CN113247983B - Coupling complexing extraction agent composition and method for treating triazone production wastewater - Google Patents
Coupling complexing extraction agent composition and method for treating triazone production wastewater Download PDFInfo
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract
The invention relates to a coupling complexing extraction agent composition and a method for treating triazone production wastewater. Comprising a first composition and a second composition; the first composition comprises a first complexing agent and a first diluent; the second composition comprises a second complexing agent and a second diluent; the first complexing agent comprises at least one of N503, dibutyl butyl phosphate, quaternary ammonium chloride salt and tertiary amine; the second complexing agent comprises at least one of naphthenic acid and 2-ethylhexyl phosphoric acid. Firstly, adjusting the pH value of the triazone production wastewater to 2-4, adding the first composition, reacting, and layering to obtain an upper first extraction phase and a lower first water phase. Adjusting the pH value of the first water phase to 6-8, adding a second composition, reacting, and layering to obtain an upper second extraction phase and a lower second water phase. The invention can extract and separate organic acid, organic base and toxic organic pollutants in the wastewater, the removal rate of COD is higher than that of the prior art, and the water after the extraction can be reused in the production process.
Description
Technical Field
The invention relates to the technical field of wastewater treatment, and particularly relates to a coupling complexing extractant composition and a method for treating triazone production wastewater.
Background
Triazinone, chemical name: diethylhexyl butamido triazone. The pymetrozine is a heterocyclic compound with potential biological activity, and the pymetrozine with insecticidal activity is a typical representation of triazinone compounds, and has the characteristics of high efficiency, low toxicity and environmental friendliness. Triazineone is an intermediate in the manufacture of the herbicide metribuzin product.
The triazinone is prepared by hydrolysis, catalytic oxidation, neutralization and cyclization, and specifically comprises the following components: adding certain water and caustic soda liquid into dichloro pinacolone to perform hydrolysis reaction to prepare an aqueous solution of 3, 3-dimethyl-2-sodium hydroxybutyrate, adding an oxidation catalyst into the aqueous solution, and performing oxidation reaction by using a sodium hypochlorite solution as an oxidant to prepare 3, 3-dimethyl-sodium butyrate-2-one; then 3, 3-dimethyl-butyric acid-2-ketone is prepared by neutralization with hydrochloric acid; and then carrying out cyclization reaction on 3, 3-dimethyl-butyric acid-2-ketone and thiocarbamomide in the presence of a catalyst, adjusting the pH value to be 2, heating for reaction, filtering and drying to obtain triazinone. A large amount of high-concentration organic wastewater is generated in the above production process. The wastewater has complex components, high concentration, high chromaticity and pungent odor. Most of organic substances in water are raw materials which are not completely reacted and byproducts produced by synthetic reaction, and the substances are difficult to be biochemically degraded and even belong to biological toxic substances. The production process has acid and alkali regulation and other neutralization steps to produce great amount of sodium chloride salt with salt content of about 15%. The characteristics of the waste water determine that the waste water can not be treated by traditional methods such as coagulating sedimentation, biochemistry and the like, so that the treatment difficulty is very high.
The prior art reports a plurality of treatment methods of triazone production wastewater, which mainly comprise means such as resin adsorption, reduced pressure distillation, complex extraction and the like, wherein the resin adsorption and reduced pressure distillation involve expensive equipment, and the time cost during large-scale treatment is too high, so that the treatment methods are not suitable for large-scale popularization. The cost performance of the complex extraction wastewater is high, however, the reported complex treatment process has too low removal rate of COD, and the application of the complex treatment process is limited.
The invention is therefore proposed.
Disclosure of Invention
The first purpose of the invention is to provide a coupling complexing extraction agent composition for treating triazone production wastewater, which can extract and separate toxic organic pollutants such as organic acids, organic bases and organic bases in the triazone production wastewater, the COD (chemical oxygen demand) of the wastewater after complexing extraction is low, the removal rate of the COD is higher than that of the prior art, and the water after complexing extraction can be reused in the production process.
The second purpose of the invention is to provide a method for treating the wastewater from the triazinone production, the method utilizes the principle of coupling complex extraction to extract and separate toxic organic pollutants of organic acid and organic alkali, thereby greatly reducing COD in the wastewater, and the treated wastewater can be evaporated for desalting, and the evaporated water is nontoxic and has good biodegradability; simultaneously, white byproduct salt sodium chloride is obtained, and the harmlessness and the resource of the salt are realized; after the treatment by the process, 60-70% of water in the total amount of the wastewater can be reused in the production process.
In order to achieve the above object, the present invention provides the following technical solutions.
A coupling complex extractant composition for treating triazone production wastewater comprises a first composition and a second composition;
the first composition comprises a first complexing agent and a first diluent; the second composition comprises a second complexing agent and a second diluent;
the first complexing agent comprises at least one of N503 (N, N-bis (1-methylheptyl) acetamide), dibutyl butyl phosphate, quaternary ammonium chloride salt and tertiary amine, and the first diluent is used for dissolving the first complexing agent;
the second complexing agent comprises at least one of naphthenic acid and 2-ethylhexyl phosphoric acid, and the second diluent is used for dissolving the second complexing agent.
The coupling complexing extractant composition provided by the invention mainly comprises a first composition and a second composition, wherein the two compositions are complexing agents reacting with different organic pollutants under different acid-base conditions. When the method is used for treating wastewater in triazone production, the pH value of the wastewater is adjusted to enable the wastewater to react with the first composition and the second composition step by step, both organic phase and water phase are extracted and separated, organic pollutants are separated and extracted in the organic phase, so that the wastewater is purified, COD is reduced, chromaticity is removed, and the treated wastewater is nearly colorless and odorless.
The organic matters separated by the coupling complex extractant composition comprise organic acid organic base toxic pollutants such as thiocarbohydrazide, dichloropinacolone, 3-dimethyl-2-hydroxybutyric acid, 3-dimethyl-sodium butyrate-2-one and 3, 3-dimethyl-butyric acid-2-one. Specifically, the first composition can separate organic substances such as 3, 3-dimethyl-2-hydroxybutyric acid, 3-dimethyl-sodium butyrate-2-one, and 3, 3-dimethyl-2-butanoic acid-one, and the second composition can separate organic substances such as thiocarbohydrazine and dichloropinacolone.
Compared with the prior art, the coupling complexing extraction agent composition provided by the invention has the advantages that more organic matters are removed, the removal rate is high, and the removal rate of COD (chemical oxygen demand) on the triazone production wastewater reaches more than 78%.
In some embodiments, the volume percent of the first complexing agent in the first composition is from 5% to 40%, preferably from 20% to 40%. The proper content of the complexing agent can improve the removal rate of organic matters on one hand and control the treatment cost in a lower range on the other hand. To this end, the volume percentage of the first complexing agent in the first composition may be 5%, 7%, 10%, 13%, 15%, 20%, 22%, 25%, 28%, 30%, 33%, 35%, 37%, 40%, etc.
In some embodiments, the volume percent of the second complexing agent in the second composition is from 10% to 50%, preferably from 36% to 50%. The concentration of the second complexing agent also considers the COD removal rate, the cost and other factors, and in order to achieve greater economic benefit, the volume percentage of the second complexing agent in the second composition can be 10%, 13%, 15%, 20%, 22%, 25%, 28%, 30%, 33%, 35%, 37%, 40%, 43%, 45%, 47%, 50% and the like.
In order to improve the solubility of the first complexing agent and the second complexing agent and promote the complex extraction reaction, the first diluent and the second diluent respectively and independently preferably comprise C8-C20 alkane; for example, the alkane may be a C8 alkane, a C9 alkane, a C10 alkane, a C11 alkane, a C12 alkane, a C13 alkane, a C14 alkane, a C15 alkane, a C16 alkane, a C17 alkane, a C18 alkane, a C19 alkane, a C20 alkane, and may be a straight-chain alkane or an isomer thereof, i.e., a branched alkane, in which the solubility of the complexing agent is a main consideration.
In some embodiments, the first diluent comprises a C10 alkane and a C18 alkane, or comprises a C8 alkane and a C16 alkane; the second diluent comprises a C10 alkane and a C18 alkane. These alkanes may be linear or branched alkanes.
In addition, the first diluent and the second diluent may be changed according to the change of the first complexing agent and the second complexing agent, for example, when the complexing agent is a single complexing agent, a single type of alkane is preferably used, and if the complexing agent is a mixed complexing agent, a mixed alkane is preferably used.
In some embodiments, the first complexing agent may be N503, dibutyl butyl phosphate, a quaternary ammonium chloride salt, or a tertiary amine.
In some embodiments, the first complexing agent may be a mixture of N503 and dibutyl butyl phosphate.
In some embodiments, the first complexing agent may be a mixture of N503 and a quaternary ammonium chloride salt.
In some embodiments, the first complexing agent may be a mixture of a tertiary amine and N503.
In some embodiments, the first complexing agent may be a mixture of dibutyl butyl phosphate and a quaternary ammonium chloride salt.
In some embodiments, the first complexing agent may be a mixture of dibutyl butyl phosphate and a tertiary amine.
In some embodiments, the first complexing agent may be a mixture of N503, dibutyl butyl phosphate and a quaternary ammonium chloride salt.
In some embodiments, the first complexing agent may be N503, dibutyl butyl phosphate, a mixture of quaternary ammonium chloride salts and tertiary amines.
In some embodiments, the first composition further comprises a co-solvent, wherein the co-solvent comprises isomeric alcohols having a carbon number of from 8 to 18, such as isodecanol and its isomeric alcohols, isononyl alcohol and its isomeric alcohols, octanol, undecanol, dodecanol, tridecanol, and the like. The cosolvent is helpful for the uniform dispersion of the complexing agent, and not only improves the utilization rate of the complexing agent, but also improves the reaction rate.
In some embodiments, the co-solvent in the first composition is 3% to 20% by volume, for example, 3%, 5%, 7%, 10%, 13%, 15%, 20%, etc.
As described above, when the coupling complex extractant composition of the present invention is used to treat triazone production wastewater, the first composition and the second composition need to be added into the wastewater step by step, theoretically, the order of adding the two is not limited, but considering that the triazone production wastewater is acidic, in order to reduce the treatment cost and save time, the first composition is preferably added for reaction, and then the second composition is added for reaction, and the preferred treatment method comprises the following steps:
firstly, adjusting the pH value of the triazone production wastewater to 2-4, adding the first composition, wherein the volume ratio of the first composition to the triazone production wastewater is preferably 1: and 5-15, mixing, reacting, and standing for layering to obtain an upper first extract phase and a lower first water phase.
Adjusting the pH value of the first water phase to 6-8, adding the second composition, wherein the volume ratio of the second composition to the triazinone production wastewater is preferably 1: and 5-15, carrying out mixing reaction, and standing for layering to obtain an upper second extract phase and a lower second water phase, wherein the lower second water phase is the treated wastewater.
In the process, the first complexing agent is firstly reacted with organic matters in the wastewater, such as 3, 3-dimethyl-2-hydroxybutyric acid, 3-dimethyl-sodium butyrate-2-ketone, 3-dimethyl-butyric acid-2-ketone and the like, under an acidic condition to generate an organic phase, so that oil-water separation is carried out, extraction is carried out, and the extracted first water phase is continuously subjected to the next treatment. The second complexing agent reacts with organic matters such as thiocarbohydrazide and dichloropinacolone in the first water phase under the alkaline condition to generate an organic phase, so that oil-water separation is carried out, extraction is carried out, the extracted second water phase is the treated wastewater, the COD value in the wastewater is very low, and the removal rate is far higher than that of the conventional treatment method. Of course, the second step extraction waste water (i.e. the second aqueous phase) can also be continued to other conventional typical treatments including but not limited to biochemical reactions, evaporative desalination, etc., and the water after these fine treatments can be recovered for further use in the triazineone production.
The method only involves complex reaction, and can be carried out in a normal environment without high temperature, high pressure and complex equipment, so that the investment cost is low, and the burden of enterprises can be reduced.
In addition, the amounts of the first and second compositions are primarily related to their concentrations, and are preferably arbitrarily adjusted within the ranges provided above. To increase the reaction rate, a variety of mass transfer means may be employed including, but not limited to, stirring, sonication, vibration, and the like.
As noted above, in some embodiments, the second aqueous phase is subjected to an evaporative concentration process to obtain sodium chloride salt and distilled water; optionally, part of the distilled water is recycled for treating the wastewater in the triazone production, and the rest distilled water is subjected to biochemical treatment. Because the amount of the treated wastewater is still large, 60-70% of the amount of the treated wastewater can be reused for production.
In some embodiments, sodium hydroxide solution or ammonia water solution is further added into the first extraction phase for reaction, and then the first extraction phase is placed still for layering, wherein the upper layer contains the regenerated first complexing agent, and the lower layer is a salt solution containing organic matters. The scheme realizes the regeneration of the first complexing agent, and meanwhile, the obtained salt solution containing the organic matters can also be subjected to extraction processes (including but not limited to acid precipitation, resin adsorption, distillation and the like) to obtain certain raw materials or products, and the raw materials or products can be recycled after refining.
In some embodiments, the concentration of the sodium hydroxide solution or the aqueous ammonia solution is 10% to 32% (weight percentage) when the first complexing agent is regenerated, and the volume ratio of the added amount of the sodium hydroxide solution or the aqueous ammonia solution to the first extraction phase is 1: 4 to 12.
In some embodiments, an acid solution is further added to the second extraction phase for reaction, and then the mixture is placed still for layering, wherein the upper layer contains the regenerated second complexing agent, and the lower layer is a salt solution containing organic matters. The scheme realizes the regeneration of the second complexing agent, and the obtained salt solution containing the organic matters can also be subjected to extraction processes (including but not limited to acid precipitation, resin adsorption, distillation and the like) to obtain certain raw materials or products, and can be recycled after being refined.
In some embodiments, the concentration of the acid solution is 10% to 20% (weight percentage) when the second complexing agent is regenerated, and the volume ratio of the acid solution to the second extraction phase is 1: 5 to 15.
In summary, compared with the prior art, the invention achieves the following technical effects:
the coupling complex extraction method is adopted to extract and separate toxic organic pollutants of organic acids, organic bases, such as thiocarbohydrazide, dichloropinacolone, 3-dimethyl-2-hydroxybutyric acid, 3-dimethyl-sodium butyrate-2-ketone, 3-dimethyl-butyric acid-2-ketone and the like in the wastewater, and the extracted wastewater has low COD, no color and no pungent smell; the subsequent evaporation desalting treatment is carried out, and the evaporated water is nontoxic and has good biodegradability; simultaneously, white byproduct salt sodium chloride is obtained, and the harmlessness and the resource of the salt are realized; after the treatment by the process, 60-70% of water in the total amount of the wastewater can be reused in the production process. Meanwhile, the treatment process is simple, the COD removal rate is high, the treatment cost is low, and the method has a wide application prospect.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The raw materials, reagents or instruments used are not indicated by manufacturers, and all the raw materials, the reagents or the instruments are conventional products which can be obtained by commercial purchase or can be prepared according to the prior art.
Example 1
The wastewater used in this example was obtained from the waste water from the triazone production in a chemical plant of Jiangsu, and the water quality was as shown in Table 1 below.
TABLE 1 Water quality table of waste water from triazinone production
| Name of waste water | pH | Appearance of the product | COD (mg/L) | Salt content (wt%) | Chloride ion (mg/L) | Smell(s) | Principal compound |
| Triazone wastewater | 1.5 | Yellow malodor | 20000 | 16% | 98010 | Irritation property | Thiocarbazone, dichloropinacolone, other organic carboxylic acids Compounds of the class |
Firstly, respectively taking 50mL of dibutyl butyl phosphate, 300mL of N503, 150mL of isodecyl alcohol and 600mL of mixed alkane with 10 and 18 carbon atoms (volume ratio of 1: 1), uniformly mixing, and completely preparing a complex extracting agent I. Then measuring 2000mL of the above triazinone production wastewater, starting stirring, adjusting the pH value to 4, adding 400mL of complexing extractant to the wastewater, carrying out liquid-liquid mass transfer for 20-25 minutes, and standing for layering. The upper layer is an extraction phase I and is subjected to regeneration treatment; the lower layer is extracted waste water.
Then 150mL of naphthenic acid and 600mL of mixed alkane (1: 1) with 10 and 18 carbon atoms are respectively taken and mixed evenly, the whole is transparent and uniform, and the preparation of the complexing extractant is finished. Then measuring 2000mL of the extracted water, starting stirring, adjusting the pH value to 8, adding 200mL of complexing extraction agent II into the wastewater, transferring liquid-liquid mass for 20-25 minutes, and standing for layering. The upper layer is an extraction phase II, and regeneration treatment is carried out; the lower layer is extracted waste water, detection and analysis show that the effluent is nearly colorless, and the COD: 4308 mg/L, the removal rate is 78%, and the chroma removal rate is 95%. And (3) evaporating effluent to remove salt to obtain white byproduct salt sodium chloride, recycling 60-70% of the evaporated water for the production of triazone, and performing biochemical treatment on the rest.
Adding 50mL of 20 wt% sodium hydroxide solution into the extraction phase I, starting stirring, reacting for 20 minutes, standing and layering for 1 hour, wherein the upper layer is regenerated complexing extractant I which is reused for next complexing extraction and is circulated, and the lower layer is organic matter-containing sodium salt solution.
Adding 30mL of 12 wt% hydrochloric acid solution into the extraction phase II, starting stirring, reacting for 20 minutes, standing and layering for 1 hour, wherein the upper layer is regenerated complexing extraction agent II, the upper layer is reused for next complexing extraction, and the lower layer is organic matter-containing salt solution in a circulating reciprocating manner.
Example 2
The wastewater used in this example was the same as in example 1, and the following was carried out:
firstly, 80mL of dibutyl butyl phosphate, 50g of quaternary ammonium chloride salt, 100mL of isononyl alcohol and 650m of mixed alkane with 8 and 16 carbon atoms (volume ratio of 1: 1) are respectively taken and uniformly mixed, the whole is transparent and uniform, and the complexing extraction agent I is prepared. Then measuring 2000mL of the above-mentioned triazone production wastewater, starting stirring, regulating pH to 3, adding 400mL of complexing extraction agent to the wastewater, transferring mass of liquid and liquid for 35-40 min, standing and demixing. The upper layer is an extraction phase I and is subjected to regeneration treatment; the lower layer is extracted waste water.
Then respectively taking 350mL of 2-ethylhexyl phosphoric acid and 700mL of mixed alkane with 10 and 18 carbon atoms (the volume ratio is 1: 1), uniformly mixing, and finishing the preparation of the complexing extraction agent. Then measuring 2000mL of the extracted water, starting stirring, adjusting the pH value to 8, adding 200mL of complexing extraction agent II into the wastewater, transferring liquid-liquid mass for 30-40 minutes, and standing for layering. The upper layer is an extraction phase II, and regeneration treatment is carried out; the lower layer is extracted waste water, detection and analysis show that the effluent is nearly colorless, and the COD: 3396 mg/L, removal rate of 83 percent and chroma removal rate of 95 percent. And (3) evaporating and desalting the effluent to obtain a white byproduct salt sodium chloride, recycling 60-70% of the evaporated water for the triazinone production, and performing biochemical treatment on the rest.
Adding 60mL of 18 wt% sodium hydroxide solution into the extraction phase I, starting stirring, reacting for 20 minutes, standing and layering for 1 hour, wherein the upper layer is regenerated complexing extractant I which is reused for next complexing extraction and is circulated, and the lower layer is organic matter-containing sodium salt solution.
Adding 25mL of 15 wt% hydrochloric acid solution into the extraction phase II, starting stirring, reacting for 20 minutes, standing and layering for 1 hour, wherein the upper layer is regenerated complexing extraction agent II, the upper layer is reused for next complexing extraction, and the lower layer is organic matter-containing salt solution in a circulating reciprocating manner.
Example 3
The wastewater used in this example was the wastewater from the production of triazone from a chemical plant in Hebei, and the water quality was as shown in Table 2 below.
TABLE 2 Water quality table of waste water from triazinone production
| Name of waste water | Water amount t/d | pH | Appearance of the product | COD (mg/L) | Salt content (%) | Chloride ion (mg/L) | Smell(s) |
| Triazone wastewater | 200 | 1.5 | Yellow malodor | 18000 | 15% | 10250 | Irritation property |
Firstly, 350mL of tertiary amine, 100mL of isodecyl alcohol and 650mL of mixed alkane with 10 and 18 carbon atoms (the volume ratio is 1: 1) are respectively taken and uniformly mixed, the whole is transparent and uniform, and the preparation of the complexing extractant I is finished. Then measuring 2000mL of the above-mentioned triazone production wastewater, starting stirring, regulating pH to 2, adding 400mL of complexing extraction agent to the wastewater, transferring mass of liquid and liquid for 20-25 min, standing and demixing. The upper layer is an extraction phase I and is subjected to regeneration treatment; the lower layer is extracted waste water.
Then 50mL of naphthenic acid, 350mL of 2-ethylhexyl phosphoric acid and 600mL of mixed alkane with 10 and 18 carbon atoms (volume ratio of 1: 1) are respectively taken and mixed uniformly, the whole is transparent and uniform, and the preparation of the complexing extractant is finished. Then measuring 2000mL of the extracted water, starting stirring, adjusting the pH value to 6, adding 200mL of complexing extractant II into the wastewater, transferring liquid-liquid mass for 20-25 minutes, and standing for layering. The upper layer is an extraction phase II, and regeneration treatment is carried out; the lower layer is extracted waste water, detection and analysis show that the effluent is nearly colorless, and the COD: 3256 mg/L, removal rate of 82% and chroma removal rate of 95%. And (3) evaporating and desalting the effluent to obtain a white byproduct salt sodium chloride, recycling 60-70% of the evaporated water for the triazinone production, and performing biochemical treatment on the rest.
Adding 50mL of 20 wt% sodium hydroxide solution into the extraction phase I, starting stirring, reacting for 20 minutes, standing and layering for 1 hour, wherein the upper layer is regenerated complexing extractant I which is reused for next complexing extraction and is circulated, and the lower layer is organic matter-containing sodium salt solution.
Adding 30mL of 12 wt% hydrochloric acid solution into the extraction phase II, starting stirring, reacting for 20 minutes, standing and layering for 1 hour, wherein the upper layer is regenerated complexing extraction agent II, the upper layer is reused for next complexing extraction, and the lower layer is organic matter-containing salt solution in a circulating reciprocating manner.
Example 4
The wastewater used in this example was the same as in example 3, and the following was carried out:
firstly, 200mL of tertiary amine, 200mL of N503, 40 mL of isononyl alcohol and 600mL of mixed alkane with 10 and 18 carbon atoms (volume ratio of 1: 1) are respectively taken and uniformly mixed, the whole is transparent and uniform, and the complexing extractant I is completely prepared. Then measuring 2000mL of the above triazinone production wastewater, starting stirring, adjusting the pH to 2, adding 400mL of complexing extraction agent into the wastewater, carrying out liquid-liquid mass transfer for 20-25 minutes, and standing for layering. The upper layer is an extraction phase I and is subjected to regeneration treatment; the lower layer is extracted waste water.
Then 100mL of naphthenic acid, 350mL of 2-ethylhexyl phosphoric acid and 700mL of mixed alkane with 10 and 18 carbon atoms (volume ratio of 1: 1) are respectively taken and mixed uniformly, the whole is transparent and uniform, and the preparation of the complexing extractant is finished. Then measuring 2000mL of the extracted water, starting stirring, adjusting the pH value to 6, adding 200mL of complexing extraction agent into the wastewater, carrying out liquid-liquid mass transfer for 20-25 minutes, and standing for layering. The upper layer is an extraction phase II, and regeneration treatment is carried out; the lower layer is extracted waste water, and the effluent is nearly colorless after detection and analysis. COD: 3012 mg/L, removal rate 83%, and chroma removal rate 95%. And (3) evaporating and desalting the effluent to obtain a white byproduct salt sodium chloride, recycling 60-70% of the evaporated water for the triazinone production, and performing biochemical treatment on the rest.
Example 5
The wastewater used in this example was the wastewater from the triazone production in a chemical plant of Heilongjiang, and the water quality was as shown in Table 3 below.
TABLE 3 Water quality table of waste water from triazinone production
| Name of waste water | pH | Appearance of the product | COD (mg/L) | Salt content (%) | Chloride ion (mg/L) | Smell(s) |
| Triazone wastewater | 1.5 | Yellow colour | 19000 | 16% | 80877 | Malodor |
Firstly, respectively taking 50mL of tertiary amine, 150mL of N503, 80mL of isodecyl alcohol and 600mL of mixed alkane with 10 and 18 carbon atoms (the volume ratio is 1: 1), uniformly mixing, and completely preparing a complex extracting agent I. Then measuring 2000mL of the above-mentioned triazone production wastewater, starting stirring, regulating pH to 2, adding 400mL of complexing extraction agent to the wastewater, transferring mass of liquid and liquid for 20-25 min, standing and demixing. The upper layer is an extraction phase I and is subjected to regeneration treatment; the lower layer is extracted waste water.
Then 100mL of naphthenic acid, 300mL of 2-ethylhexyl phosphoric acid and 700mL of mixed alkane with 10 and 18 carbon atoms (volume ratio of 1: 1) are respectively taken and evenly mixed, the whole is transparent and uniform, and the complexing extractant is prepared. Then measuring 2000mL of the extracted water, starting stirring, adjusting the pH value to 6, adding 200mL of complexing extractant II into the wastewater, transferring liquid-liquid mass for 20-25 minutes, and standing for layering. The upper layer is an extraction phase II, and regeneration treatment is carried out; the lower layer is extracted waste water, and the effluent is nearly colorless after detection and analysis. COD: 3774 mg/L, removal rate of 80% and chroma removal rate of 95%. And (3) evaporating and desalting the effluent to obtain a white byproduct salt sodium chloride, recycling 60-70% of the evaporated water for the triazinone production, and performing biochemical treatment on the rest.
Comparative example
The wastewater used in the comparative example was the wastewater from the triazone production in a chemical plant of Jiangsu, and the water quality was as shown in Table 4 below.
TABLE 4 Water quality table of waste water from triazinone production
| Name of waste water | pH | Appearance of the product | COD (mg/L) | Salt content (wt%) | Chloride ion (mg/L) | Smell(s) | Principal compound |
| Triazone wastewater | 1.5 | Yellow malodor | 20000 | 16% | 98010 | Irritation property | Thiocarbazone, dichloropinacolone, other organic compounds Carboxylic acid compound |
The comparison example adopts MIBK (methyl isobutyl ketone) to carry out physical extraction, and utilizes the principle of similarity and intermiscibility to extract and separate toxic organic pollutants in wastewater. Measuring 2000mL of the above triazinone production wastewater, starting stirring, adjusting the pH value to 2, adding 400mL of MIBK extractant into the wastewater, carrying out liquid-liquid mass transfer for 20-25 minutes, and standing for layering. The upper layer is an extraction phase, and the lower layer is extracted wastewater. And detecting and analyzing, wherein the effluent is yellow and has pungent smell, and then rectifying to recover residual MIBK. Effluent COD: 9092 mg/L, removal rate of 55 percent and chroma removal rate of 42 percent. The effluent is evaporated to obtain yellow sodium chloride salt which contains tar and has pungent smell, and the evaporated water cannot be recycled and has no biodegradability.
In the above treatment process, since MIBK has a high water solubility, a large amount of MIBK is dissolved in the wastewater, and conversely, COD in the wastewater is increased. The physical extraction method has relatively poor effect, high COD of treated water and strong smell. And the subsequent treatment needs to additionally increase the rectifying process of a rectifying tower to recover the MIBK medicament, so the process is complex and the energy consumption is high.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the appended claims.
Claims (12)
1. A method for treating triazone production wastewater by using a coupling complexing extraction agent composition is characterized in that the coupling complexing extraction agent composition comprises a first composition and a second composition; the first composition comprises a first complexing agent and a first diluent; the second composition comprises a second complexing agent and a second diluent; the first complexing agent comprises at least one of N503, dibutyl butyl phosphate, quaternary ammonium chloride salt and tertiary amine, and the first diluent is used for dissolving the first complexing agent; the second complexing agent comprises at least one of naphthenic acid and 2-ethylhexyl phosphoric acid, and the second diluent is used for dissolving the second complexing agent;
the method comprises the following steps:
adjusting the pH value of the triazone production wastewater to 2-4, adding the first composition, mixing, reacting, standing and layering to obtain an upper first extraction phase and a lower first water phase;
and adjusting the pH value of the first water phase to 6-8, adding the second composition, mixing, reacting, standing and layering to obtain an upper second extract phase and a lower second water phase, wherein the lower second water phase is the treated wastewater.
2. The method of claim 1, wherein the volume ratio of the first composition to the triazinone production wastewater is 1: 5-15, wherein the volume ratio of the second composition to the triazinone production wastewater is 1: 5 to 15.
3. The process according to claim 1, characterized in that the second aqueous phase is subjected to an evaporative concentration treatment obtaining sodium chloride salts and distilled water; optionally, part of the distilled water is recycled for treating the wastewater in the triazone production, and the rest distilled water is subjected to biochemical treatment.
4. The method of claim 1, wherein the first extract phase is further added with sodium hydroxide solution or ammonia water solution for reaction, and then is placed still for layering, wherein the upper layer comprises the regenerated first complexing agent, and the lower layer is a salt solution containing organic matters.
5. The method of claim 4, wherein the concentration of the sodium hydroxide solution or the aqueous ammonia solution is 10% to 32% by weight; the volume ratio of the added volume of the sodium hydroxide solution or the ammonia water solution to the first extraction phase is 1: 4 to 12.
6. The method according to claim 1, wherein an acid solution is further added to the second extraction phase for reaction, and then the second extraction phase is allowed to stand for layering, wherein the upper layer contains the regenerated second complexing agent, and the lower layer is a salt solution containing organic matters.
7. The method of claim 6, wherein the acid solution has a concentration of 10% to 20% by weight; wherein the volume ratio of the added volume of the acid solution to the second extract phase is 1: 5 to 15.
8. The method of claim 1, wherein the first complexing agent is present in the first composition in a volume percent of from 5% to 40%;
the volume percentage of the second complexing agent in the second composition is 10-50%.
9. The method of claim 8, wherein the first complexing agent is present in the first composition in an amount of 20% to 40% by volume and the second complexing agent is present in the second composition in an amount of 36% to 50% by volume.
10. The method of claim 1 or 8, wherein the first diluent and the second diluent each independently comprise a C8-C20 alkane.
11. The method of claim 1 or 8, wherein the first diluent comprises a C10 alkane and a C18 alkane, or comprises a C8 alkane and a C16 alkane; the second diluent comprises a C10 alkane and a C18 alkane.
12. The method of claim 1 or 8, wherein the first composition further comprises a co-solvent comprising an isomeric alcohol having from C8 to C18; the volume percentage of the cosolvent in the first composition is 3-20%.
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