CN115626746A

CN115626746A - Treatment method of comprehensive high-concentration wastewater in fine chemical industry park

Info

Publication number: CN115626746A
Application number: CN202211436749.1A
Authority: CN
Inventors: 史政伟; 程迪; 闫巍; 许传东; 李闰吉; 刘帅; 杨峻; 李明
Original assignee: Shenyang Huiyu Chemical Environmental Protection Technology Co ltd; Beijing Huiyu Lebang Environmental Protection Technology Co ltd
Current assignee: Shenyang Huiyu Chemical Environmental Protection Technology Co ltd; Beijing Huiyu Lebang Environmental Protection Technology Co ltd
Priority date: 2022-11-16
Filing date: 2022-11-16
Publication date: 2023-01-20

Abstract

The invention relates to a treatment method of comprehensive high-concentration wastewater of a fine chemical industry park, which can effectively reduce COD of the comprehensive high-concentration wastewater of the fine chemical industry park and effectively remove toxic and harmful pollutants such as ammonia nitrogen, total nitrogen, chromaticity, aniline, phenol and the like in the wastewater, and the distilled water is nontoxic and has good biodegradability after the wastewater is evaporated and desalted; meanwhile, white by-product salt sodium chloride or sodium sulfate can be obtained, and harmless and recycling of the salt is realized. The water quality of the wastewater treated by the combined process can reach the connection standard of sewage plants in fine chemical industry parks.

Description

Treatment method of comprehensive high-concentration wastewater in fine chemical industry park

Technical Field

The invention relates to the field of fine chemical wastewater treatment, in particular to a method for treating comprehensive high-concentration wastewater in a fine chemical park.

Background

Fine chemistry is one of the most active emerging fields in the chemical industry today and is an important component of new materials. The fine chemical products have various types, high added value, wide application and large industrial relevance. The fine chemical industry comprises more than 40 industries and departments such as medicines, pesticides, synthetic dyes, organic pigments, coatings, spices and essences, cosmetics and toilet sanitary products, soaps and synthetic detergents, surfactants, printing ink and auxiliaries thereof, adhesives, photosensitive materials, magnetic materials, catalysts, reagents, water treatment agents and high-molecular flocculants, paper making auxiliaries, leather auxiliaries, synthetic material auxiliaries, textile dyeing agents and finishing agents, food additives, feed additives, animal medicines, oil field chemicals, petroleum additives and refining auxiliaries, cement additives, mineral flotation agents, casting chemicals, metal surface treatment agents, synthetic lubricating oil and lubricating oil additives, automobile chemicals, aromatic deodorants, industrial antibacterial and mildewproof agents, electronic chemicals and materials, functional high-molecular materials, biochemical products and the like. There are various methods for classifying fine chemical wastewater. Pharmaceutical wastewater, pesticide wastewater, dye wastewater, daily chemical wastewater and the like are classified according to the industry; if the pollutant types contained in the wastewater are classified, the wastewater contains polar organic matters, low-boiling-point organic matters, high-boiling-point organic matters, heterocyclic compound-containing wastewater, ammonia nitrogen-containing wastewater and the like; according to water quality or biodegradability, the wastewater can be classified into solvent type wastewater, biodegradable wastewater, nonbiodegradable wastewater, wastewater containing toxic and harmful substances and the like. The industrial wastewater generated by the production enterprises in the fine chemical industry has high content of toxic organic pollutants, deep chromaticity and high salt content, and the wastewater contains a plurality of 'three-cause' compounds and non-biodegradable substances. Most pollutants in the fine chemical wastewater are organic substances with complex structures, toxicity, harm and difficult biodegradation, the treatment difficulty is high, the cost is high, the wastewater is typical toxic and difficult-to-degrade industrial organic wastewater, the wastewater has the characteristics of high COD, high ammonia nitrogen, high chromaticity and the like, the main components harmful to microorganisms comprise COD, ammonia nitrogen, dye, decomposition products thereof and the like, the biological system has a serious inhibition effect, and the wastewater is the main reason for causing the effluent to be not up to the standard. The treatment principle of the fine chemical wastewater is to adopt a production process without public hazard or with less public hazard as far as possible. The high-concentration wastewater synthesized in the fine chemical industry park is easy to cause environmental pollution and economic loss if the wastewater is not properly treated. However, the treatment of such waste water has not been solved effectively.

Therefore, a method for effectively treating the comprehensive high-concentration wastewater in the fine chemical engineering park is required to be found, effluent water is ensured to reach the standard, and the recovery of byproduct salt is realized.

Disclosure of Invention

The invention aims to overcome the problems in the prior art and provide a method for treating comprehensive high-concentration wastewater in a fine chemical industry park.

In order to achieve the above object, the present invention provides the following technical solutions.

A treatment method of comprehensive high-concentration wastewater in a fine chemical industry park comprises the following steps:

carrying out coagulation treatment on the comprehensive high-concentration wastewater in the fine chemical industry park;

carrying out physical adsorption on the wastewater subjected to coagulation treatment; and

and (5) evaporating to remove salt.

The "comprehensive high-concentration wastewater of the fine chemical industry park" of the present invention refers to comprehensive high-concentration wastewater generated in the fine chemical industry park, for example, wastewater containing polar organic matter, wastewater containing low boiling point organic matter, wastewater containing high boiling point organic matter, wastewater containing heterocyclic compounds, wastewater containing ammonia nitrogen, and the like.

The treatment method can effectively reduce the COD of the comprehensive high-concentration wastewater in the fine chemical industry park, effectively remove toxic and harmful pollutants such as ammonia nitrogen, total nitrogen, chromaticity, aniline, phenol and the like in the wastewater, and the distilled water is nontoxic and has good biodegradability after the wastewater is evaporated and desalted; meanwhile, white by-product salt sodium chloride or sodium sulfate can be obtained, and harmless and recycling of the salt is realized. The water quality of the wastewater treated by the combined process can reach the connection standard of sewage plants in fine chemical industry parks.

The coagulation treatment is a pretreatment process of the whole combined process, and can separate colloidal particle substances in the wastewater by coagulation and flocculation so as to purify the wastewater. Specifically, the comprehensive high-concentration wastewater of the fine chemical industry park can be added into a coagulating sedimentation device for coagulation treatment. The coagulation treatment may include: adding sodium hydroxide, polyferric oxide and polyacrylamide into the waste water.

In some embodiments of the invention, the sodium hydroxide may be added in an amount of 10-30mg of sodium hydroxide per liter of wastewater, for example, 10mg, 15mg, 20mg, 25mg, or 30mg of sodium hydroxide per liter of wastewater. Preferably, 20mg of sodium hydroxide per liter of wastewater is added.

In some embodiments of the invention, the amount of polyferric added may be from 200 to 400mg per liter of wastewater, for example, 200mg, 250mg, 300mg, 350mg or 400mg per liter of wastewater. Preferably, 300mg of polyferric per litre of wastewater is added.

In some embodiments of the invention, the polyacrylamide may be added in an amount of 2-4mg polyacrylamide per liter of wastewater, for example, 2mg, 2.5mg, 3mg, 3.5mg, or 4mg polyacrylamide per liter of wastewater. Preferably, 3mg polyacrylamide per liter of wastewater is added.

In some embodiments of the invention, the polyacrylamide is added as a solution. In some embodiments, the polyacrylamide solution is added to a mass fraction of 1% o. In some embodiments, 1% polyacrylamide solution may be added in an amount of 2000-4000mg of 1% polyacrylamide solution per liter of wastewater, for example, 2000mg, 2500mg, 3000mg, 3500mg, or 4000mg of 1% polyacrylamide solution per liter of wastewater. Preferably, 3000mg of 1 per thousand polyacrylamide solution is added per liter of wastewater.

In some embodiments of the invention, the reaction is carried out for 0.4 to 0.6h, for example for 0.45h, 0.5h, 0.55h or 0.6h, after the addition of sodium hydroxide, polyferric oxide and polyacrylamide to the wastewater. After the reaction is finished, the obtained coagulating sedimentation effluent can enter a subsequent treatment working section.

Preferably, the coagulation treatment comprises: adding 20mg of sodium hydroxide, 300mg of polyferric and 3000mg of 1 per mill polyacrylamide solution into each liter of wastewater, reacting for 0.5h, and then carrying out coagulating sedimentation to obtain effluent which enters a subsequent treatment working section.

In some embodiments of the invention, after the coagulation treatment and before the physical adsorption, further comprising: and (3) rectifying and desolventizing to remove the solvent with the boiling point of below 100 ℃ in the wastewater. The rectification desolventizing can be carried out in a rectification desolventizing device. The rectification and desolventization are carried out for the purpose of removing low boiling point organic matters such as alcohols.

In some embodiments of the invention, after the coagulation treatment and before the physisorption, the method further comprises: and carrying out stripping deamination to remove ammonia nitrogen in the wastewater. The stripping deamination may be performed in a stripping deamination apparatus. The purpose of stripping deamination is to remove ammonia nitrogen from the wastewater, which refers to the combined nitrogen in the form of free ammonia (NH 3) and ammonium ions (NH 4 +).

In some embodiments, the stripping deamination comprises: sodium hydroxide was added to the wastewater. The amount of sodium hydroxide added may be 1800-2000mg of sodium hydroxide per liter of wastewater, for example 1800, 1850, 1900, 1950 or 2000mg of sodium hydroxide per liter of wastewater. Preferably, 1900mg of sodium hydroxide per liter of wastewater may be added.

The wastewater after rectification, desolventizing and stripping deamination can enter a subsequent treatment working section.

The steps of rectification desolventizing and stripping deamination can be optionally carried out according to the property of the waste water.

In some embodiments of the invention, after the coagulation treatment and before the physisorption, the method of the invention further comprises: and carrying out chemical separation to remove polar organic matters in the wastewater. Particularly, in the case of waste water containing low boiling point organic matter and/or ammonia nitrogen, it is necessary to first perform distillation desolventizing and/or stripping deamination and then perform chemical separation. Under the condition that the wastewater does not contain low-boiling-point organic matters and ammonia nitrogen, chemical separation can be directly carried out after coagulation treatment without rectification desolventizing and stripping deamination.

The chemical separation may be performed in a chemical separation device. The chemical separation is carried out for removing polar organic substances such as organic carboxylic acids, phenols, benzenesulfonic acids, naphthols, naphthalenesulfonic acids, organic amines, anilines, benzothiazoles, benzotriazoles and the like in the wastewater.

In some embodiments, the chemical separation comprises: adjusting the pH of the wastewater to 1.5-2.5 (such as 1.5, 1.6, 1.7, 1.8, 1.9, 2, 2.1, 2.2, 2.3, 2.4 or 2.5, preferably 2), mixing the wastewater after the pH adjustment with a separating agent for reaction, standing for layering after the reaction is finished, and separating. The separating agent is selected from Shenyang Hui Yu chemical industry environmental protection science and technology company FLJ332. The volume of the separating agent is 15% -25% of the volume of the wastewater, such as 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24% or 25%. The reaction time may be from 0.3 to 1h, for example from 0.3 to 0.7h.

After standing and layering, the upper layer is a chemical separation phase, namely an organic phase, and the lower layer is a water phase. And mixing the organic phase with alkali for reaction to obtain the regenerated separating agent. The regenerated separating agent is recycled. Optionally, the alkali is an alkali solution with the mass fraction of 10% -20%, and the volume ratio of the organic phase to the alkali solution is (4-8): 1. For example, the base is a 15% alkali solution and the volume ratio of the organic phase to the alkali solution is 6:1. Alternatively, the reaction temperature is 30-50 deg.C (e.g., 30 deg.C, 35 deg.C, 40 deg.C, 45 deg.C, or 50 deg.C), and the reaction time is 0.3-0.8h (e.g., 0.3h, 0.4h, 0.5h, 0.6h, 0.7h, or 0.8 h).

In one particular embodiment, the chemical separation comprises: adding sulfuric acid or hydrochloric acid into the wastewater, adjusting the pH of the wastewater to 1.5-2.5, adding the wastewater after the pH adjustment into a chemical separation device, mixing the wastewater with a separating agent (the volume accounts for 15-25% of the volume of the wastewater) by using a mixer, adding the mixture into a chemical separation reactor together, carrying out chemical separation reaction for 0.3-1h, overflowing the obtained mixed process liquid into a separator, standing and layering for 7h, overflowing a chemical separation phase into a separation phase storage tank from the top of the chemical separator, allowing an aqueous phase to automatically flow out of the bottom of the separator to a water oil separator system, carrying out secondary separation and oil separation by an outlet oil separator, and then allowing the aqueous phase to enter subsequent treatment. Separating phase pumped from the separating phase storage tank and dilute alkali pumped from a 10% -20% dilute alkali storage tank are mixed according to the following separating phase: and (4-8) mixing the dilute alkali with the ratio of 1, heating the mixture to 30-50 ℃ by a heat exchanger, feeding the mixture into a reverse reactor, carrying out chemical separation and regeneration reaction for 0.3-0.8h, overflowing the obtained mixed process liquid into a reverse reaction separator, standing and separating to obtain a regenerated separating agent, and recycling the regenerated separating agent.

The chemical separation of the present invention may be optionally performed depending on the nature of the wastewater. In the case of wastewater containing polar organic matter, chemical separation is required.

In some embodiments of the invention, after the coagulation treatment and before the physisorption, the method further comprises: and carrying out catalytic oxidation to remove refractory organic matters in the wastewater. In particular, the catalytic oxidation may be carried out directly after the coagulation treatment. Alternatively, in the case where the rectification desolventizing is required, the rectification desolventizing may be performed after the rectification desolventizing. Alternatively, in the case where the stripping deamination is required, it may be performed after the stripping deamination. Alternatively, in the case where the distillation desolventization and the stripping deamination are required, they may be performed after the completion of the two steps. Alternatively, in the case where chemical separation is required, it may be performed after the chemical separation.

The catalytic oxidation may be carried out in a catalytic oxidation unit. The catalytic oxidation is carried out for the purpose of removing refractory organic substances from the wastewater. The refractory organic matter comprises heterocyclic compounds and the like.

In some embodiments, the catalytic oxidation comprises: adjusting the pH value of the wastewater to 3-4, and then adding a catalyst and an oxidant to react to obtain oxidized water. Preferably, the catalyst is ferrous sulfate, and the oxidant is hydrogen peroxide.

Alternatively, the wastewater pH may be adjusted by adding sodium hydroxide.

Alternatively, the catalyst may be added in an amount of 2000-4000mg of catalyst per liter of wastewater, for example 2000mg, 2500mg, 3000mg, 3500mg or 4000mg of catalyst per liter of wastewater. Preferably, 3000mg of catalyst per liter of wastewater may be added.

Optionally, the oxidant is 27.5% by mass of hydrogen peroxide. The 27.5% hydrogen peroxide can be added in an amount of 9000-11000mg of 27.5% hydrogen peroxide per liter of wastewater, for example, 9000mg, 9500mg, 10000mg, 10500mg or 11000mg of 27.5% hydrogen peroxide per liter of wastewater. Preferably, 10000mg of 27.5% hydrogen peroxide per liter of wastewater can be added.

Alternatively, the reaction time for the catalytic oxidation is 1-5h, such as 1h, 2h, 3h, 4h, or 5h.

Optionally, after the catalytic oxidation is finished, adding alkali and a defoaming agent into the obtained catalytic oxidation effluent to neutralize and degas, then adjusting the pH of the obtained neutralized and degassed effluent to 7-8, adding polyacrylamide to perform a flocculation reaction, then settling, and allowing the obtained effluent to enter a subsequent physical adsorption section. The base may be sodium hydroxide. The amount of the base added may be 7000-9000mg of the base per liter of wastewater, for example 7000mg, 7500mg, 8000mg, 8500mg or 9000mg of the base per liter of wastewater. Preferably, 8000mg of the base per liter of wastewater may be added. The defoamer can be a polyether modified silicone defoamer. Optionally, the defoamer is a 1% polyether modified silicone based defoamer. The 1% defoamer may be added in an amount of 4000-6000mg of 1% defoamer per liter of wastewater, for example 4000mg, 4500mg, 5000mg, 5500mg or 6000mg of 1% defoamer per liter of wastewater. Preferably, 5000mg of 1% defoamer per liter of wastewater may be added. Preferably, the time for neutralization degassing is 1-5h, e.g. 1h, 2h, 3h, 4h or 5h. In some embodiments, the polyacrylamide is added as a solution. In some embodiments, the polyacrylamide solution is added as a 1% by weight polyacrylamide solution. In some embodiments, 1% polyacrylamide solution may be added in an amount of 2000-4000mg of 1% polyacrylamide solution per liter of wastewater, for example, 2000mg, 2500mg, 3000mg, 3500mg, or 4000mg of 1% polyacrylamide solution per liter of wastewater. Preferably, 3000mg of 1 per thousand polyacrylamide solution is added per liter of wastewater. Preferably, the time of the flocculation reaction may be 10-60min, such as 10min, 20min, 30min, 40min, 50min or 60min. Preferably, the settling time may be 1-5h, e.g. 1h, 2h, 3h, 4h or 5h.

In a specific embodiment, before catalytic oxidation, firstly adding sodium hydroxide into wastewater to adjust the pH to 3-4, then adding the wastewater into a catalytic oxidation device, adding 2000-4000mg of ferrous sulfate heptahydrate catalyst into each liter of wastewater, adding 9000-11000mg of 27.5% hydrogen peroxide into each liter of wastewater, performing catalytic oxidation reaction for 1-5h to obtain catalytic oxidation effluent, adding 7000-9000mg of sodium hydroxide and 4000-6000mg of 1% defoaming agent into each liter of catalytic oxidation effluent, performing neutralization degassing for 1-5h, then adjusting the pH to 7-8 to obtain neutralization degassing effluent, adding 2000-4000mg of polyacrylamide solution into each liter of neutralization degassing effluent, performing flocculation reaction for 10-60min, then settling for 1-5h, and enabling supernatant to enter a subsequent treatment section.

The catalytic oxidation may be optionally performed depending on the nature of the wastewater.

In some embodiments of the invention, the physisorption comprises: activated carbon is used for adsorption decoloration.

In some embodiments, the physical adsorption may be performed in an adsorption apparatus. Specifically, powdered activated carbon can be added into the wastewater to carry out adsorption decoloration reaction so as to ensure the quality of the salt. The absorbed water can enter a subsequent evaporation treatment section. Alternatively, the amount of activated carbon added may be 900-1100mg of activated carbon per liter of wastewater, for example 900mg, 950mg, 1000mg, 1050mg or 1100mg of activated carbon per liter of wastewater. Preferably, 1000mg of activated carbon per liter of wastewater may be added. Alternatively, the adsorption decoloring reaction time may be 0.2 to 1h, and for example, may be 0.2h, 0.3h, 0.4h, 0.5h, 0.6h, 0.7h, 0.8h, 0.9h, or 1h.

In some embodiments of the invention, the evaporation may be performed in an evaporation apparatus. White byproduct salt can be obtained after evaporation treatment, the harmlessness and the resource of the salt are realized, the obtained distilled water is nontoxic and has good biodegradability, and the water quality can reach the connection standard of sewage plants in fine chemical industry parks.

Compared with the prior art, the invention has the beneficial effects that:

the invention provides a treatment method of comprehensive high-concentration wastewater of a fine chemical industry park, which can effectively reduce COD of the comprehensive high-concentration wastewater of the fine chemical industry park and effectively remove toxic and harmful pollutants such as ammonia nitrogen, total nitrogen, chromaticity, aniline, phenol and the like in the wastewater; meanwhile, white by-product salt sodium chloride or sodium sulfate can be obtained, and harmless and recycling of the salt is realized. The water quality of the wastewater treated by the combined process can reach the take-over standard of sewage plants in fine chemical industry parks.

Drawings

FIG. 1 is an exemplary flow diagram of the integrated high-strength wastewater treatment process of the present invention.

Detailed Description

In view of the defects of the prior art, the inventor of the present invention has made long-term research and has proposed the technical solution of the present invention. The embodiments of the present invention are described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments of the present invention. Other embodiments, which are not inventive improvements based on the embodiments of the present invention, and which can be obtained by a person skilled in the art without departing from the scope of the present invention.

Unless defined otherwise, technical terms used in the following examples have the same meanings as commonly understood by one of ordinary skill in the art to which the present invention belongs. The experimental reagents used in the following examples, unless otherwise specified, are all conventional biochemical reagents; the raw materials, instruments, equipment and the like used in the following examples are either commercially available or available by existing methods; the dosage of the experimental reagent is the dosage of the reagent in the conventional experimental operation if no special description exists; the experimental methods are all conventional methods unless otherwise specified.

Example 1

The wastewater used in this example was obtained from the wastewater produced in methyl anthranilate from a chemical plant in the Liaoning Shushun chemical park, and the water quality conditions are shown in Table 1 below.

TABLE 1 Water quality of methyl anthranilate production wastewater

Name of waste water	Colour(s)	pH	COD mg/L	Chloride ion mg/L	Salinity
						Methyl anthranilate wastewater	Black color	9	55732	41163	11.3%

The pollutant components contained in the wastewater are anthranilic acid, phthalic acid, methanol, sodium chloride and the like.

(1) 2000mL of the methyl anthranilate production wastewater is measured, 0.04g of sodium hydroxide, 0.6g of polyferric and 6g of polyacrylamide solution with the mass fraction of 1 per mill are added, reaction is carried out for 0.5h, filtration treatment is carried out, the filtrate is the coagulated wastewater, and the COD of the wastewater is 52836mg/L.

(2) Taking 1800ml of the wastewater obtained in the step (1), rectifying and desolventizing the wastewater, wherein COD of the wastewater after desolventizing is 21086mg/L, and the pollutant removed in the process is methanol.

(3) Taking 1500ml of the wastewater obtained in the step (2), adding 34.5g of hydrochloric acid with the mass fraction of 31% to adjust the pH to 2, adding 300ml of chemical separating agent FLJ332 sold by Shenyang Hui Yu chemical environmental protection technology company into the wastewater after adjusting the pH, stirring and reacting for 0.5h, standing and layering to obtain a chemical separation phase (organic phase) as an upper layer, a chemical separation water phase as a lower layer, wherein COD (chemical oxygen demand) of the chemically separated water is 2155mg/L, and the pollutants removed in the process are anthranilic acid and phthalic acid.

(4) And (4) taking 1000ml of the wastewater obtained in the step (3), adding 1g of powdered activated carbon, stirring and reacting for 0.5h, filtering to obtain filtrate, namely the adsorbed effluent, and removing residual chromaticity in the process to ensure the quality of the evaporated salt.

Detection and analysis show that the adsorbed water is colorless, COD is 1880 mg/L, and the COD removal rate in the whole process is 96%. The adsorbed water is subjected to evaporation and desalination, the COD of the evaporated water is 256mg/L, BOD5/CODCr =0.42, and the biodegradability is good; simultaneously, white byproduct salt sodium chloride is obtained.

And (3) adding 50mL of 15 mass percent sodium hydroxide solution into 300mL of the chemical separation phase in the step (3), starting stirring, heating in a water bath to 40 ℃, reacting for 0.5h, standing for layering, and recycling the regenerated chemical separating agent as the upper layer for next chemical separation, wherein the cycle is repeated. The lower layer is organic waste liquid.

Example 2

The wastewater used in this example was obtained from the production wastewater of a photoinitiator from a chemical plant in a chemical park of inner Mongolia, and the water quality was as shown in Table 2 below.

TABLE 2 quality of photoinitiator production wastewater

Name of waste water	Appearance of the product	pH	Salt (%)	COD (mg/L)	Phenol (mg/L)
						Waste water from production of photoinitiator	Brown rice	5	25	42462	2509

The pollutant components contained in the wastewater are toluene, m-diethylbenzene, sulfodiethylbenzene, thiosalicylic acid, phenol, sodium chloride and the like.

(1) 2000mL of the photoinitiator production wastewater is measured, 0.04g of sodium hydroxide, 0.6g of polyferric and 6g of polyacrylamide solution with the mass fraction of 1 per mill are added, reaction is carried out for 0.5h, filtration treatment is carried out, the filtrate is coagulated wastewater, COD of the wastewater is 41498mg/L, and the phenol content is 2498mg/L.

(2) Taking 1800ml of the wastewater obtained in the step (1), rectifying and desolventizing the wastewater, wherein COD of the wastewater after desolventizing is 21330mg/L, the phenol content is 2498mg/L, and toluene and m-diethylbenzene are mainly removed in the process.

(3) And (3) taking 1500ml of the wastewater obtained in the step (2), adding 34.5g of hydrochloric acid with the mass fraction of 31% to adjust the pH to 2, adding 300ml of a chemical separating agent FLJ332 into the wastewater after adjusting the pH, stirring and reacting for 0.5h, standing and layering to obtain an upper layer of a chemical separation phase and a lower layer of a water phase after chemical separation, wherein COD (chemical oxygen demand) of the chemically separated water is 1338mg/L, the phenol content is 56mg/L, and polar organic matters such as sulfodiethylbenzene, thiosalicylic acid, phenol and the like are mainly removed in the process.

(4) Taking 1200ml of the wastewater obtained in the step (3), adding 0.36g of sodium hydroxide, adjusting the pH value to 3-4, continuously adding 3.6g of catalyst ferrous sulfate heptahydrate and 12g of hydrogen peroxide with the mass fraction of 27.5% of oxidant, carrying out catalytic oxidation reaction for 2h, adding 9.6g of sodium hydroxide and 6g of polyether modified organosilicon defoamer AF-1125 (Shenyang Ruichi surface technology Co., ltd.) with the mass fraction of 1% to the effluent, carrying out neutralization and degassing for 2h, adding 3.6g of polyacrylamide solution with the mass fraction of 1% to the obtained neutralized and degassed effluent, carrying out flocculation reaction for 20min, then carrying out sedimentation for 2h, wherein the supernatant is the catalytic oxidation effluent, the COD is 355mg/L, and the phenol content is 0.5mg/L, and removing the residual pollutants in the process.

(5) And (4) taking 1000ml of the wastewater obtained in the step (4), adding 1g of powdered activated carbon, stirring and reacting for 0.5h, filtering to obtain filtrate, namely the adsorbed effluent, and removing residual chromaticity in the process to ensure the quality of the evaporated salt.

Detection and analysis show that the adsorbed water is colorless, the COD is 235 mg/L, the COD removal rate in the whole process is 99 percent, and the phenol: not detected, and the phenol removal rate in the whole process is 100 percent. The adsorbed water is subjected to evaporation and desalination, the COD of the evaporated water is 46mg/L, phenol is not detected, B/C =0.46, and good biodegradability is achieved; simultaneously, white byproduct salt sodium chloride is obtained.

And (4) adding 50mL of 15% mass fraction sodium hydroxide solution into 300mL of the chemical separation phase obtained in the step (3), starting stirring, heating in a water bath to 40 ℃, reacting for 0.5h, standing for layering, and recycling the upper layer as a regenerated chemical separating agent for next chemical separation, wherein the process is repeated in a circulating manner. The lower layer is organic waste liquid.

Example 3

The wastewater used in this example was allyl amine production wastewater from a chemical plant in a chemical park of Shandong, and the water quality was as shown in Table 3 below.

TABLE 3 quality of allylamine production wastewater

Name of waste water

Colour(s)

pH

COD （mg/L）

Ammonia nitrogen (mg/L)

Chloride ion (mg/L)

Salt content

Wastewater from allylamine production

Dark brown color

13

9375

2380

75653

12.6%

(1) Weighing 3000mL of the wastewater, adding 0.06g of sodium hydroxide, 0.9g of polyferric and 9g of polyacrylamide solution with the mass fraction of 1 per mill, reacting for 0.5h, and filtering to obtain a filtrate, wherein the filtrate is coagulated wastewater, COD (chemical oxygen demand) of the wastewater is 9120mg/L, and the ammonia nitrogen content is 2375mg/L.

(2) And (2) adding 4.75g of sodium hydroxide into 2500ml of wastewater obtained in the step (1), and performing stripping deamination treatment, wherein COD (chemical oxygen demand) of the deaminated wastewater is 3750mg/L, and the ammonia nitrogen content is 5mg/L.

(3) Adding 50g of hydrochloric acid with the mass fraction of 31% into 2000ml of wastewater obtained in the step (2), adjusting the pH to 3-4, continuously adding 6g of ferrous sulfate heptahydrate catalyst and 20g of hydrogen peroxide with the mass fraction of 27.5% oxidant, carrying out catalytic oxidation reaction for 2h, adding 16g of sodium hydroxide and 10g of polyether modified organosilicon defoamer AF-1125 (purchased from Shenyang Ruichi surface technology Co., ltd.) into the effluent, carrying out neutralization and degassing for 2h, adding 6g of polyacrylamide solution with the mass fraction of 1 thousandth into the neutralized and degassed effluent, carrying out flocculation reaction for 20min, then carrying out sedimentation for 2h, obtaining the supernatant as catalytic oxidation effluent, wherein the COD is 1360mg/L, and the ammonia nitrogen content is 4mg/L.

(4) And (4) adding 1.5g of powdered activated carbon into 1500ml of the wastewater obtained in the step (3), stirring and reacting for 0.5h, and filtering to obtain filtrate, namely the adsorbed effluent.

Detection and analysis show that the adsorbed water is colorless, the COD is 1020 mg/L, the ammonia nitrogen content is 4mg/L, the COD removal rate in the whole process is 89%, and the ammonia nitrogen removal rate is 99%. The adsorbed water is subjected to evaporation and desalination, the COD of the evaporated water is 205mg/L, the ammonia nitrogen content is 3mg/L, B/C =0.41, and the biodegradability is good; simultaneously, white byproduct salt sodium chloride is obtained.

Example 4

The wastewater used in this example was obtained from the waste water produced in the production of imazethapyr from a chemical plant in a chemical park of inner Mongolia, and the water quality was as shown in Table 4 below.

TABLE 4 quality of Imazethapyr production wastewater

Name of waste water

Colour(s)

pH

Salt content

COD （mg/L）

Cl- （mg/L）

Ammonia nitrogen (mg/L)

Imazethapyr production wastewater

Yellow colour

2

11.6%

82925

9976

11936

The pollutant components contained in the wastewater are imazethapyr, ammonium sulfamate, ethanol, acetonitrile, ammonia nitrogen, sodium chloride and the like.

(1) 4000mL of the imazethapyr production wastewater is measured, 0.08g of sodium hydroxide, 1.2g of polyferric and 12g of polyacrylamide solution with the mass fraction of 1 per mill are added, after 0.5h of reaction, filtration treatment is carried out, the filtrate is the coagulated wastewater, and the COD of the wastewater is 79828mg/L.

(2) Taking 3600ml of the wastewater obtained in the step (1), rectifying and desolventizing, wherein COD (chemical oxygen demand) of the wastewater after desolventizing is 11888mg/L, and pollutants removed in the process are ethanol and acetonitrile.

(3) Taking 3000ml of the wastewater obtained in the step (2), adding 5.7g of sodium hydroxide, and performing stripping deamination treatment, wherein COD (chemical oxygen demand) of the deaminated wastewater is 10308mg/L, and the ammonia nitrogen content is 12mg/L.

(4) Adding 34.5g of hydrochloric acid with the mass fraction of 31% into 1500ml of the wastewater obtained in the step (3) to adjust the pH value to 2, adding 300ml of chemical separating agent FLJ332 sold by Shenyang Hui Yu chemical environmental protection technology Co., ltd into the wastewater after adjusting the pH value, stirring and reacting for 0.5h, standing and layering to obtain an upper layer which is a chemical separation phase (organic phase) and a lower layer which is a water phase after chemical separation, wherein COD of the chemically separated water is 7391mg/L, and pollutants removed in the process are imazethapyr and ammonium sulfamate.

(5) Taking 1200ml of the wastewater obtained in the step (4), adding 0.36g of sodium hydroxide, adjusting the pH value to 3-4, continuously adding 3.6g of ferrous sulfate heptahydrate serving as a catalyst and 12g of hydrogen peroxide serving as an oxidant, wherein the mass fraction of the hydrogen peroxide is 27.5%, carrying out catalytic oxidation reaction for 2h, adding 9.6g of sodium hydroxide and 6g of polyether modified organosilicon defoamer AF-1125 (purchased from Shenyang Ruichi surface technology Co., ltd.) to neutralize and degas for 2h, adding 3.6g of polyacrylamide solution with the mass fraction of 1 per thousand into the neutralized and degassed effluent, carrying out flocculation reaction for 20min, then settling for 2h, obtaining supernatant which is catalytic oxidation effluent, wherein the COD is 5865mg/L, and removing residual pollutants in the process.

(6) And (4) taking 1000ml of the wastewater obtained in the step (5), adding 1g of powdered activated carbon, stirring and reacting for 0.5h, filtering to obtain filtrate, namely the adsorbed effluent, removing residual chromaticity in the process, and ensuring the quality of the distilled salt.

Detection and analysis show that the adsorbed water is colorless, the COD is 5185 mg/L, and the COD removal rate in the whole process is 96%. The adsorbed water is subjected to evaporation desalting, the COD of the evaporated water is 1362mg/L, B/C =0.46, and good biodegradability is achieved; simultaneously, white byproduct salt sodium chloride is obtained.

And (3) adding 50mL of 15 mass percent sodium hydroxide solution into 300mL of the chemical separation phase obtained in the step (4), starting stirring, heating in a water bath to 40 ℃, reacting for 0.5h, standing for layering, and recycling the regenerated chemical separating agent as the upper layer for next chemical separation, wherein the cycle is repeated. The lower layer is organic waste liquid.

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

1. A treatment method of comprehensive high-concentration wastewater in a fine chemical industry park is characterized by comprising the following steps:

carrying out physical adsorption on the wastewater after the coagulation treatment; and

and (5) evaporating to remove salt.

2. The treatment method according to claim 1, further comprising, after the coagulation treatment and before the physical adsorption: and (3) rectifying and desolventizing to remove the solvent with the boiling point of below 100 ℃ in the wastewater.

3. The process of claim 1, further comprising, after the coagulation process and before the physical adsorption: and carrying out stripping deamination to remove ammonia nitrogen in the wastewater.

4. The process of claim 1, further comprising, after the coagulation process and before the physical adsorption: and carrying out chemical separation to remove polar organic matters in the wastewater.

5. The treatment method according to claim 1, further comprising, after the coagulation treatment and before the physical adsorption: and carrying out catalytic oxidation to remove refractory organic matters in the wastewater.

6. The process of claim 3, wherein the stripping deamination comprises: sodium hydroxide was added to the wastewater.

7. The process of claim 4, wherein said chemical separation comprises: adjusting the pH value of the wastewater to 1.5-2.5, mixing the wastewater after the pH value is adjusted with a separating agent for reaction, standing for layering after the reaction is finished, and separating.

8. The treatment method according to claim 5, wherein the catalytic oxidation comprises: adjusting the pH value of the wastewater to 3-4, and then adding a catalyst and an oxidant to react to obtain oxidized water.

9. The processing method according to any one of claims 1 to 5,

the coagulation treatment comprises the following steps: adding sodium hydroxide, polyferric oxide and polyacrylamide into the waste water.

10. The process of any one of claims 1 to 5, wherein the physical adsorption comprises: activated carbon is used for adsorption decoloration.