CN112573748A - Integrated treatment process for printing and dyeing wastewater - Google Patents

Integrated treatment process for printing and dyeing wastewater Download PDF

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CN112573748A
CN112573748A CN202011402367.8A CN202011402367A CN112573748A CN 112573748 A CN112573748 A CN 112573748A CN 202011402367 A CN202011402367 A CN 202011402367A CN 112573748 A CN112573748 A CN 112573748A
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printing
wastewater
dyeing wastewater
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毛强平
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Nanjing Xiaoxiang Engineering 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
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D3/00—Halides of sodium, potassium or alkali metals in general
    • C01D3/04—Chlorides
    • C01D3/06—Preparation by working up brines; seawater or spent lyes
    • 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
    • C02F1/02—Treatment of water, waste water, or sewage by heating
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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
    • C02F1/26—Treatment of water, waste water, or sewage by extraction
    • 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
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    • 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
    • C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
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    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • C02F1/442—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by nanofiltration
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    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • C02F1/444—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
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    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
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    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/722—Oxidation by peroxides
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/308—Dyes; Colorants; Fluorescent agents
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/34—Organic compounds containing oxygen
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/36—Organic compounds containing halogen
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/38—Organic compounds containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/40—Organic compounds containing sulfur
    • 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
    • C02F2305/00—Use of specific compounds during water treatment
    • C02F2305/02—Specific form of oxidant
    • C02F2305/026—Fenton's reagent

Abstract

The invention relates to an integrated treatment process of printing and dyeing wastewater, belonging to the technical field of water treatment. The method comprises the following steps: step 1, filtering the printing and dyeing wastewater by using a microfiltration membrane to remove the precipitated dye which is not removed; step 2, mixing the microfiltration filtrate with an extracting agent for extraction; step 3, adopting adsorption treatment on the raffinate obtained in the step 2; step 4, sequentially carrying out iron-carbon micro-electrolysis and Fenton oxidation treatment on the wastewater obtained in the step 3; step 5, filtering the wastewater obtained in the step 4 by using a nanofiltration membrane, and returning the nanofiltration membrane concentrated solution to the step 3 for treatment; and 6, concentrating the nanofiltration membrane permeate through a reverse osmosis membrane, evaporating, concentrating and drying in sequence to obtain the industrial NaCl salt. The treatment method can effectively treat the acyl chloride printing and dyeing wastewater.

Description

Integrated treatment process for printing and dyeing wastewater
Technical Field
The invention relates to an integrated treatment process of printing and dyeing wastewater, in particular to a treatment technology of reactive dye wastewater containing acyl chloride compounds, belonging to the technical field of water treatment.
Background
With the development of the dye industry, the production wastewater thereof has become one of the main water pollution sources. At present, there are tens of thousands of dyes, which not only have specific colors, but also have complex structures, and the structures are difficult to break by taking polymer complexes as a plurality, and the dyes have low biodegradability and most have potential toxicity; meanwhile, the dye industry also belongs to the high-energy-consumption and high-pollution industry, according to measurement and calculation, about 10% -20% of dye is released into water in the production and use processes, and 7.56-15.12 million tons of dye wastewater directly enters the water environment according to the total amount of the dye produced in 2010. The reactive dye is widely used for dyeing cotton, hemp, silk, wool and other textiles, and has large dosage and much pollution discharge.
The bromopropionamido reactive dye is mainly applied to dyeing of protein fibers and has the advantages of bright color, high color fastness and good uniform dyeing. Wherein, the most widely used dyes in the market are prepared by taking dibromopropionyl chloride as a raw material. The preparation process mainly comprises the following steps: dissolving 2, 4-diaminobenzene sulfonic acid serving as an active group in water, then dropwise adding dibromopropionyl chloride, adjusting the pH value of the reaction solution to be 6-7, adding NaCl to salt out after the reaction is finished, separating out the dye, and centrifuging or filtering for separation to obtain the dye. The reaction equation is as follows:
Figure 867809DEST_PATH_IMAGE002
in the synthesis process, after salting out and separation, a large amount of wastewater containing salt, sulfonic acid dye, unreacted dibromopropionyl chloride and 2, 4-diaminobenzene sulfonic acid is generated, and the wastewater has low biodegradability and extremely high salt content and is not easy to be treated by a biochemical method, so that a process for efficiently treating the wastewater is urgently needed.
Disclosure of Invention
The purpose of the invention is: provides a method for treating high-salt-content wastewater in the production process of a bromopropionamido reactive dye.
An integrated treatment process of printing and dyeing wastewater comprises the following steps:
step 1, filtering the printing and dyeing wastewater by using a microfiltration membrane to remove the precipitated dye which is not removed; the printing and dyeing wastewater is preferably generated by adopting 2, 4-diaminobenzene sulfonic acid as an active group, reacting with dibromopropionyl chloride, salting out and filtering;
step 2, mixing the microfiltration filtrate with an extracting agent for extraction;
step 3, adopting adsorption treatment on the raffinate obtained in the step 2;
step 4, sequentially carrying out iron-carbon micro-electrolysis and Fenton oxidation treatment on the wastewater obtained in the step 3;
step 5, filtering the wastewater obtained in the step 4 by using a nanofiltration membrane, and returning the nanofiltration membrane concentrated solution to the step 3 for treatment;
and 6, concentrating the nanofiltration membrane permeate through a reverse osmosis membrane, evaporating, concentrating and drying in sequence to obtain the industrial NaCl salt.
Further, the average pore diameter of the microfiltration membrane in the step 1 is preferably 50-500 nm.
Further, the extractant in the step 2 is n-hexane; the volume ratio of the filtrate to the extracting agent is preferably 0.5-1: 1; the temperature in the extraction process is preferably 20-30 ℃, and the extraction time is preferably 10-40 min.
Further, in the step 3, the hydraulic retention time in the adsorption process is preferably 40-60 min, and the adsorption temperature is preferably 25-30 ℃; the adsorption process adopts sulfonated polyether sulfone modified attapulgite microsphere adsorbent; the preparation method of the adsorbent comprises the following steps: s1, soaking the attapulgite in 2-4 mol/L hydrochloric acid for activation treatment for 80-100 min, filtering, washing with deionized water, and roasting at 180-190 ℃ for 1-2 h to obtain acid-activated attapulgite; s2, dispersing 3-5 parts by weight of acid-activated attapulgite and 1-3 parts by weight of hexadecyl trimethyl ammonium bromide in 100-110 parts by weight of 40-50 vol.% ethanol water solution, stirring for 10-15 hours at 25-35 ℃, filtering the product, and drying to obtain surface cation-modified attapulgite; s3, preparing a dimethylformamide mixed solution containing 10-15 wt% of sulfonated polyether sulfone and 12-16 wt% of surface cation modified attapulgite, dispersing uniformly at a high speed, then dropwise adding the mixed solution into deionized water, centrifugally separating the formed microspheres, and drying in vacuum to obtain the sulfonated polyether sulfone modified attapulgite microsphere adsorbent.
Further, in the step 4, the pH value is preferably 3-5 in the Fenton oxidation treatment process, and Fe2+The concentration is preferably about 0.5-5 g/L, the treatment temperature is preferably 25-35 ℃, and the treatment time is preferably 10-50 min.
Further, in the step 5, the cut-off molecular weight of the nanofiltration membrane is preferably 200-400 Da, and the operation pressure in the nanofiltration process is preferably 1.0-3.0 Mpa.
An integrated treatment apparatus for printing and dyeing wastewater, comprising:
the infiltration side and the extraction tower of micro-filtration membrane are connected, and the raffinate export and the adsorption tower of extraction tower are connected, and the feed liquid export and the little electrolytic tower of iron carbon of adsorption tower are connected, and the feed liquid export and the fenton reactor of the little electrolytic tower of iron carbon are connected, and the feed liquid export and the receive filter membrane of fenton reactor are connected, and the infiltration side and the reverse osmosis membrane of receiving the filter membrane are connected, and the concentrated side and the evaporimeter of reverse osmosis membrane are connected.
The average pore diameter of the microfiltration membrane is 50-500 nm.
An extracting agent is filled in the extraction tower, and the extracting agent is n-hexane.
The molecular weight cut-off of the nanofiltration membrane is 200-400 Da.
The interception side of the nanofiltration membrane is connected with the feed liquid inlet of the adsorption tower.
The evaporator is a multiple effect evaporator.
The invention also provides the application of the sulfonated polyether sulfone modified attapulgite microsphere adsorbent in printing and dyeing wastewater treatment.
The invention also provides the application of the integrated treatment device in the treatment of printing and dyeing wastewater.
Advantageous effects
The wastewater to be treated is the wastewater generated by adopting 2, 4-diaminobenzene sulfonic acid as an active group, reacting with dibromopropionyl chloride, salting out (NaCl salting out) and filtering; after the reaction, the wastewater mainly contains NaCl, unseparated sulfonic acid dye, and unreacted dibromopropionyl chloride and 2, 4-diaminobenzene sulfonic acid. Therefore, in the step 1 of the invention, firstly, the wastewater is filtered by the microfiltration membrane, so that some precipitated sulfonic acid dye can be removed; the microfiltration filtrate is sent into an extraction tower and extracted by normal hexane, the aim is to remove unreacted 2, 4-diaminobenzene sulfonic acid in the microfiltration filtrate to be extracted and separated, although subsequent operations adopt iron-carbon microelectrolysis and oxidation treatment, the elimination rate of the steps on the 2, 4-diaminobenzene sulfonic acid is not high, and the removal of other organic impurities is influenced, so the operation load of the subsequent steps can be effectively reduced by adopting an extraction separation mode; the sulfonated polyether sulfone modified adsorbent in the extracted wastewater shows high selective adsorption on sulfonic impurities, so that the unseparated sulfonic dye can be further removed; because the reaction solution contains more unreacted dibromopropionyl chloride, the hydrolysis of acyl chloride groups can be promoted in the iron-carbon micro-electrolysis process, carboxylic acid and hydrogen chloride can be generated, and because the Fenton oxidation treatment is adopted in the subsequent steps, the hydrogen chloride generated after the hydrolysis can make the wastewater acidic, so that the Fenton oxidation reaches the corresponding pH range; filtering the wastewater after oxidation treatment by using a nanofiltration membrane to remove residual COD organic impurities in the wastewater, so that NaCl permeates the nanofiltration membrane to be purified; in the invention, Fe is generated in the micro-electrolysis process of iron and carbon2+A part of Fe is generated after oxidation3+In the filtering process of the nanofiltration membrane, the high-valence salt ions generate a south-of-the-road effect on the surface of the nanofiltration membrane due to the fact that the nanofiltration membrane is a charged membrane, the high-valence salt ions are intercepted, and in order to keep the charge balance on two sides of the membrane, NaCl is promoted to permeate the membrane, so that the permeation of NaCl is improvedThe phenomenon of 'negative interception' of monovalent salt even occurs, so that the iron-carbon micro-electrolysis, Fenton oxidation and nanofiltration membrane in the invention are taken as a complete technical concept, and the synergistic technical effects of treatment of acyl chloride wastewater and NaCl recovery are realized. The penetrating fluid of the nanofiltration membrane mainly contains NaCl, and industrial NaCl salt can be obtained by using a reverse osmosis membrane and evaporating and crystallizing the penetrating fluid in sequence.
Drawings
FIG. 1 is a process flow diagram of the present invention.
FIG. 2 is a diagram of the apparatus of the present invention.
FIG. 3 is a comparison of the permeability of the nanofiltration membrane to NaCl in the examples and the comparative examples.
1 is a microfiltration membrane, 2 is an extraction tower, 3 is an adsorption tower, 4 is an iron-carbon micro-electrolysis tower, 5 is a Fenton reactor, 6 is a nanofiltration membrane, 7 is a reverse osmosis membrane, and 8 is an evaporator.
Detailed Description
The source process of the printing and dyeing wastewater treated in the following examples is as follows:
2.25Kg of 2, 4-diaminobenzene sulfonic acid is dissolved in 120L of water, 3.20Kg of dibromopropionyl chloride is added dropwise, and a small amount of Na is added2CO3Adjusting the pH value of the reaction solution to be 6-7, reacting for 3 hours at 10-15 ℃, adding 18Kg of NaCl for salting out to separate out the dye, and performing centrifugal separation to obtain the dye, wherein the water quality of the centrifugal wastewater is as follows:
NaCl 15wt%, COD 6450ppm, SS 80ppm, sulfonate (calculated as 2, 4-diaminobenzene sulfonic acid) 425 ppm.
Example 1
Step 1, filtering the printing and dyeing wastewater by adopting a 50nm microfiltration membrane to remove the precipitated dye which is not removed;
step 2, mixing the microfiltration filtrate with an extracting agent n-hexane according to a volume ratio of 0.5: 1, mixing and extracting, wherein the temperature in the extraction process is 20 ℃, and the extraction time is 30 min;
step 3, adsorbing the raffinate obtained in the step 2 by using a sulfonated polyether sulfone modified attapulgite microsphere adsorbent, wherein the hydraulic retention time in the adsorption process is 50min, and the adsorption temperature is 30 ℃; the preparation method of the adsorbent comprises the following steps: s1, soaking the attapulgite in 2mol/L hydrochloric acid for activation treatment for 80min, filtering, washing with deionized water, and roasting at 180 ℃ for 1h to obtain acid-activated attapulgite; s2, dispersing 3 parts of attapulgite after acid activation and 1 part of hexadecyl trimethyl ammonium bromide into 100 parts of 40vol.% ethanol water solution, stirring for 10 hours at 25 ℃, filtering the product, and drying to obtain surface cation modified attapulgite; s3, preparing a dimethylformamide mixed solution containing 10wt% of sulfonated polyether sulfone and 12wt% of surface cation modified attapulgite, dispersing uniformly at a high speed, dropwise adding the mixed solution into deionized water, centrifugally separating the formed microspheres, and drying in vacuum to obtain the sulfonated polyether sulfone modified attapulgite microsphere adsorbent;
step 4, sequentially carrying out iron-carbon micro-electrolysis and Fenton oxidation treatment on the wastewater obtained in the step 3, wherein the hydraulic retention time of the iron-carbon micro-electrolysis process is 30min, the pH value of the wastewater is 3 in the Fenton oxidation treatment process, and Fe2+The concentration is about 0.5g/L, the treatment temperature is 25 ℃, and the treatment time is 10 min;
step 5, filtering the wastewater obtained in the step 4 by using a nanofiltration membrane, wherein the molecular weight cut-off of the nanofiltration membrane is 200Da, the operating pressure in the nanofiltration process is 1.0Mpa, and the nanofiltration membrane concentrated solution is returned to the step 3 for treatment;
and 6, concentrating the nanofiltration membrane permeate through a reverse osmosis membrane, evaporating, concentrating and drying in sequence to obtain the industrial NaCl salt.
Example 2
Step 1, filtering the printing and dyeing wastewater by using a 500nm microfiltration membrane to remove the unremoved precipitated dye;
step 2, mixing the microfiltration filtrate with an extracting agent n-hexane according to a volume ratio of 1: 1, mixing and extracting, wherein the temperature in the extraction process is 30 ℃, and the extraction time is 40 min;
step 3, adsorbing the raffinate obtained in the step 2 by using a sulfonated polyether sulfone modified attapulgite microsphere adsorbent, wherein the hydraulic retention time in the adsorption process is 50min, and the adsorption temperature is 30 ℃; the preparation method of the adsorbent comprises the following steps: s1, soaking the attapulgite in 4mol/L hydrochloric acid for activation treatment for 100min, filtering, washing with deionized water, and roasting at 190 ℃ for 2h to obtain acid-activated attapulgite; s2, dispersing 5 parts of attapulgite after acid activation and 3 parts of hexadecyl trimethyl ammonium bromide into 100 parts of 50vol.% ethanol water solution, stirring for 15 hours at 35 ℃, filtering the product, and drying to obtain surface cation modified attapulgite; s3, preparing a dimethylformamide mixed solution containing 15wt% of sulfonated polyether sulfone and 16wt% of surface cation modified attapulgite, dispersing uniformly at a high speed, dropwise adding the mixed solution into deionized water, centrifugally separating the formed microspheres, and drying in vacuum to obtain the sulfonated polyether sulfone modified attapulgite microsphere adsorbent;
step 4, sequentially carrying out iron-carbon micro-electrolysis and Fenton oxidation treatment on the wastewater obtained in the step 3, wherein the hydraulic retention time of the iron-carbon micro-electrolysis process is 30min, the pH value of the wastewater is 5 in the Fenton oxidation treatment process, and Fe2+The concentration is about 5g/L, the treatment temperature is 35 ℃, and the treatment time is 50 min;
step 5, filtering the wastewater obtained in the step 4 by using a nanofiltration membrane, wherein the molecular weight cut-off of the nanofiltration membrane is 400Da, the operating pressure in the nanofiltration process is 3.0Mpa, and the nanofiltration membrane concentrated solution is returned to the step 3 for treatment;
and 6, concentrating the nanofiltration membrane permeate through a reverse osmosis membrane, evaporating, concentrating and drying in sequence to obtain the industrial NaCl salt.
Example 3
Step 1, filtering the printing and dyeing wastewater by using a 200nm microfiltration membrane to remove the unremoved precipitated dye;
step 2, mixing the microfiltration filtrate with an extracting agent n-hexane according to a volume ratio of 0.8: 1, mixing and extracting, wherein the temperature in the extraction process is 25 ℃, and the extraction time is 30 min;
step 3, adsorbing the raffinate obtained in the step 2 by using a sulfonated polyether sulfone modified attapulgite microsphere adsorbent, wherein the hydraulic retention time in the adsorption process is 50min, and the adsorption temperature is 30 ℃; the preparation method of the adsorbent comprises the following steps: s1, soaking the attapulgite in 3mol/L hydrochloric acid for activation treatment for 90min, filtering, washing with deionized water, and roasting at 185 ℃ for 1.5h to obtain acid-activated attapulgite; s2, dispersing 4 parts of attapulgite after acid activation and 2 parts of hexadecyl trimethyl ammonium bromide in 100 parts of 45vol.% ethanol water solution, stirring for 12 hours at 30 ℃, filtering the product, and drying to obtain surface cation modified attapulgite; s3, preparing a dimethylformamide mixed solution containing 12wt% of sulfonated polyether sulfone and 15wt% of surface cation modified attapulgite, dispersing uniformly at a high speed, dropwise adding the mixed solution into deionized water, centrifugally separating the formed microspheres, and drying in vacuum to obtain the sulfonated polyether sulfone modified attapulgite microsphere adsorbent;
step 4, sequentially carrying out iron-carbon micro-electrolysis and Fenton oxidation treatment on the wastewater obtained in the step 3, wherein the hydraulic retention time of the iron-carbon micro-electrolysis process is 30min, the pH value of the wastewater is 3-5 in the Fenton oxidation treatment process, and Fe2+The concentration is about 3g/L, the treatment temperature is 30 ℃, and the treatment time is 40 min;
step 5, filtering the wastewater obtained in the step 4 by using a nanofiltration membrane, wherein the molecular weight cut-off of the nanofiltration membrane is 300Da, the operating pressure in the nanofiltration process is 2.0Mpa, and the nanofiltration membrane concentrated solution is returned to the step 3 for treatment;
and 6, concentrating the nanofiltration membrane permeate through a reverse osmosis membrane, evaporating, concentrating and drying in sequence to obtain the industrial NaCl salt.
Comparative example 1
The differences from example 3 are: the Fenton oxidation treatment is not adopted, but the ozone oxidation treatment is adopted.
Step 1, filtering the printing and dyeing wastewater by using a 200nm microfiltration membrane to remove the unremoved precipitated dye;
step 2, mixing the microfiltration filtrate with an extracting agent n-hexane according to a volume ratio of 0.8: 1, mixing and extracting, wherein the temperature in the extraction process is 25 ℃, and the extraction time is 30 min;
step 3, adsorbing the raffinate obtained in the step 2 by using a sulfonated polyether sulfone modified attapulgite microsphere adsorbent, wherein the hydraulic retention time in the adsorption process is 50min, and the adsorption temperature is 30 ℃; the preparation method of the adsorbent comprises the following steps: s1, soaking the attapulgite in 3mol/L hydrochloric acid for activation treatment for 90min, filtering, washing with deionized water, and roasting at 185 ℃ for 1.5h to obtain acid-activated attapulgite; s2, dispersing 4 parts of attapulgite after acid activation and 2 parts of hexadecyl trimethyl ammonium bromide in 100 parts of 45vol.% ethanol water solution, stirring for 12 hours at 30 ℃, filtering the product, and drying to obtain surface cation modified attapulgite; s3, preparing a dimethylformamide mixed solution containing 12wt% of sulfonated polyether sulfone and 15wt% of surface cation modified attapulgite, dispersing uniformly at a high speed, dropwise adding the mixed solution into deionized water, centrifugally separating the formed microspheres, and drying in vacuum to obtain the sulfonated polyether sulfone modified attapulgite microsphere adsorbent;
step 4, sequentially carrying out iron-carbon micro-electrolysis and ozone oxidation treatment on the wastewater obtained in the step 3, wherein the hydraulic retention time of the iron-carbon micro-electrolysis process is 30min, the ozone concentration is 500ppm, the ozone treatment time is 30min, and the ozone treatment temperature is 25 ℃;
step 5, filtering the wastewater obtained in the step 4 by using a nanofiltration membrane, wherein the molecular weight cut-off of the nanofiltration membrane is 300Da, the operating pressure in the nanofiltration process is 2.0Mpa, and the nanofiltration membrane concentrated solution is returned to the step 3 for treatment;
and 6, concentrating the nanofiltration membrane permeate through a reverse osmosis membrane, evaporating, concentrating and drying in sequence to obtain the industrial NaCl salt.
Comparative example 2
The differences from example 3 are: instead of the fenton oxidation treatment, a wet oxidation treatment is used.
Step 1, filtering the printing and dyeing wastewater by using a 200nm microfiltration membrane to remove the unremoved precipitated dye;
step 2, mixing the microfiltration filtrate with an extracting agent n-hexane according to a volume ratio of 0.8: 1, mixing and extracting, wherein the temperature in the extraction process is 25 ℃, and the extraction time is 30 min;
step 3, adsorbing the raffinate obtained in the step 2 by using a sulfonated polyether sulfone modified attapulgite microsphere adsorbent, wherein the hydraulic retention time in the adsorption process is 50min, and the adsorption temperature is 30 ℃; the preparation method of the adsorbent comprises the following steps: s1, soaking the attapulgite in 3mol/L hydrochloric acid for activation treatment for 90min, filtering, washing with deionized water, and roasting at 185 ℃ for 1.5h to obtain acid-activated attapulgite; s2, dispersing 4 parts of attapulgite after acid activation and 2 parts of hexadecyl trimethyl ammonium bromide in 100 parts of 45vol.% ethanol water solution, stirring for 12 hours at 30 ℃, filtering the product, and drying to obtain surface cation modified attapulgite; s3, preparing a dimethylformamide mixed solution containing 12wt% of sulfonated polyether sulfone and 15wt% of surface cation modified attapulgite, dispersing uniformly at a high speed, dropwise adding the mixed solution into deionized water, centrifugally separating the formed microspheres, and drying in vacuum to obtain the sulfonated polyether sulfone modified attapulgite microsphere adsorbent;
step 4, sequentially carrying out iron-carbon micro-electrolysis and wet oxidation treatment on the wastewater obtained in the step 3, wherein the hydraulic retention time in the iron-carbon micro-electrolysis process is 30min, the wet oxidation temperature is 165 ℃, the pressure is 2Mpa, and the oxygen addition amount is 3 g/L;
step 5, filtering the wastewater obtained in the step 4 by using a nanofiltration membrane, wherein the molecular weight cut-off of the nanofiltration membrane is 300Da, the operating pressure in the nanofiltration process is 2.0Mpa, and the nanofiltration membrane concentrated solution is returned to the step 3 for treatment;
and 6, concentrating the nanofiltration membrane permeate through a reverse osmosis membrane, evaporating, concentrating and drying in sequence to obtain the industrial NaCl salt.
Comparative example 3
The differences from example 3 are: the adsorption process adopts activated carbon adsorption.
Step 1, filtering the printing and dyeing wastewater by using a 200nm microfiltration membrane to remove the unremoved precipitated dye;
step 2, mixing the microfiltration filtrate with an extracting agent n-hexane according to a volume ratio of 0.8: 1, mixing and extracting, wherein the temperature in the extraction process is 25 ℃, and the extraction time is 30 min;
step 3, adopting activated carbon to adsorb the raffinate obtained in the step 2, wherein the hydraulic retention time in the adsorption process is 50min, and the adsorption temperature is 30 ℃;
step 4, sequentially carrying out iron-carbon micro-electrolysis and Fenton oxidation treatment on the wastewater obtained in the step 3,the hydraulic retention time of the iron-carbon micro-electrolysis process is 30min, the pH value in the Fenton oxidation treatment process is 3-5, and Fe2+The concentration is about 3g/L, the treatment temperature is 30 ℃, and the treatment time is 40 min;
step 5, filtering the wastewater obtained in the step 4 by using a nanofiltration membrane, wherein the molecular weight cut-off of the nanofiltration membrane is 300Da, the operating pressure in the nanofiltration process is 2.0Mpa, and the nanofiltration membrane concentrated solution is returned to the step 3 for treatment;
and 6, concentrating the nanofiltration membrane permeate through a reverse osmosis membrane, evaporating, concentrating and drying in sequence to obtain the industrial NaCl salt.
Comparative example 4
The differences from example 3 are: polyether sulfone is adopted to modify the attapulgite.
Step 1, filtering the printing and dyeing wastewater by using a 200nm microfiltration membrane to remove the unremoved precipitated dye;
step 2, mixing the microfiltration filtrate with an extracting agent n-hexane according to a volume ratio of 0.8: 1, mixing and extracting, wherein the temperature in the extraction process is 25 ℃, and the extraction time is 30 min;
step 3, adsorbing the raffinate obtained in the step 2 by using a polyether sulfone modified attapulgite microsphere adsorbent, wherein the hydraulic retention time in the adsorption process is 50min, and the adsorption temperature is 30 ℃; the preparation method of the adsorbent comprises the following steps: s1, soaking the attapulgite in 3mol/L hydrochloric acid for activation treatment for 90min, filtering, washing with deionized water, and roasting at 185 ℃ for 1.5h to obtain acid-activated attapulgite; s2, dispersing 4 parts of attapulgite after acid activation and 2 parts of hexadecyl trimethyl ammonium bromide in 100 parts of 45vol.% ethanol water solution, stirring for 12 hours at 30 ℃, filtering the product, and drying to obtain surface cation modified attapulgite; s3, preparing a dimethylformamide mixed solution containing 12wt% of polyether sulfone and 15wt% of surface cation modified attapulgite, dispersing uniformly at a high speed, dropwise adding the mixed solution into deionized water, centrifugally separating formed microspheres, and drying in vacuum to obtain the polyether sulfone modified attapulgite microsphere adsorbent;
step 4, sequentially adopting iron-carbon micro-electrolysis and Fenton to the wastewater obtained in the step 3Oxidation treatment, wherein the hydraulic retention time in the iron-carbon micro-electrolysis process is 30min, the pH value in the Fenton oxidation treatment process is 3-5, and Fe2+The concentration is about 3g/L, the treatment temperature is 30 ℃, and the treatment time is 40 min;
step 5, filtering the wastewater obtained in the step 4 by using a nanofiltration membrane, wherein the molecular weight cut-off of the nanofiltration membrane is 300Da, the operating pressure in the nanofiltration process is 2.0Mpa, and the nanofiltration membrane concentrated solution is returned to the step 3 for treatment;
and 6, concentrating the nanofiltration membrane permeate through a reverse osmosis membrane, evaporating, concentrating and drying in sequence to obtain the industrial NaCl salt.
Comparative example 5
The differences from example 3 are: the wastewater is not treated by iron-carbon micro-electrolysis.
Step 1, filtering the printing and dyeing wastewater by using a 200nm microfiltration membrane to remove the unremoved precipitated dye;
step 2, mixing the microfiltration filtrate with an extracting agent n-hexane according to a volume ratio of 0.8: 1, mixing and extracting, wherein the temperature in the extraction process is 25 ℃, and the extraction time is 30 min;
step 3, adsorbing the raffinate obtained in the step 2 by using a sulfonated polyether sulfone modified attapulgite microsphere adsorbent, wherein the hydraulic retention time in the adsorption process is 50min, and the adsorption temperature is 30 ℃; the preparation method of the adsorbent comprises the following steps: s1, soaking the attapulgite in 3mol/L hydrochloric acid for activation treatment for 90min, filtering, washing with deionized water, and roasting at 185 ℃ for 1.5h to obtain acid-activated attapulgite; s2, dispersing 4 parts of attapulgite after acid activation and 2 parts of hexadecyl trimethyl ammonium bromide in 45vol.% ethanol water solution, stirring for 12 hours at 30 ℃, filtering the product, and drying to obtain surface cation modified attapulgite; s3, preparing a dimethylformamide mixed solution containing 12wt% of sulfonated polyether sulfone and 15wt% of surface cation modified attapulgite, dispersing uniformly at a high speed, dropwise adding the mixed solution into deionized water, centrifugally separating the formed microspheres, and drying in vacuum to obtain the sulfonated polyether sulfone modified attapulgite microsphere adsorbent;
step 4, sequentially adopting the wastewater obtained in the step 3Performing Fenton oxidation treatment, wherein the pH is adjusted to 3-5 from 6.7 in the process of the Fenton oxidation treatment, and Fe2+The concentration is about 1.2g/L, the treatment temperature is 30 ℃, and the treatment time is 40 min;
step 5, filtering the wastewater obtained in the step 4 by using a nanofiltration membrane, wherein the molecular weight cut-off of the nanofiltration membrane is 300Da, the operating pressure in the nanofiltration process is 2.0Mpa, and the nanofiltration membrane concentrated solution is returned to the step 3 for treatment;
and 6, concentrating the nanofiltration membrane permeate through a reverse osmosis membrane, evaporating, concentrating and drying in sequence to obtain the industrial NaCl salt.
The wastewater treatment effects of the above examples and comparative examples are as follows:
Figure DEST_PATH_IMAGE003
in this table, the pH of the water produced after adsorption is used as a control, not the pH of the water produced after iron char treatment.
As can be seen from the above table, the mode of treating printing and dyeing wastewater of the invention can effectively remove sulfonate and acyl chloride in acyl chloride wastewater, and the comparison between the embodiment 3 and the comparative examples 1 and 2 shows that Fe ions can be effectively generated in wastewater by Fenton oxidation treatment, so that the permeability of NaCl in the nanofiltration process is improved, and the recovery amount of NaCl is increased; as can be seen from the examples 3 and the comparative examples 3, the selective adsorption of the activated carbon to the printing and dyeing wastewater to be treated by the invention is poor, so that the COD of the wastewater after adsorption is higher; as can be seen from example 3 and comparative example 4, the attapulgite modified by sulfonated polyethersulfone has higher selective adsorption to sulfonate compared with the adsorption microspheres which are not sulfonated; it can be seen from the examples 3 and the comparative examples 5 that, after the iron-carbon microelectrolysis treatment is adopted, the acyl chloride in the wastewater can be better hydrolyzed to generate hydrogen chloride, so that the pH value after the reaction is relatively low, the pH value range required by the subsequent Fenton reaction process is more suitable, and the Fe in the solution is caused by not adopting the iron-carbon microelectrolysis2+The concentration is not high, so that the permeability of NaCl cannot be better improved through the charge channel south effect in the subsequent nanofiltration process, and the NaCl is ensuredThe purity is low.

Claims (5)

1. An integrated treatment process of printing and dyeing wastewater is characterized by comprising the following steps:
step 1, filtering the printing and dyeing wastewater by using a microfiltration membrane to remove the precipitated dye which is not removed; the printing and dyeing wastewater is preferably generated by adopting 2, 4-diaminobenzene sulfonic acid as an active group, reacting with dibromopropionyl chloride, salting out and filtering;
step 2, mixing the microfiltration filtrate with an extracting agent for extraction;
step 3, carrying out adsorption impurity removal treatment on the raffinate obtained in the step 2;
step 4, sequentially carrying out iron-carbon micro-electrolysis and Fenton oxidation treatment on the wastewater obtained in the step 3;
step 5, filtering the wastewater obtained in the step 4 by using a nanofiltration membrane, and returning the nanofiltration membrane concentrated solution to the step 3 for treatment;
and 6, concentrating the nanofiltration membrane permeate obtained in the step 5 by a reverse osmosis membrane, evaporating, concentrating and drying to obtain industrial NaCl.
2. The integrated treatment process of printing and dyeing wastewater according to claim 1, characterized in that the average pore size of the microfiltration membrane in step 1 is preferably 50 to 500 nm.
3. The integrated treatment process for printing and dyeing wastewater according to claim 1, characterized in that the extractant in step 2 is n-hexane; the volume ratio of the filtrate to the extracting agent is preferably 0.5-1: 1; the temperature in the extraction process is preferably 20-30 ℃, and the extraction time is preferably 10-40 min.
4. The integrated treatment process of printing and dyeing wastewater according to claim 1, characterized in that in step 4, the pH value in Fenton oxidation treatment is preferably 3-5, and Fe2+The concentration is preferably about 0.5-5 g/L, the treatment temperature is preferably 25-35 ℃, and the treatment time is preferably 10-50 min。
5. The integrated treatment process of the printing and dyeing wastewater according to claim 1, characterized in that in the step 5, the molecular weight cut-off of the nanofiltration membrane is preferably 200-400 Da, and the operating pressure of the nanofiltration process is preferably 1.0-3.0 MPa.
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