocculation decolorizing agent.
Background
The waste water produced in the printing and dyeing industry is produced after natural, synthetic and blended textiles are treated, mainly comes from dyeing and finishing processes such as desizing, boiling, bleaching, dyeing, printing, after-finishing and the like, the pollutants mainly comprise dyes and chemical agents such as anhydrous sodium sulphate, penetrant, sodium hydrosulfite, various functional finishing agents and the like added in the dyeing process for obtaining better dyeing effect (color yield and uniformity), and the most serious pollution to water is the dyes in numerous pollutant components. The dye has specific color and complex structure, and aromatic rings, amino, nitro, some heavy metal atoms and the like contained in the structure of the dye have toxicity and have great harm to human health and growth of animals and plants. The dye is difficult to degrade by itself, and degradation products generated by the degradable part of the dye are often intermediates with higher toxicity. The colorful printing and dyeing wastewater is not only viewed, but also substances such as dyes in the wastewater can absorb sunlight emitted into water, block photosynthesis of plants and destroy the ecosystem of aquatic organisms. The chroma becomes an important index for testing whether the printing and dyeing wastewater is qualified or not, and the decolorization is a research hotspot and a key point in the field of printing and dyeing wastewater treatment at present.
The most important purpose of treating the printing and dyeing wastewater is to remove the dye in the wastewater, and the treatment methods of the printing and dyeing wastewater can be divided into physical methods, biological methods and chemical methods according to the action principle. The current flocculation method widely applied to the decoloration of printing and dyeing wastewater has the advantages of convenient operation, simple process, good treatment effect, low investment cost and the like, and has good development prospect.
Disclosure of Invention
The invention aims to provide a method for preparing a modified magnetic Fe-based material by using chitosan as a grafting main chain and using L-allyl glycine and modified magnetic Fe3O4The preparation method of the flocculation decolorizing agent with nano particles as graft comonomer has the functions of decolorizing, flocculating and sterilizingMultiple functions such as salt resistance and magnetic response performance.
The technical scheme adopted by the invention for realizing the purpose is as follows:
the preparation method of the flocculation decolorizing agent comprises the following steps:
step 1, preparing magnetic Fe by adopting a solvothermal method3O4Nanoparticles;
step 2, adopting alliin and silane coupling agent to obtain modified silane coupling agent;
step 3, adopting a modified silane coupling agent to carry out magnetic Fe3O4Modifying the nano particles to obtain modified magnetic Fe3O4Nanoparticles;
step 4, modified magnetic Fe is adopted3O4The chitosan is subjected to graft copolymerization reaction by the nano particles and the L-allyl glycine to obtain the flocculation decolorizing agent.
The preparation method takes chitosan as a grafting main chain, and takes L-allyl glycine and modified magnetic Fe3O4The nano particles are graft comonomer to prepare the flocculation decolorizing agent, and a large amount of carboxyl, amino active groups and magnetic particles are introduced to chitosan to prepare the chitosan-based flocculation decolorizing agent with multiple functions of decolorization, flocculation, sterilization, salt resistance, magnetic response performance and the like.
Preferably, the step 2 is specifically: adding anhydrous ethanol into alliin and a silane coupling agent KH560, carrying out oil bath reaction for 4-8h at the temperature of 150 ℃ under the protection of nitrogen, carrying out reduced pressure distillation, collecting target fractions, and drying to obtain the modified silane coupling agent.
More preferably, the dosage ratio of the alliin to the silane coupling agent KH560 is 1.0-1.4mmol:1 mmol.
Preferably, the step 3 is specifically: magnetic Fe3O4Ultrasonically dispersing the nanoparticles in a modified silane coupling agent ethanol solution, stirring for 10-15h, repeatedly separating the solution by using a magnet, washing the solution for 2-4 times by using absolute ethyl alcohol, and drying to obtain modified magnetic Fe3O4Nanoparticles.
More preferably, the concentration of the ethanol solution of the modified silane coupling agent is 15-25 wt%, and the magnetic Fe3O4The dosage ratio of the nano particles to the modified silane coupling agent is 1mmol:1.1-1.2 mmol.
Preferably, the step 4 is specifically: modifying magnetic Fe3O4Adding deionized water into the nano particles, L-allyl glycine and chitosan, uniformly mixing, adding an initiator under the protection of nitrogen, stirring and reacting for 6-12h at 50-70 ℃, cooling to room temperature, removing homopolymers and unreacted monomers in the mixture, drying, and grinding to obtain the flocculation decolorizing agent.
The invention also discloses the flocculation decolorizing agent prepared by the preparation method.
The flocculation decolorizing agent has higher decolorizing capacity and COD removing capacity, and can be effectively applied to deep decolorization treatment of printing and dyeing wastewater, because the flocculation decolorizing agent contains a large amount of carboxyl, amino and hydroxyl which are mutually combined with dye molecules through electrostatic attraction action, ion exchange action, complexation and the like, thereby achieving the purpose of removing dyes and organic pollutants, and being effectively applied to deep decolorization treatment of printing and dyeing wastewater. The flocculation decolorizing agent also has good magnetic response performance and magnetic separation performance, can realize quick separation and has renewable reusability. In addition, the flocculation decolorant also has sterilization and salt tolerance.
Preferably, the flocculation decolorant has a grafting rate of > 100%.
The invention also discloses the application of the flocculation decolorizing agent in printing and dyeing wastewater treatment.
Preferably, the flocculation decolorant is used in the treatment of salt-containing printing and dyeing wastewater.
The invention adopts chitosan as a grafting main chain, L-allyl glycine and modified magnetic Fe3O4The nano particles are graft comonomer to prepare the flocculation decolorizing agent, thereby having the following beneficial effects: according to the preparation method, a large number of carboxyl and amino active groups and magnetic particles are introduced to chitosan, so that the chitosan-based flocculation decolorizing agent with multiple functions of decolorization, flocculation, sterilization, salt tolerance, magnetic response performance and the like is prepared; the flocculation decolorizing agent contains a large amount of carboxyl, amino and hydroxyl, and is prepared by electrostatic attractionThe functions, ion exchange function, complexation and the like are combined with dye molecules, so that the aim of removing the dye and the organic pollutant is fulfilled, and the method can be effectively applied to deep decolorization treatment of printing and dyeing wastewater. In addition, the rubber accelerator can also enhance the effect of an antistatic agent used for the outer rubber layer. Therefore, the invention provides a method for preparing a magnetic material by using chitosan as a grafting main chain, L-allyl glycine and modified magnetic Fe3O4The preparation method of the flocculation decolorizing agent with the nano particles as the graft comonomer has multiple functions of decolorizing, flocculating, sterilizing, salt tolerance, magnetic response performance and the like.
Drawings
FIG. 1 shows the grafting efficiency of the graft copolymerization reaction;
FIG. 2 shows the grafting yield of the flocculation decolorant;
FIG. 3 is an FTIR spectrum of chitosan and a flocculation decolorant;
FIG. 4 shows the decolorization rate and COD removal rate of the flocculation decolorant on the dye wastewater;
FIG. 5 shows the decolorization rate and COD removal rate of the flocculation decolorant on the saline dye wastewater;
FIG. 6 shows the turbidity removal rate of a kaolin suspension by a flocculation decolorant;
FIG. 7 shows the turbidity removal rate and bacteria removal rate of a Salmonella suspension by a flocculation decolorant;
fig. 8 shows the saturation magnetization of the flocculation decolorant.
Detailed Description
The exemplary embodiments will be described herein in detail, and the embodiments described in the following exemplary embodiments do not represent all embodiments consistent with the present disclosure. Rather, they are merely examples of methods consistent with certain aspects of the present disclosure, as detailed in the appended claims.
The embodiment of the disclosure provides a preparation method of a flocculation decolorizing agent, which comprises the following procedures:
step 1, preparing magnetic Fe by adopting a solvothermal method3O4Nanoparticles;
step 2, adopting alliin and silane coupling agent to obtain modified silane coupling agent;
step 3, adopting a modified silane coupling agent to carry out magnetic Fe3O4Modifying the nano particles to obtain modified magnetic Fe3O4Nanoparticles;
step 4, modified magnetic Fe is adopted3O4The chitosan is subjected to graft copolymerization reaction by the nano particles and the L-allyl glycine to obtain the flocculation decolorizing agent.
The preparation method of the embodiment takes chitosan as a grafting main chain, and takes L-allyl glycine and modified magnetic Fe3O4The nano particles are graft comonomer to prepare the flocculation decolorizing agent, and a large amount of carboxyl, amino active groups and magnetic particles are introduced on the chitosan to prepare the chitosan-based flocculation decolorizing agent with multiple functions of decolorization, flocculation, sterilization, magnetic response performance and the like.
In an alternative embodiment, the preparation method of the flocculation decolorant comprises the following steps:
step 1, FeCl3·6H2Dissolving O and sodium acetate in ethylene glycol, adding polyethylene glycol, stirring to dissolve completely, reacting at 220 deg.C for 3-8h, cooling to room temperature, repeatedly separating with magnet, washing with anhydrous ethanol for 2-4 times, and drying to obtain magnetic Fe3O4Nanoparticles; FeCl3·6H2The dosage ratio of O, sodium acetate, glycol and polyethylene glycol is 1mmol:3.0-3.5mmol:5-10mL:0.1-0.12 mmol;
step 2, adding absolute ethyl alcohol into alliin and a silane coupling agent KH560, carrying out oil bath reaction for 4-8h at the temperature of 100-150 ℃ under the protection of nitrogen, carrying out reduced pressure distillation, collecting target fractions, and drying to obtain a modified silane coupling agent; the dosage ratio of the alliin to the silane coupling agent KH560 to the ethanol is 1.0-1.4mmol to 1mmol to 5-10 mL;
step 3, adding magnetic Fe3O4Ultrasonically dispersing the nanoparticles in a modified silane coupling agent ethanol solution, stirring for 10-15h, repeatedly separating the solution by using a magnet, washing the solution for 2-4 times by using absolute ethyl alcohol, and drying to obtain modified magnetic Fe3O4Nanoparticles; magnetic Fe3O4Nanoparticle, modified silane coupling agent and BThe dosage ratio of the alcohol is 1mmol:1.1-1.2mmol:5-10 mL.
Step 4, modifying the magnetic Fe3O4Adding deionized water into the nano particles, L-allyl glycine and chitosan, uniformly mixing, adding an initiator ammonium ceric nitrate under the protection of nitrogen, stirring at 50-70 ℃ for reacting for 6-12h, cooling to room temperature, purifying in acetone and absolute ethyl alcohol for several times to remove homopolymers and unreacted monomers in the solution, drying, and grinding to obtain the flocculation decolorizing agent. The total monomer in the solution is 12-18 wt%, the cerium ammonium nitrate is 3-8 wt%, and the modified magnetic Fe3O4The mol ratio of the nano particles to the L-allyl glycine to the chitosan monomer is 0.2-0.4:0.5-0.8: 1.
In an alternative embodiment, the grafting efficiency of the graft copolymerization is > 75%.
In an alternative embodiment, in step 4, lanthanum titanate is added at the same time as the initiator is added. The addition of the lanthanum titanate can improve the grafting efficiency and the grafting rate of the graft copolymerization reaction, thereby improving the effects of decoloring, flocculating, sterilizing and salt tolerance of the flocculating and decoloring agent. Preferably, the lanthanum titanate in the solution is 0.5-1.2 wt%.
The invention also discloses the flocculation decolorizing agent prepared by the preparation method.
The flocculation decolorizing agent has higher decolorizing capacity and COD removing capacity, and can be effectively applied to deep decolorization treatment of printing and dyeing wastewater, because the flocculation decolorizing agent contains a large amount of carboxyl, amino and hydroxyl which are mutually combined with dye molecules through electrostatic attraction action, ion exchange action, complexation and the like, thereby achieving the purpose of removing dyes and organic pollutants, and being effectively applied to deep decolorization treatment of printing and dyeing wastewater. The flocculation decolorizing agent also has good magnetic response performance and magnetic separation performance, can realize quick separation and has renewable reusability. In addition, the flocculation decolorant also has sterilization and salt tolerance.
In an alternative embodiment, the flocculation decolorant has a grafting rate of > 100%.
In an optional embodiment, the flocculation decolorant has a decoloration rate of 90% or more and a COD removal rate of 75% or more.
The invention also discloses the application of the flocculation decolorizing agent in printing and dyeing wastewater treatment.
In an alternative embodiment, the use of a flocculation decolorant in the treatment of saline printing wastewater.
The invention also discloses the application of the flocculation decolorizing agent and PAC in printing and dyeing wastewater treatment.
The flocculation decolorizing agent and PAC are compounded to generate a synergistic effect, so that the decolorizing capacity is improved, the using amount of the flocculation decolorizing agent is reduced, and the printing and dyeing wastewater treatment cost is reduced; in addition, the salt tolerance of the flocculation decolorizing agent can be improved by compounding the flocculation decolorizing agent and PAC.
In an alternative embodiment, the weight ratio of the flocculation decolorant to the PAC is 1:1 to 3.
In an alternative embodiment, the use of a flocculation decolorant and PAC in the treatment of saline printing wastewater.
The technical solution of the present invention is further described in detail below with reference to the following detailed description and the accompanying drawings:
chitosan with molecular weight of 5.4X 104Degree of deacetylation 90%, technical grade, purchased from Qingdao Haihui bioengineering limited. All other compounds and reagents were commercially available chemicals without further purification.
Example 1:
the preparation method of the flocculation decolorizing agent comprises the following steps:
step 1, FeCl3·6H2Dissolving O and sodium acetate in ethylene glycol, adding polyethylene glycol, stirring to dissolve completely, reacting at 200 deg.C for 5 hr, cooling to room temperature, repeatedly separating with magnet, washing with anhydrous ethanol for 3 times, and drying to obtain magnetic Fe3O4Nanoparticles; FeCl3·6H2The dosage ratio of O, sodium acetate, glycol and polyethylene glycol is 1mmol:3.2mmol:8mL:0.11 mmol;
step 2, adding absolute ethyl alcohol into alliin and a silane coupling agent KH560, carrying out oil bath reaction for 6 hours at 120 ℃ under the protection of nitrogen, carrying out reduced pressure distillation, collecting target fractions, and drying to obtain a modified silane coupling agent; the dosage ratio of the alliin to the silane coupling agent KH560 to the ethanol is 1.15mmol to 1mmol to 8 mL;
step 3, adding magnetic Fe3O4Ultrasonically dispersing the nanoparticles in a modified silane coupling agent ethanol solution, stirring for 12h, repeatedly separating the solution by using a magnet, washing the solution for 3 times by using absolute ethyl alcohol, and drying to obtain modified magnetic Fe3O4Nanoparticles; magnetic Fe3O4The dosage ratio of the nano particles, the modified silane coupling agent and the ethanol is 1mmol:1.15mmol:8 mL.
Step 4, modifying the magnetic Fe3O4Adding deionized water into the nano particles, L-allyl glycine and chitosan, uniformly mixing, adding an initiator ammonium ceric nitrate under the protection of nitrogen, stirring at 60 ℃ for reaction for 10 hours, cooling to room temperature, purifying in acetone and absolute ethyl alcohol for several times to remove homopolymers and unreacted monomers in the mixture, drying, and grinding to obtain the flocculation decolorizing agent. 15 wt% of total monomers, 5 wt% of ammonium ceric nitrate and modified magnetic Fe in the solution3O4The molar ratio of the nanoparticles to the L-allyl glycine to the chitosan monomer is 0.35:0.75: 1.
Example 2:
the preparation method of the flocculation decolorizing agent comprises the following steps:
step 1, FeCl3·6H2Dissolving O and sodium acetate in ethylene glycol, adding polyethylene glycol, stirring to dissolve completely, reacting at 220 deg.C for 3 hr, cooling to room temperature, repeatedly separating with magnet, washing with anhydrous ethanol for 2 times, and drying to obtain magnetic Fe3O4Nanoparticles; FeCl3·6H2The dosage ratio of O, sodium acetate, glycol and polyethylene glycol is 1mmol:3.5mmol:10mL:0.12 mmol;
step 2, adding absolute ethyl alcohol into alliin and a silane coupling agent KH560, carrying out oil bath reaction for 5 hours at 110 ℃ under the protection of nitrogen, carrying out reduced pressure distillation, collecting target fractions, and drying to obtain a modified silane coupling agent; the dosage ratio of the alliin to the silane coupling agent KH560 to the ethanol is 1.4mmol to 1mmol to 10 mL;
step 3, adding magnetic Fe3O4Ultrasonic dispersion of nano particlesStirring in the ethanol solution of the silane coupling agent for 10h, repeatedly separating with a magnet, washing with anhydrous ethanol for 2 times, and drying to obtain modified magnetic Fe3O4Nanoparticles; magnetic Fe3O4The dosage ratio of the nano particles, the modified silane coupling agent and the ethanol is 1mmol:1.2mmol:10 mL.
Step 4, modifying the magnetic Fe3O4Adding deionized water into the nano particles, L-allyl glycine and chitosan, uniformly mixing, adding an initiator ammonium ceric nitrate under the protection of nitrogen, stirring and reacting for 6 hours at 70 ℃, cooling to room temperature, purifying for several times in acetone and absolute ethyl alcohol to remove homopolymers and unreacted monomers in the mixture, drying, and grinding to obtain the flocculation decolorizing agent. The total monomer in the solution is 18 wt%, the cerium ammonium nitrate is 8 wt%, and the modified magnetic Fe3O4The molar ratio of the nanoparticles to the L-allyl glycine to the chitosan monomer is 0.4:0.8: 1.
Example 3:
the preparation method of the flocculation decolorizing agent comprises the following steps:
step 1, FeCl3·6H2Dissolving O and sodium acetate in ethylene glycol, adding polyethylene glycol, stirring to dissolve completely, reacting at 190 deg.C for 7 hr, cooling to room temperature, repeatedly separating with magnet, washing with anhydrous ethanol for 4 times, and drying to obtain magnetic Fe3O4Nanoparticles; FeCl3·6H2The dosage ratio of O, sodium acetate, glycol and polyethylene glycol is 1mmol:3.0mmol:8mL:0.1 mmol;
step 2, adding absolute ethyl alcohol into alliin and a silane coupling agent KH560, carrying out oil bath reaction for 4-8h at 140 ℃ under the protection of nitrogen, carrying out reduced pressure distillation, collecting target fractions, and drying to obtain a modified silane coupling agent; the dosage ratio of the alliin to the silane coupling agent KH560 to the ethanol is 1.3mmol to 1mmol to 8 mL;
step 3, adding magnetic Fe3O4Ultrasonically dispersing the nanoparticles in a modified silane coupling agent ethanol solution, stirring for 14h, repeatedly separating the solution by using a magnet, washing the solution for 4 times by using absolute ethyl alcohol, and drying to obtain modified magnetic Fe3O4Nanoparticles; magnetic Fe3O4The dosage ratio of the nano particles, the modified silane coupling agent and the ethanol is 1mmol:1.1mmol:8 mL.
Step 4, modifying the magnetic Fe3O4Adding deionized water into the nano particles, L-allyl glycine and chitosan, uniformly mixing, adding an initiator ammonium ceric nitrate under the protection of nitrogen, stirring and reacting for 10 hours at 55 ℃, cooling to room temperature, purifying for several times in acetone and absolute ethyl alcohol to remove homopolymers and unreacted monomers in the mixture, drying, and grinding to obtain the flocculation decolorizing agent. The total monomer content in the solution is 14 wt%, the cerium ammonium nitrate content is 4 wt%, and the modified magnetic Fe3O4The molar ratio of the nanoparticles to the L-allyl glycine to the chitosan monomer is 0.4:0.6: 1.
Example 4:
the preparation method of the flocculation decolorizing agent comprises the following steps:
step 1, FeCl3·6H2Dissolving O and sodium acetate in ethylene glycol, adding polyethylene glycol, stirring to dissolve completely, reacting at 200 deg.C for 5 hr, cooling to room temperature, repeatedly separating with magnet, washing with anhydrous ethanol for 3 times, and drying to obtain magnetic Fe3O4Nanoparticles; FeCl3·6H2The dosage ratio of O, sodium acetate, glycol and polyethylene glycol is 1mmol:3.2mmol:8mL:0.11 mmol;
step 2, adding absolute ethyl alcohol into alliin and a silane coupling agent KH560, carrying out oil bath reaction for 6 hours at 120 ℃ under the protection of nitrogen, carrying out reduced pressure distillation, collecting target fractions, and drying to obtain a modified silane coupling agent; the dosage ratio of the alliin to the silane coupling agent KH560 to the ethanol is 1.15mmol to 1mmol to 8 mL;
step 3, adding magnetic Fe3O4Ultrasonically dispersing the nanoparticles in a modified silane coupling agent ethanol solution, stirring for 12h, repeatedly separating the solution by using a magnet, washing the solution for 3 times by using absolute ethyl alcohol, and drying to obtain modified magnetic Fe3O4Nanoparticles; magnetic Fe3O4The dosage ratio of the nano particles, the modified silane coupling agent and the ethanol is 1mmol:1.15mmol:8 mL.
Step 4, modifying the magnetic Fe3O4Nanoparticles, LAdding deionized water into allyl glycine and chitosan, uniformly mixing, adding an initiator ammonium ceric nitrate under the protection of nitrogen, stirring and reacting for 10 hours at 60 ℃, cooling to room temperature, purifying in acetone and absolute ethyl alcohol for several times to remove homopolymers and unreacted monomers in the mixture, drying, and grinding to obtain the flocculation decolorizing agent. 15 wt% of total monomers, 5 wt% of ammonium ceric nitrate, 0.75 wt% of lanthanum titanate and modified magnetic Fe in the solution3O4The molar ratio of the nanoparticles to the L-allyl glycine to the chitosan monomer is 0.35:0.75: 1.
Example 4:
grafting efficiency of graft copolymerization
The grafting efficiency of the graft copolymerization reaction is calculated by the following formula:
graft efficiency (%) - (m-m)1)/(m2+m3) X is 100%; in the formula (I), the compound is shown in the specification,
m-mass of the graft copolymer after extraction, g;
m1-feed chitosan mass, g;
m2modified magnetic Fe3O4Mass of nanoparticles, g;
m3mass of L-allylglycine fed, g.
The grafting efficiency of the graft copolymerization is shown in FIG. 1, and it can be seen that the grafting efficiency of the graft copolymerization of examples 1 to 4 was > 75%. Meanwhile, the grafting efficiency of the graft copolymerization reaction in example 4 is higher than that in example 1, which shows that the addition of lanthanum titanate can improve the grafting efficiency of the graft copolymerization reaction.
Example 5:
characterization of flocculation decolorant Properties
1. Determination of graft ratio of flocculation decolorizing agent
The weight method is adopted for measurement, and the calculation formula is as follows:
percent graft ratio (%) - (m-m)1)/m1X is 100%; in the formula (I), the compound is shown in the specification,
m-mass of the graft copolymer after extraction, g;
m1-feed chitosan mass, g.
The grafting ratio of the flocculation decolorant is shown in FIG. 2, and it can be seen that the grafting ratio of the flocculation decolorant of examples 1 to 4 is > 100%. Meanwhile, the grafting efficiency of the graft copolymerization reaction in example 4 is higher than that in example 1, which shows that the addition of lanthanum titanate can improve the grafting rate of the graft copolymerization reaction.
2. Fourier transform Infrared Spectroscopy (FTIR) analysis of flocculation decolorants
Taking a sample with proper mass, tabletting by adopting KBr (potassium bromide), measuring an infrared absorption Spectrum by using a Spectrum GX type Fourier transform infrared spectrometer, wherein the wave number scanning range is 4000-400cm-1。
FTIR spectra of chitosan and flocculation decolorant are shown in FIG. 3, wherein a is chitosan and b is flocculation decolorant of example 1. As can be seen from FIG. 3, in the FTIR spectrum of the flocculation decolorant in example 1, 1693.58cm-1Where is an absorption peak due to stretching vibration of C ═ O, 1103.14cm-1Is the absorption peak at 1043.82cm, which is caused by stretching vibration of Si-O bond-1Where is an absorption peak due to stretching vibration of S ═ O bond, 581.16cm-1Is an absorption peak caused by the vibration of Fe-O bond, and the above analysis results show that the modified magnetic Fe3O4Nanoparticles and L-allyl glycine are successfully grafted onto chitosan.
3. Decolorization experiment of flocculation decolorizing agent
Preparing reactive brilliant blue KN-R dye into dye wastewater with the concentration of 100mg/L, adding NaCl and a flocculation decolorizing agent into the dye wastewater, firstly violently stirring the reaction solution for 5min at the fast rotation speed of 200rpm, then slowly stirring for 1h at the slow rotation speed of 50rpm, and then standing the reaction solution for 30 min. Then taking the supernatant liquid for three times at a position 2cm below the surface of the solution to measure the decolorization rate and the COD removal rate of the flocculant on the dye wastewater.
Measuring the absorbance of the sample supernatant at the wavelength of 598nm by using an ultraviolet-visible spectrophotometer, and calculating the decolorization ratio (%) according to the following formula:
decolorization ratio (%) (COD)0-COD)/COD0X is 100%; in the formula (I), the compound is shown in the specification,
A0-absorbance of the dye wastewater before decolorization; a-dye wastewater removalAbsorbance after coloring.
When the solution reaches the adsorption balance, measuring the COD value of the solution after the flocculant is adsorbed by using a COD tester, and calculating the removal rate (%) of COD according to the following formula:
COD removal rate (%) - (a)0-A)/A0X is 100%; in the formula (I), the compound is shown in the specification,
COD0-chemical oxygen demand of the dye wastewater before flocculation; COD-chemical oxygen demand of the dye wastewater after flocculation.
Under the conditions that the adding amount of NaCl is 0, the adding amount of a flocculation decolorizing agent is 200mg/L, and the pH of a water body is adjusted to 5.0, the decolorizing rate and the COD removal rate of the flocculation decolorizing agent on dye wastewater are shown in figure 4, wherein A is the flocculation decolorizing agent of example 1, B is the flocculation decolorizing agent of example 2, C is the flocculation decolorizing agent of example 3, D is the flocculation decolorizing agent of example 4, A1 is the flocculation decolorizing agent of example 1 and PAC with the mass ratio of 1:2, B1 is the flocculation decolorizing agent of example 2 and PAC with the mass ratio of 1:2, C1 is the flocculation decolorizing agent of example 3 and PAC with the mass ratio of 1:2, D1 is the flocculation decolorizing agent of example 4 and PAC with the mass ratio of 1:2, and K is chitosan. As can be seen from fig. 4, the decoloring rate and the COD removal rate of the flocculation decolorant in examples 1 to 4 on the dye wastewater are both higher than those of chitosan, the decoloring rate of the flocculation decolorant in examples 1 to 4 on the dye wastewater is above 90%, and the COD removal rate is above 75%, wherein the decoloring rate and the COD removal rate of the flocculation decolorant in example 4 on the dye wastewater are both higher than those in example 1, which indicates that the flocculation decolorant has good decoloring effect, and when the flocculation decolorant is prepared, lanthanum titanate is added while the initiator is added, so that the decoloring effect of the flocculation decolorant can be improved; when the flocculation decolorant and PAC are used together in the examples 1-4, the decoloration rate of the dye wastewater is above 95%, and the COD removal rate is above 80%, which shows that the combined use of the flocculation decolorant and PAC can generate synergistic effect and improve the decoloration capability.
Under the conditions that the adding amount of NaCl is 20mg/L, the adding amount of a flocculation decolorant is 200mg/L, the pH of a water body is adjusted to 5.0, the decoloration rate of the flocculation decolorant on saline dye wastewater and the removal rate of COD are shown in figure 5, wherein A is the flocculation decolorant of example 1, B is the flocculation decolorant of example 2, C is the flocculation decolorant of example 3, D is the flocculation decolorant of example 4, A1 is the flocculation decolorant and PAC of example 1 with the mass ratio of 1:2, B1 is the flocculation decolorant and PAC of example 2 with the mass ratio of 1:2, C1 is the flocculation decolorant and PAC of example 3 with the mass ratio of 1:2, D1 is the flocculation decolorant and PAC of example 4 with the mass ratio of 1:2, and K is chitosan. As can be seen from fig. 5, the decoloring rate and the COD removal rate of the flocculation decolorant in examples 1 to 4 on the saline dye wastewater are both higher than those of chitosan, while the decoloring rate and the COD removal rate of the flocculation decolorant in examples 1 to 4 on the saline dye wastewater are both lower than those of chitosan, the decoloring rate of the flocculation decolorant in examples 1 to 4 on the saline dye wastewater is more than 80%, and the COD removal rate is more than 70%, which indicates that the flocculation decolorant in examples 1 to 4 has certain salt tolerance, and the salt tolerance is better than that of chitosan; examples 1-4 flocculation decolorant and PAC when using together, the decoloration rate to containing salt dyestuff waste water is above 90%, and the COD clearance is above 85%, this shows that the combined use of flocculation decolorant and PAC can improve the salt tolerance of flocculation decolorant.
4. Flocculation experiment of flocculation decolorizing agent
Adding kaolin particle powder with the total mass of 1.0g into 1.0L of distilled water, preparing 0.1 wt% kaolin suspension under ultrasonic full dispersion, and adjusting the pH value to 5.0; before each experiment, a fresh stock solution of flocculant was prepared by dissolving 0.1g of flocculant in 100mL of distilled water; adding the flocculant stock solution into the synthetic wastewater to ensure that the dosage of the flocculation decolorant is 0.5mg/L, stirring at 200rpm for 5min until the flocculant is completely mixed, and then slowly stirring at 50rpm for 15min to promote the growth of the flocculant. Finally, the flocs were allowed to settle for 30min to maintain flocculation equilibrium.
The supernatant 2cm below the water surface of the flocculated sample solution was collected by a syringe, and the turbidity thereof was measured by a portable turbidimeter, and the turbidity removal rate (%) was calculated according to the following formula:
turbidity removal rate (%) - (T)0-T)/T0X is 100%; in the formula (I), the compound is shown in the specification,
T0-turbidity of the supernatant before flocculation, NTU; t-turbidity of supernatant after flocculation, NTU.
The turbidity removal rate of the flocculation decolorant on the kaolin suspension is shown in fig. 6, wherein a is the flocculation decolorant of example 1, B is the flocculation decolorant of example 2, C is the flocculation decolorant of example 3, D is the flocculation decolorant of example 4, a1 is the flocculation decolorant and PAC of example 1 with a mass ratio of 1:2, B1 is the flocculation decolorant and PAC of example 2 with a mass ratio of 1:2, C1 is the flocculation decolorant and PAC of example 3 with a mass ratio of 1:2, D1 is the flocculation decolorant and PAC of example 4 with a mass ratio of 1:2, and K is chitosan. As can be seen from fig. 6, the turbidity removal rates of the flocculation decolorants in examples 1 to 4 to the kaolin suspension are all higher than that of chitosan, the turbidity removal rates of the flocculation decolorants in examples 1 to 4 to the kaolin suspension are above 95%, wherein the turbidity removal rate of the flocculation decolorants in example 4 to the kaolin suspension is higher than that in example 1, which indicates that the flocculation decolorants in examples 1 to 4 have better flocculation performance, the flocculation performance thereof is better than that of chitosan, and the flocculation decolorants can be improved by adding lanthanum titanate while adding the initiator when preparing the flocculation decolorants; examples 1-4 flocculation decolorant and PAC when using together, to the kaolin suspension turbidity removal rate is above 98%, this shows that flocculation decolorant and PAC combined use can improve flocculation decolorant.
5. Sterilization experiment of flocculation decolorant
Scraping small amount of Salmonella from slant of strain, inoculating in M-H broth (MHB) at 37 deg.C, culturing for 16H, centrifuging at 3000rpm for 5min to obtain Salmonella cells, precipitating appropriate amount of Salmonella in 1.0L beaker, and diluting with phosphate buffer solution (PBS, 0.01M, pH 7.3) to prepare about 1 × 107CFU/mL of Salmonella suspension. Before each experiment, a fresh stock solution of flocculant was prepared by dissolving 0.1g of flocculant in 100mL of distilled water; the flocculant stock solution was added to the salmonella suspension in an amount of 5mg/L of the flocculation decolorant, the pH was adjusted to 5.0, stirred at 200rpm for 5min until complete mixing, and then slowly stirred at 50rpm for 15min to promote the growth of the flocculant. Finally, the flocs were allowed to settle for 30min to maintain flocculation equilibrium. Collecting supernatant 2cm below water surface of the flocculated sample solution with a syringe, and measuring the concentration at 600nm by using an ultraviolet spectrophotometerTurbidity removal and bacteria removal (%) were calculated from absorbance values of the supernatant before and after treatment:
OD600lg (1/T); in the formula (I), the compound is shown in the specification,
OD600-testing the supernatant for optical density at a wavelength of 600 nm.
Bacteria removal rate (%) ═ OD0(600)-OD1(600))/OD0(600)(ii) a In the formula (I), the compound is shown in the specification,
OD0(600)-optical density of the supernatant at wavelength 600nm before flocculation; OD1(600)-optical density of supernatant after flocculation at wavelength 600 nm.
The turbidity removal rate and bacteria removal rate of the flocculation decolorant on the salmonella suspension are shown in fig. 7, wherein a is the flocculation decolorant of example 1, B is the flocculation decolorant of example 2, C is the flocculation decolorant of example 3, D is the flocculation decolorant of example 4, and K is chitosan. As can be seen from fig. 7, the turbidity removal rate and the bacteria removal rate of the flocculation decolorant in examples 1 to 4 to the salmonella suspension are both higher than those of chitosan, the turbidity removal rate of the flocculation decolorant in examples 1 to 4 to the salmonella suspension is above 90%, and the bacteria removal rate to the salmonella suspension is above 90%, wherein the turbidity removal rate and the bacteria removal rate of the flocculation decolorant in example 4 to the salmonella suspension are higher than those of example 1, which shows that the flocculation decolorant in examples 1 to 4 has better bactericidal property, and the bactericidal property is better than that of chitosan, and when the flocculation decolorant is prepared, lanthanum titanate is added while the initiator is added, so that the bactericidal property of the flocculation decolorant can be improved.
6. Magnetic property test of flocculation decolorant
The magnetic performance of the sample is tested by adopting the function of a vibrating magnetometer, 5.0mg of powder sample is weighed and put into a magnetic capsule, the magnetic capsule is fixed on a sample holder, and the magnetic property test of the sample is carried out under the test of 10K and 300K.
The saturation magnetization of the flocculation decolorant is shown in fig. 8, wherein a is the flocculation decolorant of example 1, B is the flocculation decolorant of example 2, C is the flocculation decolorant of example 3, and D is the flocculation decolorant of example 4. As can be seen from FIG. 8, the saturated magnetization of the flocculation decolorant in examples 1 to 4 is above 40emu/g at 10K and above 20emu/g at 300K, wherein the saturated magnetization of the flocculation decolorant in example 4 is higher than that of example 1 at 10K and 300K, which shows that the flocculation decolorant in examples 1 to 4 has magnetic responsiveness, and the magnetic responsiveness of the flocculation decolorant can be improved by adding lanthanum titanate while adding the initiator when preparing the flocculation decolorant.
Conventional operations in the operation steps of the present invention are well known to those skilled in the art and will not be described herein.
The embodiments described above are intended to illustrate the technical solutions of the present invention in detail, and it should be understood that the above-mentioned embodiments are only specific embodiments of the present invention, and are not intended to limit the present invention, and any modification, supplement or similar substitution made within the scope of the principles of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. The preparation method of the flocculation decolorizing agent comprises the following steps:
step 1, preparing magnetic Fe by adopting a solvothermal method3O4Nanoparticles;
step 2, adopting alliin and silane coupling agent to obtain modified silane coupling agent;
step 3 of subjecting the magnetic Fe to the modification with the modified silane coupling agent3O4Modifying the nano particles to obtain modified magnetic Fe3O4Nanoparticles;
step 4 of using the modified magnetic Fe3O4The chitosan is subjected to graft copolymerization reaction by the nano particles and the L-allyl glycine to obtain the flocculation decolorizing agent.
2. The method of claim 1, wherein: the step 2 is specifically: adding anhydrous ethanol into alliin and a silane coupling agent KH560, carrying out oil bath reaction for 4-8h at the temperature of 150 ℃ under the protection of nitrogen, carrying out reduced pressure distillation, collecting target fractions, and drying to obtain the modified silane coupling agent.
3. The method of claim 3, wherein: the dosage ratio of the alliin to the silane coupling agent KH560 is 1.0-1.4mmol:1 mmol.
4. The method of claim 1, wherein: the step 3 is specifically: magnetic Fe3O4Ultrasonically dispersing the nanoparticles in a modified silane coupling agent ethanol solution, stirring for 10-15h, repeatedly separating the solution by using a magnet, washing the solution for 2-4 times by using absolute ethyl alcohol, and drying to obtain modified magnetic Fe3O4Nanoparticles.
5. The method according to claim 4, wherein: the magnetic Fe3O4The dosage ratio of the nano particles to the modified silane coupling agent is 1mmol to 1.1-1.2 mmol.
6. The method of claim 1, wherein: the step 4 is specifically: modifying magnetic Fe3O4Adding deionized water into the nano particles, L-allyl glycine and chitosan, uniformly mixing, adding an initiator under the protection of nitrogen, stirring and reacting for 6-12h at 50-70 ℃, cooling to room temperature, removing homopolymers and unreacted monomers in the mixture, drying, and grinding to obtain the flocculation decolorizing agent.
7. The flocculation decolorant prepared by the preparation method of any one of claims 1 to 6.
8. The flocculation decolorant of claim 7, which is characterized by: the grafting rate of the flocculation decolorizing agent is more than 100 percent.
9. Use of the flocculation decolorant of claim 7 in treatment of printing and dyeing wastewater.
10. Use according to claim 9, characterized in that: the flocculation decolorizing agent is used in the treatment of salt-containing printing and dyeing wastewater.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115196844A (en) * 2022-06-10 2022-10-18 山鹰国际控股股份公司 Method for extracting nitrogen and phosphorus nutrient salt from papermaking sludge

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115196844A (en) * 2022-06-10 2022-10-18 山鹰国际控股股份公司 Method for extracting nitrogen and phosphorus nutrient salt from papermaking sludge

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