CN110759545A - Treatment method of anthraquinone dye waste acid - Google Patents
Treatment method of anthraquinone dye waste acid Download PDFInfo
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- C02F9/00—Multistage treatment of water, waste water or sewage
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- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
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- C02F1/72—Treatment of water, waste water, or sewage by oxidation
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- C02F2101/00—Nature of the contaminant
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- C02F2101/308—Dyes; Colorants; Fluorescent agents
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/08—Chemical Oxygen Demand [COD]; Biological Oxygen Demand [BOD]
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- C02F2303/00—Specific treatment goals
- C02F2303/16—Regeneration of sorbents, filters
Abstract
The invention discloses a method for treating anthraquinone dye waste acid. The treatment method of the anthraquinone dye waste acid comprises the following steps: preparing resin balls, performing sulfonation modification, washing with ammonia water to neutrality, filling the resin balls into a resin column, performing adsorption and decoloration on anthraquinone dye waste acid after filtration and impurity removal through the adsorption column, adding potassium permanganate into the adsorption and decoloration waste acid, performing filtration and separation to obtain a colorless sulfuric acid solution, performing desorption treatment on the resin by using a desorbent, and reusing the desorbed resin in S2. According to the invention, by adopting the specific adsorption resin combined with the recovery process of adsorption treatment and deep oxidation treatment, the high-efficiency recovery treatment of the anthraquinone dye waste acid is realized, the recovery rate of sulfuric acid can be close to about 90%, the removal rate of COD content of the waste acid can reach more than 99%, and the method can be used for treating anthraquinone sulfate waste acid with COD content of 5000-200000 ppm.
Description
Technical Field
The invention relates to the technical field of waste acid treatment, and particularly relates to a treatment method of anthraquinone dye waste acid.
Background
Anthraquinone is an important chemical intermediate, and is widely used for industrial production of disperse dyes such as disperse blue 56, disperse blue 60, disperse red 60, disperse turquoise blue HBF and the like, reduced gray BG, acid dyes and the like. At present, the output of anthraquinone dye intermediates in China exceeds 6.3 million t/a, and dye waste acid discharged in the production process has great influence on the environment. The waste acid has high chroma, high organic matter content and high pH value, and the traditional physical and chemical method has unsatisfactory treatment effect. Meanwhile, the anthraquinone dye waste acid also contains sulfuric acid with higher content, if the chromaticity of the waste acid can be effectively removed and the COD is reduced to a lower level, the waste acid can be used for producing and preparing an aluminum sulfate water purifying agent product, the subsequent treatment cost of the waste acid is saved, and the resource recycling is realized. The prior anthraquinone dye wastewater treatment methods mainly comprise an advanced oxidation method, a complex extraction method, a liquid membrane extraction method, a resin adsorption method and the like. The advanced oxidation method can transform the structure of the compound, reduce the COD of the wastewater and improve the ratio of BOD/COD. The advanced oxidation method mainly comprises a Fenton reagent oxidation method, an ozone oxidation method and a wet oxidation method. However, the advanced oxidation method is only suitable for treating anthraquinone wastewater containing high-concentration nitrite, and has high operation cost no matter electrodialysis or concentration crystallization. The photocatalytic oxidation method has the disadvantages of poor treatment effect, TOC removal rate of 27-46% and low decolorization rate. The method can not well realize effective recovery treatment of the anthraquinone waste acid, on one hand, the recovery rate of sulfuric acid is not high, and on the other hand, the COD reduction effect of the anthraquinone waste acid is not ideal.
CN101318749A discloses a separation method of anthraquinone sulfonic acid in waste acid generated in the production process of anthraquinone and derivatives thereof, which comprises the steps of soaking adsorption resin in concentrated sulfuric acid and nitric acid, washing the soaked adsorption resin with distilled water to be neutral to prepare the adsorption resin, filling an adsorbent in an adsorption tower to adsorb anthraquinone sulfonic acid in the waste acid, desorbing and regenerating the adsorption resin adsorbed with anthraquinone sulfonic acid by using a desorption agent, and removing the desorption agent by using desorption liquid to obtain the anthraquinone sulfonic acid. But the concentration of the anthraquinone waste acid treated by the method is lower, and the COD reduction effect is still to be further improved.
Disclosure of Invention
The invention aims to solve the technical problems that the prior anthraquinone waste acid treatment technology is not suitable for recycling high-concentration anthraquinone sulfate waste acid and the COD reduction effect is not ideal, and provides a treatment method of anthraquinone dye waste acid.
The above purpose of the invention is realized by the following technical scheme:
a treatment method of anthraquinone dye waste acid comprises the following steps:
s1, preparing resin balls: preparing resin pellets by taking divinylbenzene, p-chlorostyrene and activated clay as raw materials, performing sulfonation modification, and washing with ammonia water to be neutral;
s2, waste acid adsorption treatment: filling the adsorption resin balls into a resin column, filtering and removing impurities, and then adsorbing and decoloring anthraquinone dye waste acid through the adsorption column, wherein the flow rate of the anthraquinone dye waste acid is 5-15 BV/h;
s3, deep oxidation treatment: adding potassium permanganate into the adsorption decoloration waste acid, stirring and reacting for 25-50 min at the temperature of 75-95 ℃, and filtering and separating to obtain a colorless sulfuric acid solution;
s4, desorption and recycling: and (4) desorbing the resin by using a desorbent, wherein the desorbed resin can be reused in S2.
The resin ball can be prepared by the following method:
taking divinylbenzene, p-chlorostyrene and activated clay in a weight ratio of 1:3:4, carrying out suspension polymerization reaction at a rotating speed of 4000-8000 r/min and a water bath temperature of 70-95 ℃ for 4-6 h. After the reaction is finished, evaporating and drying to obtain resin pellets.
The resin beads can be introduced with sulfonic acid groups on the surfaces thereof by sulfonation modification, so that the adsorption performance is improved.
The ammonia washing effect is as follows: on one hand, the ammonia water can perform neutralization with the sulfonated modified acid to wash the resin balls to be neutral, and on the other hand, the ammonia water can also provide amino groups to introduce ammonium groups on the surface of the resin, so that the adsorption performance is improved.
In the waste acid adsorption treatment process of S2, the flow rate of the anthraquinone dye waste acid is controlled at 5-15 BV/h, and the influence of the flow rate on the adsorption effect is as follows: the flow rate is too slow, and the treatment efficiency is low; the flow velocity is too fast, the contact time of waste acid and resin is short, and the adsorption effect of organic matters is reduced.
The invention adds deep oxidation treatment after the conventional adsorption treatment step because the COD of the waste acid is difficult to reduce to an ideal value by the conventional adsorption treatment and more adsorption resin is consumed by the single adsorption treatment
Influence of the temperature of the deep oxidation on the treatment effect: the temperature is too low, the reaction activity of the oxidant is low, and the oxidation effect is poor; the energy consumption cost is higher due to overhigh temperature, the reaction process is more violent, and the potential safety hazard is generated.
Too short deep oxidation time can cause insufficient oxidation and lower utilization rate of the oxidant; the time is too long, the oxidation process is completed, and time is wasted.
Preferably, the particle diameter of the resin pellets in S1 is 0.5-1.0 mm, and the specific surface area is 400-700 m2(ii) in terms of/g. For example, the resin pellet has a particle size of 0.5mm and a specific surface area of 650m2The grain diameter of the/g or resin pellet is 1.0mm, and the specific surface area is 400m2/g。
The smaller the particle size of the resin beads, the larger the specific surface area and the larger the reaction contact area, the better the adsorption effect, but the too small particle size can cause too small gaps among particles, which causes difficulty in liquid passing and influences the adsorption process. The inventors have unexpectedly found that the adsorption effect can be achieved within the particle size range of the present invention and the dynamic equilibrium of the adsorption process is not affected, achieving the optimum treatment effect.
Preferably, the resin pellets in S1 have a particle size of 0.5mm and a specific surface area of 650m2/g。
Preferably, the sulfonation modification in S1 is concentrated sulfuric acid sulfonation, the acidity of concentrated sulfuric acid is 70-90%, and the sulfonation time is 8-10 h.
The sulfuric acid concentration is too low, the oxidation effect is weak, and sulfonic acid groups are difficult to introduce; the sulfuric acid concentration is too high, the oxidability is too strong, and the molecular structure of the resin can be damaged. The sulfonation time is too short, and the introduction of sulfonic acid groups is too little; the resin molecular structure is destroyed by the sulfonation time.
More preferably, the sulfonation modification in S1 is concentrated sulfuric acid sulfonation, the acidity of concentrated sulfuric acid is 70%, and the sulfonation time is 8 h.
Preferably, the concentration of the ammonia water in S1 is 5-10%.
Preferably, the effective unit length-diameter ratio of the resin column in S2 is 10-30: 1. For example, the effective unit aspect ratio of the resin column may be 10:1, 20:1, or 30: 1. The length-diameter ratio is too small, the waste acid flows out too fast, and the waste acid is difficult to contact and react with resin fully; the length-diameter ratio is too large, the resistance of waste acid passing through resin is too large, and the process is difficult to realize.
Preferably, the flow rate of the anthraquinone dye waste acid in S2 is 5BV/h, and the effective unit length-diameter ratio of the resin column is 30: 1.
Preferably, S3 potassium permanganate, which is known only to be potassium permanganate, remains in the reaction solution if the oxidant is added in excess, and is purple red in color; if the addition amount is too small, the oxidation effect is limited, and the COD residual value in the reaction solution is too high. The adding amount is 3-5 times of the COD content in the waste acid. If purple-red potassium permanganate residues exist in the filtrate, the color of the potassium permanganate disappears after the reducing agent is added. The reducing agent can be one or more of sodium metabisulfite, sodium sulfite, sodium bisulfite and sodium thiosulfate.
Preferably, the desorbent in S4 is one or more of ethanol, methanol, and acetone.
Preferably, the acidity of the sulfuric acid of the anthraquinone dye waste acid is 10-60%, and the COD content is 5000-200000 ppm. In the invention, the acidity of the waste acid is determined by a sodium hydroxide standard solution titration method, and the COD is determined by a potassium dichromate national standard method.
Preferably, the sulfuric acid acidity of the anthraquinone dye waste acid is 40-60%, and the COD content is 150000-200000 ppm.
Compared with the prior art, the invention has the beneficial effects that:
(1) the invention discloses a treatment method of anthraquinone dye waste acid, which realizes high-efficiency recovery treatment of anthraquinone dye waste acid by adopting a recovery process combining specific adsorption resin with adsorption treatment and deep oxidation treatment, wherein the recovery rate of sulfuric acid can be close to about 90%, the removal rate of COD content of the waste acid can reach more than 99%, and the treatment method has the dual advantages of effectively recovering sulfuric acid and reducing COD content.
(2) The treatment method of the anthraquinone dye waste acid is suitable for the anthraquinone sulfate waste acid with different concentration ranges, can be used for treating the anthraquinone sulfate waste acid with the COD content of 5000-200000 ppm, especially the high-concentration anthraquinone sulfate waste acid with the COD content of 150000-200000 ppm, and can be widely applied to the treatment of the anthraquinone sulfate waste acid.
Detailed Description
The present invention will be further described with reference to specific embodiments, but the present invention is not limited to the examples in any way. The starting reagents employed in the examples of the present invention are, unless otherwise specified, those that are conventionally purchased.
The acidity of the waste acid is measured by a sodium hydroxide standard solution titration method, and the COD is measured by a potassium dichromate national standard method (GB 11914-89).
Example 1
A treatment method of anthraquinone dye waste acid comprises the following steps:
s1, preparing resin balls: taking divinylbenzene, p-chlorostyrene and activated clay in a weight ratio of 1:3:4, carrying out suspension polymerization reaction at a rotating speed of 5000r/min and a water bath temperature of 80 ℃ for 5h, evaporating and drying to obtain resin pellets, taking the synthesized resin pellets with a particle size of 0.5mm and a specific surface area of 650m2Sulfonating and modifying the resin balls per gram by using sulfuric acid with the concentration of 70% for 8 hours, and then neutralizing and washing the resin balls to be neutral by using 5% ammonia water;
s2, waste acid adsorption treatment: filling the adsorption resin balls into resin columns, filling and forming the adsorption columns with the length-diameter ratio of 10:1, and adsorbing and decoloring the anthraquinone dye waste acid after filtering and impurity removal through the adsorption columns, wherein the flow rate of the anthraquinone dye waste acid is 5 BV/h;
s3, deep oxidation treatment: adding potassium permanganate into the adsorption decoloration waste acid in an amount which is 17.4g/L3 times (the addition amount of the potassium permanganate is 3-5 times of the COD content in the effluent liquid after adsorption treatment), stirring and reacting for 50min under the condition of water bath at 75 ℃, and filtering to obtain colorless transparent liquid after the reaction is finished;
s4, desorption and recycling: and (3) desorbing the resin by using acetone serving as a desorbent, wherein the desorbed resin can be reused in S2.
Wherein, the acidity of the anthraquinone dye waste acid stock solution is 45 percent, and the COD content is 150000 ppm.
It was found that the COD content in the effluent of the adsorption treatment in S2 was 5800ppm, and the COD removal rate was 96.13%.
It was found that the acidity of sulfuric acid in the filtrate of S3 was 42%, the COD content was 230ppm, the recovery rate of sulfuric acid was 93.3%, and the removal rate of COD was 96.85%.
Example 2
A treatment method of anthraquinone dye waste acid comprises the following steps:
s1, preparing resin balls: taking divinylbenzene, p-chlorostyrene and activated clay in a weight ratio of 1:3:4, carrying out suspension polymerization reaction at a rotating speed of 5000r/min and a water bath temperature of 80 ℃ for 5h, evaporating and drying to obtain resin pellets, taking the synthesized resin pellets with a particle size of 0.5mm and a specific surface area of 650m2Sulfonating and modifying the resin balls per gram by using sulfuric acid with the concentration of 70% for 8 hours, and then neutralizing and washing the resin balls to be neutral by using 5% ammonia water;
s2, waste acid adsorption treatment: filling the adsorption resin balls into resin columns, filling and forming the adsorption columns with the length-diameter ratio of 30:1, and adsorbing and decoloring the anthraquinone dye waste acid after filtering and impurity removal through the adsorption columns, wherein the flow rate of the anthraquinone dye waste acid is 5 BV/h;
s3, deep oxidation treatment: adding potassium permanganate into the adsorption decoloration waste acid in an amount of 4.5g/L (3 times), stirring and reacting for 50min under the condition of water bath at 75 ℃, and filtering to obtain colorless transparent liquid after the reaction is finished;
s4, desorption and recycling: and (3) desorbing the resin by using acetone serving as a desorbent, wherein the desorbed resin can be reused in S2.
Wherein, the acidity of the anthraquinone dye waste acid stock solution is 45 percent, and the COD content is 150000 ppm.
It was found that the COD content in the effluent of the adsorption treatment in S2 was 1500ppm, and the COD removal rate was 99.00%.
It was found that the acidity of sulfuric acid in the filtrate of S3 was 42.8%, the COD content was 110ppm, the recovery rate of sulfuric acid was 95.1%, and the removal rate of COD was 99.93%.
Example 3
A treatment method of anthraquinone dye waste acid comprises the following steps:
s1, preparing resin balls: taking divinylbenzene, p-chlorostyrene and activated clay in a weight ratio of 1:3:4, carrying out suspension polymerization reaction at a rotating speed of 5000r/min and a water bath temperature of 80 ℃ for 5h, evaporating and drying to obtain resin pellets, taking the synthesized resin pellets with a particle size of 0.5mm and a specific surface area of 650m2Sulfonating and modifying the resin balls per gram by using sulfuric acid with the concentration of 70% for 8 hours, and then neutralizing and washing the resin balls to be neutral by using 5% ammonia water;
s2, waste acid adsorption treatment: filling the adsorption resin balls into resin columns, filling and forming the adsorption columns with the length-diameter ratio of 10:1, and adsorbing and decoloring the anthraquinone dye waste acid after filtering and impurity removal through the adsorption columns, wherein the flow rate of the anthraquinone dye waste acid is 5 BV/h;
s3, deep oxidation treatment: adding potassium permanganate into the adsorption and decoloration waste acid in an amount of 29.1g/L (5 times), stirring and reacting for 50min under the condition of water bath at 75 ℃, filtering to obtain mauve transparent liquid after the reaction is finished, and slowly adding a reducing agent sodium metabisulfite under the stirring condition until the solution becomes colorless;
s4, desorption and recycling: and (3) desorbing the resin by using acetone serving as a desorbent, wherein the desorbed resin can be reused in S2.
Wherein, the acidity of the anthraquinone dye waste acid stock solution is 45 percent, and the COD content is 150000 ppm.
It was found that the COD content in the effluent of the adsorption treatment in S2 was 5800ppm, and the COD removal rate was 96.13%.
It was found that the acidity of sulfuric acid in the filtrate of S3 was 40.1%, the COD content was 150ppm, the recovery rate of sulfuric acid was 89.1%, and the removal rate of COD was 99.99%.
Example 4
A treatment method of anthraquinone dye waste acid comprises the following steps:
s1, preparing resin balls: taking divinylbenzene, p-chlorostyrene and activated clay in a weight ratio of 1:3:4, carrying out suspension polymerization reaction at a rotating speed of 5000r/min and a water bath temperature of 80 ℃ for 5h, evaporating and drying to obtain resin pellets, taking the synthesized resin pellets with a particle size of 0.5mm and a specific surface area of 650m2Sulfonating and modifying the resin balls per gram by using sulfuric acid with the concentration of 70% for 8 hours, and then neutralizing and washing the resin balls to be neutral by using 5% ammonia water;
s2, waste acid adsorption treatment: filling the adsorption resin balls into resin columns, filling and forming the adsorption columns with the length-diameter ratio of 10:1, and adsorbing and decoloring the anthraquinone dye waste acid after filtering and impurity removal through the adsorption columns, wherein the flow rate of the anthraquinone dye waste acid is 15 BV/h;
s3, deep oxidation treatment: adding potassium permanganate into the adsorption decoloration waste acid in an amount of 85.2g/L (3 times), stirring and reacting for 50min under the condition of water bath at 75 ℃, and filtering to obtain colorless transparent liquid after the reaction is finished;
s4, desorption and recycling: and (3) desorbing the resin by using acetone serving as a desorbent, wherein the desorbed resin can be reused in S2.
Wherein, the acidity of the anthraquinone dye waste acid stock solution is 45 percent, and the COD content is 150000 ppm.
It was found that the COD content in the effluent of the adsorption treatment in S2 was 28400ppm, and the COD removal rate was 81%.
It was found that the acidity of sulfuric acid in the filtrate of S3 was 38.5%, the COD content was 180ppm, the recovery rate of sulfuric acid was 85.6%, and the removal rate of COD was 99.36%.
Example 5
A treatment method of anthraquinone dye waste acid comprises the following steps:
s1, preparing resin balls: taking divinylbenzene, p-chlorostyrene and activated clay in a weight ratio of 1:3:4, carrying out suspension polymerization reaction at a rotating speed of 5000r/min and a water bath temperature of 80 ℃ for 5h, evaporating and drying to obtain resin pellets, taking the synthesized particles with the particle size of 1.0mm and the specific surface area of 400m2Sulfonating and modifying the resin balls per gram by using sulfuric acid with the concentration of 70% for 8 hours, and then neutralizing and washing the resin balls to be neutral by using 5% ammonia water;
s2, waste acid adsorption treatment: filling the adsorption resin balls into resin columns, filling and forming the adsorption columns with the length-diameter ratio of 10:1, and adsorbing and decoloring the anthraquinone dye waste acid after filtering and impurity removal through the adsorption columns, wherein the flow rate of the anthraquinone dye waste acid is 10 BV/h;
s3, deep oxidation treatment: adding potassium permanganate into the adsorption decoloration waste acid in an amount of 49.5g/L (3 times), stirring and reacting for 20min under the condition of water bath at 95 ℃, and filtering to obtain colorless transparent liquid after the reaction is finished;
s4, desorption and recycling: and (3) desorbing the resin by using acetone serving as a desorbent, wherein the desorbed resin can be reused in S2.
Wherein, the acidity of the anthraquinone dye waste acid stock solution is 45 percent, and the COD content is 150000 ppm.
It was found that the COD content in the effluent of the adsorption treatment in S2 was 16500ppm, and the COD removal rate was 89%.
It was found that the acidity of sulfuric acid in the filtrate of S3 was 40.8%, the COD content was 143ppm, the recovery rate of sulfuric acid was 90.67%, and the removal rate of COD was 99.13%.
Example 6
A treatment method of anthraquinone dye waste acid comprises the following steps:
s1, preparing resin balls: taking divinylbenzene, p-chlorostyrene and activated clay in a weight ratio of 1:3:4, carrying out suspension polymerization reaction at a rotating speed of 5000r/min and a water bath temperature of 80 ℃ for 5h, evaporating and drying to obtain resin pellets, taking the synthesized particles with the particle size of 1.0mm and the specific surface area of 400m2Sulfonating and modifying the resin balls per gram by using sulfuric acid with the concentration of 70% for 8 hours, and then neutralizing and washing the resin balls to be neutral by using 5% ammonia water;
s2, waste acid adsorption treatment: filling the adsorption resin balls into resin columns, filling and forming the adsorption columns with the length-diameter ratio of 20:1, and adsorbing and decoloring the anthraquinone dye waste acid after filtering and impurity removal through the adsorption columns, wherein the flow rate of the anthraquinone dye waste acid is 10 BV/h;
s3, deep oxidation treatment: adding potassium permanganate into the adsorption decoloration waste acid in an amount of 2.82g/L (3 times), stirring and reacting for 20min under the condition of water bath at 95 ℃, and filtering to obtain colorless transparent liquid after the reaction is finished;
s4, desorption and recycling: and (3) desorbing the resin by using acetone serving as a desorbent, wherein the desorbed resin can be reused in S2.
Wherein, the acidity of the anthraquinone dye waste acid stock solution is 10 percent, and the COD content is 5000 ppm.
It was found that the COD content in the effluent of the adsorption treatment in S2 was 940ppm, and the COD removal rate was 81.2%.
It was found that the acidity of sulfuric acid in the filtrate of S3 was 9.2%, the COD content was 85ppm, the recovery rate of sulfuric acid was 92%, and the removal rate of COD was 90.9%.
Example 7
A treatment method of anthraquinone dye waste acid comprises the following steps:
s1, preparing resin balls: taking divinylbenzene, p-chlorostyrene and activated clay in a weight ratio of 1:3:4, carrying out suspension polymerization reaction at a rotating speed of 5000r/min and a water bath temperature of 80 ℃ for 5h, evaporating and drying to obtain resin pellets, taking the synthesized particles with the particle size of 1.0mm and the specific surface area of 400m2Sulfonating and modifying the resin balls per gram by using sulfuric acid with the concentration of 70% for 8 hours, and then neutralizing and washing the resin balls to be neutral by using 5% ammonia water;
s2, waste acid adsorption treatment: filling the adsorption resin balls into resin columns, filling and forming the adsorption columns with the length-diameter ratio of 10:1, and adsorbing and decoloring the anthraquinone dye waste acid after filtering and impurity removal through the adsorption columns, wherein the flow rate of the anthraquinone dye waste acid is 10 BV/h;
s3, deep oxidation treatment: adding potassium permanganate into the adsorption decoloration waste acid in an amount of 75.9g/L (3 times), stirring and reacting for 20min under the condition of water bath at 95 ℃, and filtering to obtain colorless transparent liquid after the reaction is finished;
s4, desorption and recycling: and (3) desorbing the resin by using acetone serving as a desorbent, wherein the desorbed resin can be reused in S2.
Wherein, the acidity of the anthraquinone dye waste acid stock solution is 60 percent, and the COD content is 200000 ppm.
It was found that the COD content in the effluent of the adsorption treatment in S2 was 25300ppm, and the COD removal rate was 87.35%.
It was found that the acidity of sulfuric acid in the filtrate of S3 was 51.5%, the COD content was 230ppm, the recovery rate of sulfuric acid was 85.8%, and the removal rate of COD was 99.1%.
Comparative example 1
A treatment method of anthraquinone dye waste acid comprises the following steps:
s1, preparing resin balls: taking divinylbenzene, p-chlorostyrene and activated clay in a weight ratio of 1:3:4, carrying out suspension polymerization reaction at a rotating speed of 5000r/min and a water bath temperature of 80 ℃ for 5h, evaporating and drying to obtain resin pellets, taking the synthesized resin pellets with a particle size of 0.5mm and a specific surface area of 650m2The resin ball is sulfonated and modified by sulfuric acid with the concentration of 70 percent for 8 hours, and then neutralized and washed by ammonia water with the concentration of 5 percent to be neutral；
S2, waste acid adsorption treatment: filling the adsorption resin balls into resin columns, filling and forming the adsorption columns with the length-diameter ratio of 10:1, and adsorbing and decoloring the anthraquinone dye waste acid after filtering and impurity removal through the adsorption columns, wherein the flow rate of the anthraquinone dye waste acid is 5 BV/h;
s3, desorption and recycling: and (3) desorbing the resin by using acetone serving as a desorbent, wherein the desorbed resin can be reused in S2.
Wherein, the acidity of the anthraquinone dye waste acid stock solution is 45 percent, and the COD content is 150000 ppm.
The COD content in the filtrate was measured to be 5800ppm, the COD removal rate was 96.13%, the acidity of the sulfuric acid in the filtrate was 44.7%, and the recovery rate of the sulfuric acid was 99.3%.
Comparative example 2
A treatment method of anthraquinone dye waste acid comprises the following steps:
s1, preparing resin balls: taking divinylbenzene, p-chlorostyrene and activated clay in a weight ratio of 1:3:4, carrying out suspension polymerization reaction at a rotating speed of 5000r/min and a water bath temperature of 80 ℃ for 5h, evaporating and drying to obtain resin pellets, taking the synthesized resin pellets with a particle size of 0.5mm and a specific surface area of 650m2Sulfonating and modifying the resin balls per gram by using sulfuric acid with the concentration of 70% for 8 hours, and then neutralizing and washing the resin balls to be neutral by using 5% ammonia water;
s2, waste acid adsorption treatment: filling the adsorption resin balls into resin columns, filling and forming the adsorption columns with the length-diameter ratio of 10:1, and adsorbing and decoloring the anthraquinone dye waste acid after filtering and impurity removal through the adsorption columns, wherein the flow rate of the anthraquinone dye waste acid is 20 BV/h;
s3, deep oxidation treatment: adding potassium permanganate into the adsorption and decoloration waste acid in an amount of 29.5g/L (0.5 time), stirring and reacting for 50min under the condition of water bath at 75 ℃, and filtering to obtain colorless transparent liquid after the reaction is finished;
s4, desorption and recycling: and (3) desorbing the resin by using acetone serving as a desorbent, wherein the desorbed resin can be reused in S2.
Wherein, the acidity of the anthraquinone dye waste acid stock solution is 45 percent, and the COD content is 150000 ppm.
It was found that the COD content in the effluent of the adsorption treatment in S2 was 59000ppm, and the COD removal rate was 60.6%.
It was found that the acidity of sulfuric acid in the filtrate of S3 was 43.1%, the COD content was 31000ppm, the recovery rate of sulfuric acid was 95.8%, and the removal rate of COD was 79.3%.
It should be understood that the above-described embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the claims of the present invention.
Claims (10)
1. A treatment method of anthraquinone dye waste acid is characterized by comprising the following steps:
s1, preparing resin balls: preparing resin pellets by taking divinylbenzene, p-chlorostyrene and activated clay as raw materials, performing sulfonation modification, and washing with ammonia water to be neutral;
s2, waste acid adsorption treatment: filling the adsorption resin balls into a resin column, filtering and removing impurities, and then adsorbing and decoloring anthraquinone dye waste acid through the adsorption column, wherein the flow rate of the anthraquinone dye waste acid is 5-15 BV/h;
s3, deep oxidation treatment: adding potassium permanganate into the adsorption decoloration waste acid, stirring and reacting for 25-50 min at the temperature of 75-95 ℃, and filtering and separating to obtain a colorless sulfuric acid solution;
s4, desorption and recycling: and (4) desorbing the resin by using a desorbent, wherein the desorbed resin can be reused in S2.
2. The method for treating the anthraquinone dye waste acid as claimed in claim 1, wherein the particle size of the resin beads in S1 is 0.5-1.0 mm, and the specific surface area is 400-700 m2/g。
3. The method for treating anthraquinone dye waste acid according to claim 1, wherein in S1, the sulfonation modification is concentrated sulfuric acid sulfonation, the acidity of concentrated sulfuric acid is 70-90%, and the sulfonation time is 8-10 h.
4. The method for treating the anthraquinone dye waste acid as claimed in claim 3, wherein the concentration of the ammonia water in S1 is 5-10%.
5. The method for treating the anthraquinone dye waste acid as claimed in claim 1, wherein the length-diameter ratio of effective units of the resin column in S2 is 10-30: 1.
6. The method for treating waste acid containing anthraquinone dye according to claim 5, wherein the flow rate of said waste acid containing anthraquinone dye in S2 is 5BV/h, and the effective unit length-diameter ratio of resin column is 30: 1.
7. The method for treating the anthraquinone dye waste acid as claimed in claim 1, wherein the addition amount of the S3 potassium permanganate is 3-5 times of the COD content in the waste acid.
8. The method for treating the waste acid generated by the anthraquinone dye in claim 1, wherein the desorbent in S4 is one or more of ethanol, methanol and acetone.
9. The method for treating the anthraquinone dye waste acid according to any one of claims 1 to 8, wherein the acidity of sulfuric acid of the anthraquinone dye waste acid is 10 to 60%, and the COD content is 5000 to 200000 ppm.
10. The method for treating the waste acid from the anthraquinone dye production according to claim 9, wherein the waste acid from the anthraquinone dye production has a sulfuric acid degree of 40 to 60% and a COD content of 150000 to 200000 ppm.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111392697A (en) * | 2020-03-18 | 2020-07-10 | 湖南吴赣药业有限公司 | Method for treating organic waste acid in synthesis of p-acetamido-benzenesulfonyl chloride |
| CN111574484A (en) * | 2020-06-10 | 2020-08-25 | 浙江博澳新材料股份有限公司 | Water-saving and environment-friendly anhydride preparation method |
| CN111825237A (en) * | 2020-05-29 | 2020-10-27 | 扬州日兴生物科技股份有限公司 | Environment-friendly production process of 1-aminoanthraquinone |
| CN114212947A (en) * | 2021-11-24 | 2022-03-22 | 杭州深瑞水务有限公司 | Process for recycling waste acid containing organic matters |
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Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6054058A (en) * | 1996-02-13 | 2000-04-25 | Kurita Water Industries, Ltd. | Method for treating water which contains nitrogen compounds |
| PL364737A1 (en) * | 2004-02-03 | 2005-08-08 | Andrzej Panuszewski | Method for water conditioning and device for water conditioning |
| US20110017098A1 (en) * | 2009-07-03 | 2011-01-27 | Board Of Regents, The University Of Texas System | Removal and recovery of dye waste from effluents using clay |
| CN102951753A (en) * | 2012-11-12 | 2013-03-06 | 天津滨环化学工程技术研究院有限公司 | Agent and method for reducing COD (chemical oxygen demand) of phenolic wastewater |
| CN104001485A (en) * | 2014-05-22 | 2014-08-27 | 宁波工程学院 | Modified macroporous resin adsorbent and processing method for removing iodine in salt water |
| CN104829505A (en) * | 2015-04-24 | 2015-08-12 | 黎明化工研究设计院有限责任公司 | Method for separating anthraquinone sulfonic acid from waste acid generated during production process of anthraquinone and derivatives thereof |
| CN106277509A (en) * | 2016-11-04 | 2017-01-04 | 金福兴 | A kind of processing method containing azo dye wastewater |
| CN106745459A (en) * | 2016-12-28 | 2017-05-31 | 天津凯英科技发展股份有限公司 | The adsorpting regenerating process of dyestuff in a kind of disperse dyestuff waste water |
| CN107176649A (en) * | 2017-06-02 | 2017-09-19 | 滨州学院 | A kind of method for carrying 2 naphthalene sulfonic acids in iron copper macroreticular resin separation waste water |
| CN108264600A (en) * | 2017-12-28 | 2018-07-10 | 中国神华能源股份有限公司 | A kind of high cross-linked cationic exchanger resin of alkalescent and its synthetic method |
| CN109437486A (en) * | 2018-12-14 | 2019-03-08 | 浙江闰土研究院有限公司 | A kind of resource utilization method of the disperse dyestuff waste water containing low-concentration sulfuric acid |
-
2019
- 2019-12-02 CN CN201911214149.9A patent/CN110759545A/en active Pending
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6054058A (en) * | 1996-02-13 | 2000-04-25 | Kurita Water Industries, Ltd. | Method for treating water which contains nitrogen compounds |
| PL364737A1 (en) * | 2004-02-03 | 2005-08-08 | Andrzej Panuszewski | Method for water conditioning and device for water conditioning |
| US20110017098A1 (en) * | 2009-07-03 | 2011-01-27 | Board Of Regents, The University Of Texas System | Removal and recovery of dye waste from effluents using clay |
| CN102951753A (en) * | 2012-11-12 | 2013-03-06 | 天津滨环化学工程技术研究院有限公司 | Agent and method for reducing COD (chemical oxygen demand) of phenolic wastewater |
| CN104001485A (en) * | 2014-05-22 | 2014-08-27 | 宁波工程学院 | Modified macroporous resin adsorbent and processing method for removing iodine in salt water |
| CN104829505A (en) * | 2015-04-24 | 2015-08-12 | 黎明化工研究设计院有限责任公司 | Method for separating anthraquinone sulfonic acid from waste acid generated during production process of anthraquinone and derivatives thereof |
| CN106277509A (en) * | 2016-11-04 | 2017-01-04 | 金福兴 | A kind of processing method containing azo dye wastewater |
| CN106745459A (en) * | 2016-12-28 | 2017-05-31 | 天津凯英科技发展股份有限公司 | The adsorpting regenerating process of dyestuff in a kind of disperse dyestuff waste water |
| CN107176649A (en) * | 2017-06-02 | 2017-09-19 | 滨州学院 | A kind of method for carrying 2 naphthalene sulfonic acids in iron copper macroreticular resin separation waste water |
| CN108264600A (en) * | 2017-12-28 | 2018-07-10 | 中国神华能源股份有限公司 | A kind of high cross-linked cationic exchanger resin of alkalescent and its synthetic method |
| CN109437486A (en) * | 2018-12-14 | 2019-03-08 | 浙江闰土研究院有限公司 | A kind of resource utilization method of the disperse dyestuff waste water containing low-concentration sulfuric acid |
Non-Patent Citations (3)
| Title |
|---|
| 何小荣等: "《药品GMP车间实训教程（上册）》", 30 June 2016, 中国医药科技出版社 * |
| 宋应华等: "《花生壳生物吸附剂的制备及其在含染料废水治理中的应用》", 31 March 2017, 重庆大学出版社 * |
| 王惠霞: "《无机及分析化学》", 31 January 2016, 重庆大学出版社 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111392697A (en) * | 2020-03-18 | 2020-07-10 | 湖南吴赣药业有限公司 | Method for treating organic waste acid in synthesis of p-acetamido-benzenesulfonyl chloride |
| CN111392697B (en) * | 2020-03-18 | 2021-10-26 | 湖南吴赣药业有限公司 | Method for treating organic waste acid in synthesis of p-acetamido-benzenesulfonyl chloride |
| CN111825237A (en) * | 2020-05-29 | 2020-10-27 | 扬州日兴生物科技股份有限公司 | Environment-friendly production process of 1-aminoanthraquinone |
| CN111574484A (en) * | 2020-06-10 | 2020-08-25 | 浙江博澳新材料股份有限公司 | Water-saving and environment-friendly anhydride preparation method |
| CN111574484B (en) * | 2020-06-10 | 2021-11-09 | 浙江博澳新材料股份有限公司 | Water-saving and environment-friendly anhydride preparation method |
| CN114212947A (en) * | 2021-11-24 | 2022-03-22 | 杭州深瑞水务有限公司 | Process for recycling waste acid containing organic matters |
| CN114804280A (en) * | 2022-05-26 | 2022-07-29 | 西安海润新材料有限公司 | Method for recovering acid, thioxanthone and derivatives thereof from waste acid |
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