CN109052741B - Synchronous decoloring and nitrogen recovery treatment method for printing wastewater - Google Patents

Synchronous decoloring and nitrogen recovery treatment method for printing wastewater Download PDF

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Publication number
CN109052741B
CN109052741B CN201811202409.6A CN201811202409A CN109052741B CN 109052741 B CN109052741 B CN 109052741B CN 201811202409 A CN201811202409 A CN 201811202409A CN 109052741 B CN109052741 B CN 109052741B
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wastewater
cation exchange
exchange resin
resin
nitrogen
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CN109052741A (en
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柳荣展
于梦楠
于晓
张宾
潘颖
石宝龙
于潘芬
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Qingdao University
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Qingdao University
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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
    • C02F1/42—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
    • C02F1/24—Treatment of water, waste water, or sewage by flotation
    • 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
    • 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
    • C02F2001/425—Treatment of water, waste water, or sewage by ion-exchange using cation exchangers
    • 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
    • C02F2101/10—Inorganic compounds
    • C02F2101/16—Nitrogen compounds, e.g. ammonia
    • 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
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2301/00—General aspects of water treatment
    • C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions

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  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Treatment Of Water By Ion Exchange (AREA)
  • Separation Of Suspended Particles By Flocculating Agents (AREA)
  • Physical Water Treatments (AREA)
  • Removal Of Specific Substances (AREA)

Abstract

The invention discloses a synchronous decoloration and nitrogen recovery treatment method for printing wastewater, which is characterized by comprising the following steps: adding cation exchange resin into printing wastewater, and stirring for 10-180 min; separating the cation exchange resin precipitate from the wastewater; separating suspended matters in the wastewater from the wastewater by adopting a conventional precipitation method or an air floatation method; dehydrating the precipitated cation exchange resin and treating with an acid solution to recover nitrogen and regenerate the resin; and adding the regenerated cation exchange resin into the printing wastewater for recycling. By adopting the treatment method, the printing wastewater decolorization rate is up to more than 99.5 percent, the ammonia nitrogen removal rate is up to more than 85 percent, and the COD (chemical oxygen demand) isCrThe removal rate reaches more than 90 percent, realizes the synchronous decolorization of the wastewater and the recovery of nitrogen, and does not increase the content of acid radical ions in the wastewater.

Description

Synchronous decoloring and nitrogen recovery treatment method for printing wastewater
The application is a divisional application of the following application, which is named as a synchronous decoloring and nitrogen recovery method of printing wastewater, and has the application number of 201610032737.0 and the application date of 2016.1.19.
Technical Field
The invention belongs to the technical field of textile printing and dyeing industry, and particularly relates to a synchronous decoloring and nitrogen recovery treatment method for printing wastewater.
Background
The ink is composed of pigment, binder, filler and additive, and can be divided into oil ink and water-based ink. The water-based ink mainly comprises water-soluble resin, pigment, alcohol, amine or ammonia and other additives and water. The water-based ink has the advantages of safety, environmental protection and the like, so the water-based ink is increasingly widely applied. At present, a large amount of plastic packaging (waterproof) materials are printed by adopting water-based ink increasingly, and a certain amount of printing wastewater is generated in the production process. The waste water contains pigment, water soluble acrylic resin, alcohol, amine and other pollutant, and has high organic matter content, high chroma, high nitrogen content and common waste water CODCr: 5000-25000 mg/L; chroma: 3000-12000 times; ammonia nitrogen: 200-1200 mg/L. The pollution is very serious and is difficult to treat.
For the treatment of the wastewater, chemical methods such as coagulation method, acid precipitation method and the like are usually adopted for pretreatment, namely coagulant or acid is directly added into the wastewater to coagulate organic pollutants into sludge, solid-liquid separation methods such as precipitation or air flotation are adopted to remove a large amount of suspended pollutants in the wastewater, and the effluent is subjected to other chemical or biological treatment. However, the coagulation method and the acidification method can only remove organic matters such as water-soluble resin and pigment in the wastewater, but cannot reduce the content of ammonia nitrogen in the wastewater, and other chemical methods or biological methods are usually required to remove the organic matters. In particular, the acid precipitation method directly adds inorganic acid into the wastewater, so that the content of acid radical ions in the wastewater is increased, and secondary pollution is caused.
Disclosure of Invention
The invention aims to provide a synchronous decoloration and nitrogen recovery treatment method for printing wastewater, which realizes the efficient removal of organic pollutants and nitrogen in the wastewater and the recovery of nitrogen at the same time without increasing the content of acid radical ions in the wastewater.
In order to achieve the purpose, the technical method comprises the following steps:
adding cation exchange resin into the printing wastewater, and stirring for 10-180min until the pollutants are fully precipitated and coagulated; separating the cation exchange resin precipitate from the wastewater; separating suspended matters in the wastewater from the wastewater by adopting a conventional precipitation method or an air floatation method; filtering and dehydrating the precipitated cation exchange resin, treating the cation exchange resin with an acid solution with the mass concentration of 2-30%, recovering nitrogen and simultaneously regenerating the resin; and adding the regenerated cation exchange resin into the printing wastewater for recycling.
Has the advantages that:
a. the printing wastewater treated by the method has the advantages of decoloration rate of over 99.5 percent, ammonia nitrogen removal rate of over 85 percent and CODCrThe removal rate reaches more than 90 percent, and the synchronous decolorization of the printing wastewater and the recovery of nitrogen are realized.
b. The cation exchange resin is added into the waste water to be ionized to release H+，H+Can be reacted with [ R ]3NH]+Various cations are subjected to ion exchange, the cations are adsorbed, and H is further released+. Released H+On the one hand, the acrylic resin can be reacted with water-soluble acrylic resin R-COO-The combination forms R-COOH, reduces the solubility of the resin, destroys the stability of a colloid system, and converts the hydrophilic resin in the wastewater into hydrophobic pollutants by acid precipitation to precipitate and agglomerate. On the other hand, released H+Can be mixed with R in waste water3N forms more R3NH]+Increasing its concentration, promoting its reaction with H+Ion exchange is carried out, and the recovery rate of nitrogen is improved. Compared with the acid precipitation method, the method can not increase the concentration of acid radical ions in the wastewater and prevent the acid radical ions from forming secondary pollution.
Detailed Description
The invention is further illustrated by the following specific examples.
Example 1
Adding hydrogen type strong acid cation exchange resin into blue printing wastewater (COD)Cr: 16200 mg/L; chroma: 5000 times of the total weight of the mixture; ammonia nitrogen: 327mg/L), stirring and reacting for 60 min; separating the cation exchange resin precipitate from the wastewater; by precipitation of waste waterSeparating suspended matters from the wastewater; the precipitated cation exchange resin is treated with a 10% by mass hydrochloric acid solution to form [ R ]3NH]+Cl-Recovering ammonia nitrogen and regenerating resin; and adding the regenerated hydrogen type strong-acid cation exchange resin into the printing wastewater for recycling.
By adopting the method for treatment, the printing wastewater decolorization rate reaches up to 99.8 percent, the ammonia nitrogen removal rate reaches up to 90.4 percent, and the COD isCrThe removal rate reaches 92.3 percent, the synchronous decolorization of the wastewater and the recovery of nitrogen are realized, the concentration of chloride ions in the wastewater cannot be obviously increased, and the secondary pollution is reduced.
Example 2
Sodium type strong acid cation exchange resin is added into blue printing wastewater (COD) after being pretreated and replaced by hydrochloric acid solution with the mass concentration of 10 percentCr: 16200 mg/L; chroma: 5000 times of the total weight of the mixture; ammonia nitrogen: 327mg/L), stirring and reacting for 60 min; separating the cation exchange resin precipitate from the wastewater; separating suspended matters in the wastewater from the wastewater by adopting a precipitation method; the precipitated cation exchange resin is treated with a 10% by mass hydrochloric acid solution to form [ R ]3NH]+Cl-Recovering ammonia nitrogen and regenerating resin; and adding the regenerated strong-acid cation exchange resin into the printing wastewater for recycling.
By adopting the method for treatment, the printing wastewater decolorization rate reaches up to 99.8 percent, the ammonia nitrogen removal rate reaches up to 90.1 percent, and the COD isCrThe removal rate reaches 92.2 percent, the synchronous decolorization of the wastewater and the recovery of nitrogen are realized, the concentration of chloride ions in the wastewater cannot be obviously increased, and the secondary pollution is reduced.
Example 3
Adding hydrogen type strong acid cation exchange resin into black printing wastewater (COD)Cr: 17800 mg/L; chroma: 6000 times; ammonia nitrogen: 351mg/L), stirring and reacting for 180 min; separating the cation exchange resin precipitate from the wastewater; separating suspended matters in the wastewater from the wastewater by adopting a precipitation method; the precipitated cation exchange resin was treated with a 4% by mass sulfuric acid solution to form (R)3NH+)2SO4 2-Recovering ammonia nitrogenAnd simultaneously regenerating the resin; and adding the regenerated cation exchange resin into the printing wastewater for recycling.
By adopting the method for treatment, the water-based ink printing wastewater decolorization rate reaches up to 100 percent, the ammonia nitrogen removal rate reaches 89.6 percent, and the COD isCrThe removal rate reaches 93.1 percent, realizes the synchronous decolorization of the wastewater and the recovery of nitrogen, does not obviously increase the concentration of sulfate ions in the wastewater, and lightens the secondary pollution.
Example 4
Sodium type strong acid cation exchange resin is added into black printing wastewater (COD) after being pretreated and replaced by sulfuric acid solution with the mass concentration of 4 percentCr: 17800 mg/L; chroma: 6000 times; ammonia nitrogen: 351mg/L), stirring and reacting for 180 min; separating the cation exchange resin precipitate from the wastewater; separating suspended matters in the wastewater from the wastewater by adopting a precipitation method; the precipitated cation exchange resin was treated with a 5% sulfuric acid solution by mass to form ([ R ]3NH]+)2SO4 2-Recovering ammonia nitrogen and regenerating resin; and adding the regenerated hydrogen type strong-acid cation exchange resin into the printing wastewater for recycling.
The printing wastewater decolorization rate reaches up to 100 percent, the ammonia nitrogen removal rate reaches up to 88.7 percent, and the COD is treated by adopting the method of the inventionCrThe removal rate reaches 92.5 percent, the synchronous decolorization of the wastewater and the recovery of nitrogen are realized, the concentration of sulfate ions in the wastewater cannot be obviously increased, and the secondary pollution is reduced.
Example 5
Adding hydrogen type strong acid cation exchange resin which is recycled for 30 times into red printing wastewater (COD)Cr: 14700 mg/L; chroma: 6000 times; ammonia nitrogen: 341mg/L), stirring and reacting for 60 min; separating the cation exchange resin precipitate from the wastewater; separating suspended matters in the wastewater from the wastewater by adopting a precipitation method; the precipitated cation exchange resin is treated with a 10% by mass hydrochloric acid solution to form [ R ]3NH]+Cl-Recovering ammonia nitrogen and regenerating resin; and adding the regenerated hydrogen type strong-acid cation exchange resin into the printing wastewater for recycling.
By adopting the method for treatment, the printing wastewater decolorization rate reaches up to 99.8 percent, the ammonia nitrogen removal rate reaches 89.2 percent, and the COD isCrThe removal rate reaches 93.3 percent, realizes the synchronous decolorization of the wastewater and the recovery of nitrogen, does not obviously increase the concentration of chloride ions in the wastewater, and lightens the secondary pollution. The treatment effect of the regenerated resin is not obviously reduced.
Example 6
Adding sodium type strong acid cation exchange resin which is recycled for 30 times into red printing wastewater (COD)Cr: 14700 mg/L; chroma: 6000 times; ammonia nitrogen: 341mg/L), stirring and reacting for 180 min; separating the cation exchange resin precipitate from the wastewater; separating suspended matters in the wastewater from the wastewater by adopting a precipitation method; the precipitated cation exchange resin is treated with a 10% by mass hydrochloric acid solution to form [ R ]3NH]+Cl-Recovering ammonia nitrogen and regenerating resin; and adding the regenerated hydrogen type weak acid cation exchange resin into the printing wastewater for recycling.
By adopting the method for treatment, the printing wastewater decolorization rate reaches up to 99.7 percent, the ammonia nitrogen removal rate reaches up to 87.6 percent, and the COD isCrThe removal rate reaches 92.8 percent, the synchronous decolorization of the wastewater and the recovery of nitrogen are realized, the concentration of chloride ions in the wastewater cannot be obviously increased, and the secondary pollution is reduced. The treatment effect of the sodium-type regenerated resin is not obviously reduced.

Claims (1)

1. A synchronous decoloration and nitrogen recovery treatment method for printing wastewater is characterized by comprising the following steps:
adding cation exchange resin into printing wastewater, stirring for 10-180min until the pollutants are fully precipitated and coagulated, adding cation exchange resin into wastewater to ionize and release H+，H+Can be reacted with [ R ]3NH]+Ion exchange occurs, cations are adsorbed and H is further released+Liberating H+On the one hand, the acrylic resin can be reacted with water-soluble acrylic resin R-COO-Combining to form R-COOH, reducing resin solubility, destroying colloid system stability, and separating hydrophilic resin from waste water by acid precipitationIs converted into hydrophobic pollutants to precipitate and agglomerate, and H released by the hydrophobic pollutants+Can be mixed with R in waste water3N forms more R3NH]+Increasing its concentration, promoting its reaction with H+Ion exchange is carried out, and the recovery rate of nitrogen is improved; separating the cation exchange resin precipitate from the wastewater; separating suspended matters in the wastewater from the wastewater by adopting a conventional precipitation method or an air floatation method; filtering and dehydrating the precipitated cation exchange resin, treating the cation exchange resin with an acid solution with the mass concentration of 2-30%, recovering nitrogen and simultaneously regenerating the resin; adding the regenerated cation exchange resin into printing wastewater for recycling;
the cation exchange resin is one of hydrogen type cation exchange resin or sodium type cation exchange resin, and if the cation exchange resin is the sodium type cation exchange resin, replacement treatment is carried out by using an acid solution in advance.
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CN109052743B (en) * 2016-01-19 2021-08-27 青岛大学 Method for decoloring printing wastewater and recovering nitrogen
CN109126708A (en) * 2018-09-20 2019-01-04 青岛大学 A kind of adsorption decolouriser preparation method containing photochemical catalyst
CN109126709A (en) * 2018-09-20 2019-01-04 青岛大学 A kind of preparation method with photo-catalysis function adsorption decolouriser
CN109126705A (en) * 2018-09-20 2019-01-04 青岛大学 A kind of method that high-concentration waste water pollutant is extracted and utilized
CN109126712A (en) * 2018-09-20 2019-01-04 青岛大学 A kind of high-efficiency decolorant preparation method containing photochemical catalyst
CN109126710A (en) * 2018-09-20 2019-01-04 青岛大学 A method of it prepares with photo-catalysis function adsorption decolouriser
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