CN112919691A - High-efficiency decolorizing agent and application thereof in printing and dyeing wastewater treatment - Google Patents

High-efficiency decolorizing agent and application thereof in printing and dyeing wastewater treatment Download PDF

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CN112919691A
CN112919691A CN202110345814.9A CN202110345814A CN112919691A CN 112919691 A CN112919691 A CN 112919691A CN 202110345814 A CN202110345814 A CN 202110345814A CN 112919691 A CN112919691 A CN 112919691A
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chitosan
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decolorizing agent
decolorant
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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
    • C02F9/00—Multistage treatment of water, waste water or sewage
    • 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
    • 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
    • C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
    • 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
    • C02F1/50—Treatment of water, waste water, or sewage by addition or application of a germicide or by oligodynamic treatment
    • 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
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/30—Nature of the water, waste water, sewage or sludge to be treated from the textile industry

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Abstract

The invention discloses a high-efficiency decolorizing agent and application thereof in printing and dyeing wastewater treatment, belonging to the technical field of printing and dyeing wastewater treatment. The chitosan-based decolorizing agent contains a large amount of carboxyl, amino active groups and cations, has multiple functions of decolorization, flocculation, sterilization and the like, and can be combined with dye molecules and organic pollutants through electrostatic attraction, ion exchange, complexation and the like, so that the aim of removing the dye and the organic pollutants is fulfilled; the chitosan-based decolorant shows excellent decoloration effect in a wider pH range; in addition, the chitosan-based decolorant also has higher adsorption capacity, adsorption rate and salt tolerance. The high-efficiency decolorizing agent can be used for treating printing and dyeing wastewater.

Description

High-efficiency decolorizing agent and application thereof in printing and dyeing wastewater treatment
Technical Field
The invention belongs to the technical field of printing and dyeing wastewater treatment, and particularly relates to a high-efficiency decolorizing agent and application thereof in printing and dyeing wastewater treatment.
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. There are many methods for decoloring a dye wastewater, for example: the activated sludge method, the activated carbon adsorption method, the coagulation sedimentation method, the redox method and the like, but the above various treatment methods have high cost for treating wastewater, unsatisfactory effect and high equipment cost and the like.
Disclosure of Invention
The invention aims to provide a preparation method of a chitosan-based decolorizing agent for introducing a large amount of carboxyl, amino active groups and cations on chitosan.
The technical scheme adopted by the invention for realizing the purpose is as follows:
a chitosan-based decolorant is prepared by graft copolymerization of allyl trimethyl ammonium chloride and cinnamic acid on chitosan.
The preparation method of the invention takes chitosan as a grafting main chain, takes allyl trimethyl ammonium chloride and cinnamic acid as grafting comonomer to prepare the chitosan-based decolorant, introduces a large amount of carboxyl, amino active groups and cations on the chitosan to prepare the chitosan-based decolorant with multiple functions of decoloring, flocculating, sterilizing and the like, and the chitosan-based decolorant has higher adsorption capacity and decoloring rate and has excellent decoloring effect under a wider pH value range or in the presence of salt.
Preferably, the graft copolymerization is carried out under the protection of nitrogen, the temperature of the graft copolymerization is 50-70 ℃, and the time is 4-10 h.
Preferably, the molar ratio of the allyl trimethyl ammonium chloride, the cinnamic acid and the chitosan monomer is 0.3-0.5:0.4-0.6: 1.
The invention also discloses a high-efficiency decolorizing agent which has multiple functions of decolorization, flocculation, sterilization and the like, shows excellent decolorization effect in a wider pH range, and has higher adsorption capacity, decolorization rate and salt tolerance, and the chitosan-based decolorizing agent prepared by the preparation method.
The chitosan-based decolorizing agent contains a large amount of carboxyl, amino active groups and cations, has multiple functions of decolorization, flocculation, sterilization and the like, and can be combined with dye molecules and organic pollutants through electrostatic attraction, ion exchange, complexation and the like, so that the aim of removing the dye and the organic pollutants is fulfilled; the chitosan-based decolorizing agent shows excellent decolorizing effect in a wider pH range (the pH value is 2.0-10.0); in addition, the chitosan-based decolorant also has higher adsorption capacity, decoloration rate and salt tolerance.
Preferably, the graft ratio of the chitosan-based decolorant is more than 120 percent.
Preferably, the decolorization rate of the chitosan-based decolorizer is more than 90%, and the removal rate of COD is more than 80%.
Preferably, the high potency decolorizing agent also includes PAC. The chitosan-based decolorant and PAC are compounded to generate a synergistic effect, so that the decoloring capacity is improved, the using amount of the chitosan-based decolorant is reduced, and the printing and dyeing wastewater treatment cost is reduced; in addition, the chitosan-based decolorizing agent and PAC are compounded for use, so that the salt tolerance of the chitosan-based decolorizing agent can be improved.
Preferably, the weight ratio of chitosan-based decolourant to PAC is 1: 1-3.
The invention also discloses the application of the high-efficiency decolorizing agent in the treatment of printing and dyeing wastewater.
The high-efficiency decolorizing agent has good decolorizing effect, shows excellent decolorizing effect in a wider pH range or in the presence of salt, and can be used for treating printing and dyeing wastewater.
Preferably, the application of the high-efficiency decolorant in the treatment of salt-containing printing and dyeing wastewater.
The invention adopts the chitosan-based decolorant containing a large amount of carboxyl, amino active groups and cations, thereby having the following beneficial effects: the high-efficiency decolorizing agent has multiple functions of decolorizing, flocculating, sterilizing and the like, and can be combined with dye molecules and organic pollutants through electrostatic attraction, ion exchange, complexation and the like, so that the aim of removing the dye and the organic pollutants is fulfilled; the high-efficiency decolorizing agent shows excellent decolorizing effect in a wider pH range (the pH value is 2.0-10.0); in addition, the high-efficiency decolorizing agent also has higher adsorption capacity, decolorizing rate and salt tolerance. Therefore, the invention provides the high-efficiency decolorizing agent which has multiple functions of decolorization, flocculation, sterilization and the like, shows excellent decolorization effect in a wider pH range, and has higher adsorption capacity, decolorization rate and salt tolerance.
Drawings
FIG. 1 shows the grafting efficiency and grafting ratio of chitosan-based decolorant;
FIG. 2 is an FTIR spectrum of chitosan and a chitosan-based destaining agent;
FIG. 3 shows the decolorization rate and COD removal rate of the high-efficiency decolorizer for the dye wastewater;
FIG. 4 shows the decolorization rate of the high-efficiency decolorizer for dye wastewater in different pH ranges;
FIG. 5 shows the standing time required for the high-efficiency decolorizing agent to reach the highest decolorizing rate for the dye wastewater;
FIG. 6 shows the decolorization rate and COD removal rate of wastewater containing salt dye by the high-efficiency decolorizer;
FIG. 7 shows the turbidity removal rate of kaolin suspensions by the high-efficiency decolorant;
FIG. 8 shows the turbidity removal and bacterial removal of a Salmonella suspension by a high performance destaining agent.
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 chitosan-based decolorizing agent A, which is obtained by performing graft copolymerization reaction on chitosan by adopting allyl trimethyl ammonium chloride and cinnamic acid. According to the preparation method, chitosan A is used as a grafting main chain, allyl trimethyl ammonium chloride and cinnamic acid are used as grafting comonomers to prepare the chitosan-based decolorant A, a large number of carboxyl and amino active groups and cations are introduced to chitosan, and the chitosan-based decolorant A with multiple functions of decoloring, flocculating, sterilizing and the like is prepared, has high adsorption capacity and decoloring rate, and has excellent decoloring effect in a wide pH value range or in the presence of salt.
In an alternative embodiment, the graft copolymerization is carried out under nitrogen protection at a temperature of 50 to 70 ℃ for 4 to 10 hours.
In an alternative embodiment, the total monomers in the solution are 12-18 wt% and the cerium ammonium nitrate is 3-8 wt%.
In an alternative embodiment, the molar ratio of allyl trimethyl ammonium chloride, cinnamic acid and chitosan monomers is 0.3-0.5:0.4-0.6: 1.
The embodiment of the disclosure provides a preparation method of a chitosan-based decolorizing agent B, which is obtained by performing graft copolymerization reaction on chitosan by adopting allyl trimethyl ammonium chloride, cinnamic acid and allyl glycine.
In an optional embodiment, a preparation method of the chitosan-based decolorant B comprises the steps of adding deionized water into allyl trimethyl ammonium chloride, cinnamic acid, L-allyl glycine and chitosan, uniformly mixing, adding an initiator under the protection of nitrogen, stirring and reacting at 50-70 ℃ for 4-10h, cooling to room temperature, removing homopolymers and unreacted monomers in the mixture, drying, and grinding to obtain the chitosan-based decolorant. Compared with the chitosan-based decolorizing agent A, the chitosan-based decolorizing agent B prepared by the preparation method of the embodiment still has the effects of decolorizing, flocculating, sterilizing and salt tolerance, is suitable for a wider pH value range, but has better decolorizing and flocculating effects and higher adsorption capacity and decolorizing rate.
In an alternative embodiment, the total monomers in the solution are 12-18 wt%, the cerium ammonium nitrate is 3-8 wt%, and the molar ratio of the allyl trimethyl ammonium chloride, cinnamic acid, L-allyl glycine and chitosan monomers is 0.3-0.5:0.4-0.6:0.1-0.3: 1.
The embodiment also discloses a high-efficiency decolorizing agent which has multiple functions of decolorizing, flocculating, sterilizing and the like, shows excellent decolorizing effect in a wider pH range, has higher adsorption capacity, decolorizing rate and salt tolerance, and comprises the chitosan-based decolorizing agent A and/or the chitosan-based decolorizing agent B prepared by the preparation method. The chitosan-based decolorizing agent contains a large amount of carboxyl, amino active groups and cations, has multiple functions of decolorization, flocculation, sterilization and the like, and can be combined with dye molecules and organic pollutants through electrostatic attraction, ion exchange, complexation and the like, so that the aim of removing the dye and the organic pollutants is fulfilled; the chitosan-based decolorizing agent shows excellent decolorizing effect in a wider pH range (the pH value is 2.0-10.0); in addition, the chitosan-based decolorant also has higher adsorption capacity, decoloration rate and salt tolerance.
In an alternative embodiment, the chitosan-based decolorant a or chitosan-based decolorant B has a grafting efficiency of > 70%.
In an alternative embodiment, the chitosan-based decolorant a or chitosan-based decolorant B has a grafting ratio of > 120%.
In an optional embodiment, the decolorization rate of the chitosan-based decolorizer A or the chitosan-based decolorizer B is above 90%, and the removal rate of COD is above 80%.
In an alternative embodiment, the weight ratio of chitosan-based decolorant A to chitosan-based decolorant B is 0-1: 0-1. The chitosan-based decoloring agent A and the chitosan-based decoloring agent B are compounded to generate a synergistic effect.
In an alternative embodiment, the high performance decolorant further includes PAC. The chitosan-based decolorant and PAC are compounded to generate a synergistic effect, so that the decoloring capacity is improved, the using amount of the chitosan-based decolorant is reduced, and the printing and dyeing wastewater treatment cost is reduced; in addition, the chitosan-based decolorizing agent and PAC are compounded for use, so that the salt tolerance of the chitosan-based decolorizing agent can be improved.
In an alternative embodiment, the weight ratio of chitosan-based decolorant to PAC is 1:1 to 3.
In an alternative embodiment, the weight ratio of chitosan-based decolorant a, chitosan-based decolorant B, and PAC is 0-1:0-1: 1-3.
The embodiment also discloses the application of the high-efficiency decolorizing agent in the treatment of printing and dyeing wastewater.
The high-efficiency decolorizing agent has good decolorizing effect, shows excellent decolorizing effect in a wider pH range or in the presence of salt, and can be used for treating printing and dyeing wastewater.
In an alternative embodiment, the use of a high efficiency decolorant 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:
a high-efficiency decolorizing agent comprises a chitosan-based decolorizing agent, and the preparation method of the chitosan-based decolorizing agent comprises the following steps: adding deionized water into allyl trimethyl ammonium chloride, cinnamic acid and chitosan, mixing uniformly, adding an initiator under the protection of nitrogen, stirring at 60 ℃ for reacting for 6h, cooling to room temperature, removing homopolymer and unreacted monomer therein, drying, and grinding to obtain the chitosan-based decolorant. The total monomer content in the solution is 15 wt%, the cerium ammonium nitrate content is 5 wt%, and the molar ratio of allyl trimethyl ammonium chloride, cinnamic acid and chitosan monomer is 0.45:0.55: 1.
Example 2:
a high-efficiency decolorizing agent comprises a chitosan-based decolorizing agent, and the preparation method of the chitosan-based decolorizing agent comprises the following steps: adding deionized water into allyl trimethyl ammonium chloride, cinnamic acid and chitosan, mixing uniformly, adding an initiator under the protection of nitrogen, stirring at 55 ℃ for reaction for 10h, cooling to room temperature, removing homopolymer and unreacted monomer therein, drying, and grinding to obtain the chitosan-based decolorant. The total monomer content in the solution is 18 wt%, the cerium ammonium nitrate content is 8 wt%, and the molar ratio of allyl trimethyl ammonium chloride, cinnamic acid and chitosan monomer is 0.3:0.6: 1.
Example 3:
a high-efficiency decolorizing agent comprises a chitosan-based decolorizing agent, and the preparation method of the chitosan-based decolorizing agent comprises the following steps: adding deionized water into allyl trimethyl ammonium chloride, cinnamic acid and chitosan, mixing uniformly, adding an initiator under the protection of nitrogen, stirring at 70 ℃ for reaction for 5h, cooling to room temperature, removing homopolymer and unreacted monomer therein, drying, and grinding to obtain the chitosan-based decolorant. The total monomer content in the solution is 13 wt%, the cerium ammonium nitrate content is 3.5 wt%, and the molar ratio of allyl trimethyl ammonium chloride, cinnamic acid and chitosan monomer is 0.5:0.6: 1.
Example 4:
a high-efficiency decolorizing agent comprises a chitosan-based decolorizing agent, and the preparation method of the chitosan-based decolorizing agent comprises the following steps: adding deionized water into allyl trimethyl ammonium chloride, cinnamic acid, L-allyl glycine and chitosan, uniformly mixing, adding an initiator under the protection of nitrogen, stirring at 60 ℃ for reacting for 6 hours, cooling to room temperature, removing homopolymers and unreacted monomers in the mixture, drying, and grinding to obtain the chitosan-based decolorant. The total monomer content in the solution is 15 wt%, the cerium ammonium nitrate content is 5 wt%, and the monomer molar ratio of allyl trimethyl ammonium chloride, cinnamic acid, L-allyl glycine and chitosan is 0.45:0.55:0.15: 1.
Example 5:
a high-efficiency decolorizing agent comprises a chitosan-based decolorizing agent, and the preparation method of the chitosan-based decolorizing agent comprises the following steps: adding deionized water into allyl trimethyl ammonium chloride, cinnamic acid, L-allyl glycine and chitosan, uniformly mixing, adding an initiator under the protection of nitrogen, stirring at 60 ℃ for reacting for 6 hours, cooling to room temperature, removing homopolymers and unreacted monomers in the mixture, drying, and grinding to obtain the chitosan-based decolorant. The total monomer content in the solution is 15 wt%, the cerium ammonium nitrate content is 5 wt%, and the monomer molar ratio of allyl trimethyl ammonium chloride, cinnamic acid, L-allyl glycine and chitosan is 0.4:0.5:0.1: 1.
Example 6:
a high-efficiency decolorizing agent comprises a chitosan-based decolorizing agent, and the preparation method of the chitosan-based decolorizing agent comprises the following steps: adding deionized water into allyl trimethyl ammonium chloride, cinnamic acid, L-allyl glycine and chitosan, uniformly mixing, adding an initiator under the protection of nitrogen, stirring and reacting for 10 hours at 55 ℃, cooling to room temperature, removing homopolymers and unreacted monomers in the mixture, drying, and grinding to obtain the chitosan-based decolorant. The total monomer content in the solution is 18 wt%, the cerium ammonium nitrate content is 8 wt%, and the monomer molar ratio of allyl trimethyl ammonium chloride, cinnamic acid, L-allyl glycine and chitosan is 0.3:0.6:0.2: 1.
Example 7:
a high-efficiency decolorizing agent comprises a chitosan-based decolorizing agent, and the preparation method of the chitosan-based decolorizing agent comprises the following steps: adding deionized water into allyl trimethyl ammonium chloride, cinnamic acid, L-allyl glycine and chitosan, uniformly mixing, adding an initiator under the protection of nitrogen, stirring at 70 ℃ for reaction for 5 hours, cooling to room temperature, removing homopolymers and unreacted monomers in the mixture, drying, and grinding to obtain the chitosan-based decolorant. The total monomer content in the solution is 13 wt%, the cerium ammonium nitrate content is 3.5 wt%, and the molar ratio of allyl trimethyl ammonium chloride, cinnamic acid, L-allyl glycine and chitosan monomer is 0.5:0.6:0.15: 1.
Example 8:
a high-efficiency decolorizing agent comprises chitosan-based decolorizing agent and PCA in example 1, and the weight ratio of the chitosan-based decolorizing agent to the PCA is 1: 2.
Example 9:
a high-efficiency decolorizing agent comprises the chitosan-based decolorizing agent and PCA in example 4, and the weight ratio of the chitosan-based decolorizing agent to the PCA is 1: 2.
Example 10:
a high-efficiency decolorizing agent comprises the chitosan-based decolorizing agent in example 1 and the chitosan-based decolorizing agent in example 4, wherein the weight ratio of the chitosan-based decolorizing agent to the chitosan-based decolorizing agent is 0.5: 0.5.
Example 11:
a high-efficiency decolorizing agent comprises the chitosan-based decolorizing agent in example 1 and the chitosan-based decolorizing agent in example 4, wherein the weight ratio of the chitosan-based decolorizing agent to the chitosan-based decolorizing agent is 0.6: 0.4.
Example 12:
a high-efficiency decolorizing agent comprises chitosan-based decolorizing agent of example 1, chitosan-based decolorizing agent of example 4 and PCA in a weight ratio of 0.5:0.5: 2.
Example 13:
a high-efficiency decolorizing agent comprises chitosan-based decolorizing agent of example 1, chitosan-based decolorizing agent of example 4 and PCA in a weight ratio of 0.6:0.4: 2.
Example 14:
1. grafting efficiency of Chitosan-based decolorizing agent
The grafting efficiency of the chitosan-based decolorant 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.
2. Graft ratio determination of chitosan-based decolorant
The weight method is adopted for measurement, and the calculation formula is as follows:
percent graft ratio (%) - (m-m)1)/m1×100％；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 efficiency and grafting ratio of the chitosan-based decolorizer are shown in FIG. 1, and it can be seen that the grafting efficiency of the chitosan-based decolorizer in examples 1-7 is more than 70%, and the grafting ratio of the chitosan-based decolorizer in examples 1-7 is more than 120%.
2. Fourier transform Infrared Spectroscopy (FTIR) analysis of Chitosan-based destaining agents
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, chitosan-based decolorant of example 1 and chitosan-based decolorant of example 4 are shown in FIG. 2, wherein a is chitosan, b is chitosan-based decolorant of example 1, and c is chitosan-based decolorant of example 4. As can be seen from FIG. 3, the FTIR spectrum of chitosan-based decolorant of example 1 compared to chitosan is 2912.30cm-1The absorption peak at position is 1986.15cm, which is caused by stretching vibration of methyl group on quaternary ammonium salt molecule-1The compound is formed by-N in quaternary ammonium salt+-CH3Absorption peak of 1700.71cm-1Where is an absorption peak due to stretching vibration of C ═ O, 1523.08cm-1The position is a deformation vibration absorption peak caused by C-H in a benzene ring skeleton, 736.92cm-1Is the absorption peak caused by the out-of-plane deformation vibration of C-H in the quaternary ammonium salt, 521.54cm-1The peak is the absorption peak caused by the stretching vibration of C-N, and the analysis result shows that the allyl trimethyl ammonium chloride and the cinnamic acid are successfully grafted to the chitosan. Example 4 Chitosan-based destaining agent FTIR spectra compared to chitosan, 2906.92cm-1The absorption peak at position is 1996.91cm, which is caused by stretching vibration of methyl group on quaternary ammonium salt molecule-1The compound is formed by-N in quaternary ammonium salt+-CH3Absorption peak of 1727.69cm-1Where is an absorption peak due to stretching vibration of C ═ O, 1544.62cm-1The part is deformation vibration absorption caused by C-H in benzene ring skeletonPeak, 710.00cm-1Is the absorption peak caused by the out-of-plane deformation vibration of C-H in the quaternary ammonium salt, 553.85cm-1The peak is the absorption peak caused by the stretching vibration of C-N, and the analysis result shows that the allyl trimethyl ammonium chloride, the cinnamic acid and the L-allyl glycine are successfully grafted to the chitosan.
3. Decolorization experiment of high-efficiency decolorizer
Preparing reactive brilliant blue KN-R dye into dye wastewater with the concentration of 100mg/L, adding NaCl and a high-efficiency 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 determine the decolorization rate and the COD removal rate of the high-efficiency decolorizer 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-absorbance of the decolorized dye wastewater.
When the solution reaches the adsorption balance, a COD tester is used for measuring the COD value of the solution after the adsorption of the high-efficiency decolorant, and the COD removal rate (%) is calculated 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 the high-efficiency decolorizing agent is 200mg/L and the pH value of a water body is adjusted to 5.0, the decolorizing rate and the COD removal rate of the high-efficiency decolorizing agent on dye wastewater are shown in figure 3, and as can be seen from figure 3, the decolorizing rate and the COD removal rate of the high-efficiency decolorizing agents of examples 1-12 on the dye wastewater are both higher than those of chitosan, the decolorizing rate of the high-efficiency decolorizing agents of examples 1-12 on the dye wastewater is more than 90%, and the COD removal rate is more than 80%, which indicates that the decolorizing effect of the high-efficiency decolorizing agents of examples 1-12 is good; examples 4 to 5, the decolorization rate and the COD removal rate of the high-efficiency decolorizer on the dye wastewater are both higher than those in example 1, example 6, the decolorization rate and the COD removal rate of the high-efficiency decolorizer on the dye wastewater are both higher than those in example 2, and example 7, the decolorization rate and the COD removal rate of the high-efficiency decolorizer on the dye wastewater are both higher than those in example 3, which shows that the decolorization effect of the chitosan-based decolorizer B obtained by graft copolymerization of the chitosan with allyl trimethyl ammonium chloride, cinnamic acid and allyl glycine is better than that of the chitosan-based decolorizer A obtained by graft copolymerization of the chitosan with allyl trimethyl ammonium chloride and cinnamic acid; example 8, the decolorization rate and the COD removal rate of the high-efficiency decolorizer on the dye wastewater are both higher than those of example 1, and example 9, the decolorization rate and the COD removal rate of the high-efficiency decolorizer on the dye wastewater are both higher than those of example 4, which shows that the chitosan-based decolorizer and PAC can generate a synergistic effect in the combined use, and the decolorization capacity is improved; examples 10-11 the decolorizing rate and the COD removal rate of the high-efficiency decolorizing agent on the dye wastewater are higher than those of examples 1 and 4, which shows that the compound use of the chitosan-based decolorizing agent A and the chitosan-based decolorizing agent B can generate a synergistic effect and improve the decolorizing capacity; the decolorization rate and the COD removal rate of the high-efficiency decolorizer for dye wastewater in examples 12 to 13 are higher than those in examples 1 and 4 and examples 10 to 11, which shows that the synergistic effect of the chitosan-based decolorizer A, the chitosan-based decolorizer B and the PCA can be generated to improve the decolorization capacity.
When the adding amount of NaCl is 0, the adding amount of the high-efficiency decolorizing agent is 200mg/L, and the decolorizing rates of the high-efficiency decolorizing agent to the dye wastewater in different pH ranges are shown in figure 4, it can be seen that the high-efficiency decolorizing agents in example 1 and examples 4-5 have higher decolorizing rates to the dye wastewater at the pH value of 2.0-10.0, and the decolorizing rates are all more than 80%, which indicates that the high-efficiency decolorizing agents in example 1 and examples 4-5 are applicable to wider pH value ranges; meanwhile, the decoloring rate of the high-efficiency decoloring agent in the embodiment 4-5 on the dye wastewater is lower than that in the embodiment 1 under the same pH value, which shows that under the same pH value, compared with the case that the chitosan-based decoloring agent A is obtained by performing graft copolymerization reaction on chitosan by adopting allyl trimethyl ammonium chloride and cinnamic acid, the chitosan-based decoloring agent B is obtained by performing graft copolymerization reaction on chitosan by adopting allyl trimethyl ammonium chloride, cinnamic acid and allyl glycine, the chitosan-based decoloring agent B has a better decoloring effect.
Under the conditions that the adding amount of NaCl is 0, the adding amount of the high-efficiency decolorizing agent is 200mg/L and the pH value of the water body is adjusted to 5.0, the standing time required by the high-efficiency decolorizing agent to reach the highest decolorizing rate of the dye wastewater is shown in figure 5, and it can be seen that the standing time required by the high-efficiency decolorizing agents of examples 1 to 7 to reach the highest decolorizing rate of the dye wastewater is lower than that of chitosan; meanwhile, the standing time required by the high-efficiency decolorizing agents in examples 4 and 5 to reach the highest decolorizing rate of the dye wastewater is lower than that in example 1, the standing time required by the high-efficiency decolorizing agents in example 6 to reach the highest decolorizing rate of the dye wastewater is lower than that in example 2, and the standing time required by the high-efficiency decolorizing agents in example 7 to reach the highest decolorizing rate of the dye wastewater is lower than that in example 3, which shows that the decolorizing rate of the chitosan-based decolorizing agent B obtained by graft copolymerization of chitosan by adopting allyl trimethyl ammonium chloride, cinnamic acid and allyl glycine to the dye wastewater is better than that of the chitosan-based decolorizing agent A obtained by adopting allyl trimethyl ammonium chloride and cinnamic acid to the chitosan.
Under the conditions that the adding amount of NaCl is 20mg/L, the adding amount of the high-efficiency decolorizing agent is 200mg/L and the pH value of a water body is adjusted to 5.0, the decolorizing rate and the COD removal rate of the high-efficiency decolorizing agent on the salt-containing dye wastewater are shown in figure 6, and as can be seen from figure 6, the decolorizing rate and the COD removal rate of the high-efficiency decolorizing agent on the salt-containing dye wastewater in the examples 1-12 are both higher than those of chitosan, the decolorizing rate of the high-efficiency decolorizing agent on the salt-containing dye wastewater in the examples 1-12 is more than 80%, and the COD removal rate is more than 70%, which indicates that the decolorizing effect of the high-efficiency decolorizing agent in the examples 1-12 on the salt-containing dye wastewater is good; examples 4 to 5, the decoloring rate and the COD removal rate of the high-efficiency decoloring agent on the saline dye wastewater are both higher than those in example 1, example 6, the decoloring rate and the COD removal rate of the high-efficiency decoloring agent on the saline dye wastewater are both higher than those in example 2, and example 7, the decoloring rate and the COD removal rate of the high-efficiency decoloring agent on the saline dye wastewater are both higher than those in example 3, which shows that the decoloring effect of the chitosan-based decoloring agent B obtained by performing graft copolymerization on chitosan by using allyl trimethyl ammonium chloride, cinnamic acid and allyl glycine on the saline dye wastewater is better than that of the chitosan-based decoloring agent a obtained by performing graft copolymerization on chitosan by using allyl trimethyl ammonium chloride and cinnamic acid; example 8, the decolorization rate and the COD removal rate of the high-efficiency decolorizer on the saline dye wastewater are both higher than those in example 1, and the decolorization rate and the COD removal rate of the high-efficiency decolorizer on the saline dye wastewater are both higher than those in example 4, which indicates that the synergistic effect can be generated by the complex use of the chitosan-based decolorizer and the PAC, and the decolorization capability on the saline dye wastewater is improved; examples 10-11 the decolorization rate and the COD removal rate of the high-efficiency decolorizer for the saline dye wastewater are higher than those of examples 1 and 4, which shows that the synergistic effect of the chitosan-based decolorizer A and the chitosan-based decolorizer B can be generated by the combined use of the chitosan-based decolorizer A and the chitosan-based decolorizer B, and the decolorization capability for the saline dye wastewater can be improved; the decolorization rate and the COD removal rate of the high-efficiency decolorizer for the saline dye wastewater in the examples 12 to 13 are higher than those in the examples 1 and 4 and the examples 10 to 11, which shows that the synergistic effect can be generated by the combined use of the chitosan-based decolorizer A, the chitosan-based decolorizer B and the PCA, and the decolorization capability for the saline dye wastewater is improved.
4. Flocculation experiment of high-efficiency 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; a fresh stock solution of high-potency decolorizing agent was prepared by dissolving 0.1g of high-potency decolorizing agent in 100mL of distilled water prior to each experiment; adding the high-efficiency decolorizing agent stock solution into the synthetic wastewater, enabling the adding amount of the high-efficiency decolorizing agent to be 0.5mg/L, stirring at 200rpm for 5min until the high-efficiency decolorizing agent is completely mixed, and then slowly stirring at 50rpm for 15min to promote the growth of the high-efficiency decolorizing agent. 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 high-efficiency decolorizing agent on the kaolin suspension is shown in fig. 7, and as can be seen from fig. 7, the turbidity removal rates of the high-efficiency decolorizing agents of examples 1 to 12 on the kaolin suspension are over 95 percent and are all higher than that of chitosan, which indicates that the high-efficiency decolorizing agents of examples 1 to 12 have better flocculation property which is better than that of chitosan; examples 4 to 5, the turbidity removal rates of the high-efficiency decoloring agents to the kaolin suspension are higher than those in example 1, example 6, the turbidity removal rates of the high-efficiency decoloring agents to the kaolin suspension are higher than those in example 2, and example 7, the turbidity removal rates of the high-efficiency decoloring agents to the kaolin suspension are higher than those in example 3, which shows that the effect of the chitosan-based decoloring agent B obtained by the graft copolymerization reaction of allyl trimethyl ammonium chloride, cinnamic acid and allyl glycine on the turbidity removal of the kaolin suspension is better than that of the chitosan-based decoloring agent A obtained by the graft copolymerization reaction of allyl trimethyl ammonium chloride and cinnamic acid; example 8, the turbidity removal rate of the high-efficiency decolorizing agent on the kaolin suspension is higher than that of example 1, and example 9, the turbidity removal rate of the high-efficiency decolorizing agent on the kaolin suspension is higher than that of example 4, which shows that the chitosan-based decolorizing agent and PAC are compounded to generate a synergistic effect and improve the flocculation effect on the kaolin suspension; examples 10-11 the high-efficiency decolorant has a higher turbidity removal rate on the kaolin suspension than examples 1 and 4, which shows that the chitosan-based decolorant A and the chitosan-based decolorant B can generate a synergistic effect when used in combination, and the flocculation effect on the kaolin suspension is improved; the turbidity removal rate of the high-efficiency decolorizing agents in examples 12 to 13 on kaolin suspensions is higher than that of the high-efficiency decolorizing agents in examples 1 and 4 and examples 10 to 11, which shows that the synergistic effect of the chitosan-based decolorizing agent A, the chitosan-based decolorizing agent B and the PCA can be generated when the chitosan-based decolorizing agent A, the chitosan-based decolorizing agent B and the PCA are compounded, and the flocculation effect on the kaolin suspensions is improved.
5. Sterilization experiment of high-efficiency 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. In each experimentPreviously, a fresh stock solution of high-potency decolorizing agent was prepared by dissolving 0.1g of high-potency decolorizing agent in 100mL of distilled water; adding the high-efficiency decolorant stock solution into the salmonella suspension to ensure that the adding amount of the high-efficiency decolorant is 5mg/L, adjusting the pH to 5.0, stirring for 5min at 200rpm until the high-efficiency decolorant is completely mixed, and then slowly stirring for 15min at 50rpm to promote the growth of the high-efficiency decolorant. Finally, the flocs were allowed to settle for 30min to maintain flocculation equilibrium. The supernatant at 2cm below the water surface of the sample solution after flocculation was collected with a syringe, and turbidity removal and bacteria removal (%) were calculated by measuring absorbance values of the supernatant before and after treatment at 600nm using an ultraviolet spectrophotometer:
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 the bacteria removal rate of the high-efficiency decolorant on the salmonella suspension are shown in fig. 8, and as can be seen from fig. 8, the turbidity removal rate and the bacteria removal rate of the salmonella suspension of the high-efficiency decolorant in examples 1 to 7 are both higher than those of chitosan, the turbidity removal rate of the salmonella suspension of the high-efficiency decolorant in examples 1 to 7 is higher than 90%, and the bacteria removal rate of the salmonella suspension is higher than 90%, which indicates that the high-efficiency decolorant in examples 1 to 7 has better bactericidal property and better bactericidal property than chitosan.
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. A chitosan-based decolorant is prepared by graft copolymerization of allyl trimethyl ammonium chloride and cinnamic acid on chitosan.
2. The method for preparing a chitosan-based decolorant according to claim 1, which is characterized in that: the graft copolymerization is carried out under the protection of nitrogen, the temperature of the graft copolymerization is 50-70 ℃, and the time is 4-10 h.
3. The method for preparing a chitosan-based decolorant according to claim 1, which is characterized in that: the molar ratio of the allyl trimethyl ammonium chloride, the cinnamic acid and the chitosan monomer is 0.3-0.5:0.4-0.6: 1.
4. A high-efficiency decolorizing agent, comprising the chitosan-based decolorizing agent prepared by the preparation method of claim 1.
5. The high-efficiency decoloring agent according to claim 4, wherein: the graft ratio of the chitosan-based decolorant is more than 120 percent.
6. The high-efficiency decoloring agent according to claim 4, wherein: the decolorization rate of the chitosan-based decolorizer is more than 90%, and the removal rate of COD is more than 80%.
7. The high-efficiency decoloring agent according to claim 4, wherein: the high performance decolorant also includes PAC.
8. The high-efficiency decoloring agent according to claim 4, wherein: the weight ratio of the chitosan-based decolorizing agent to PAC is 1: 1-3.
9. Use of the high performance decolorant of any of claims 4 to 8 in treatment of printing and dyeing wastewater.
10. Use according to claim 9, characterized in that: the application of the high-efficiency decolorizing agent in the treatment of salt-containing printing and dyeing wastewater.
CN202110345814.9A 2021-03-31 2021-03-31 High-efficiency decolorizing agent and application thereof in printing and dyeing wastewater treatment Withdrawn CN112919691A (en)

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