CN110683694A - Method for treating ethyl chloride production wastewater by ozone oxidation method - Google Patents

Method for treating ethyl chloride production wastewater by ozone oxidation method Download PDF

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Publication number
CN110683694A
CN110683694A CN201910844034.1A CN201910844034A CN110683694A CN 110683694 A CN110683694 A CN 110683694A CN 201910844034 A CN201910844034 A CN 201910844034A CN 110683694 A CN110683694 A CN 110683694A
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CN
China
Prior art keywords
ozone
oxidation
wastewater
value
ethyl chloride
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Pending
Application number
CN201910844034.1A
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Chinese (zh)
Inventor
郑茂红
李惠跃
孟祥利
刘青青
袁广志
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Zhejiang Avilive Chemical Co Ltd
Shandong Vicome Lunan Pesticide Co Ltd
Original Assignee
Zhejiang Avilive Chemical Co Ltd
Shandong Vicome Lunan Pesticide Co Ltd
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Priority to CN201910844034.1A priority Critical patent/CN110683694A/en
Publication of CN110683694A publication Critical patent/CN110683694A/en
Pending legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F9/00—Multistage treatment of water, waste water or sewage
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/02—Treatment of water, waste water, or sewage by heating
    • C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/101—Sulfur compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/105—Phosphorus compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
    • C02F2103/36—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds

Abstract

The invention relates to a method for treating ethyl chloride production wastewater by ozone oxidation, which comprises the following steps of 1) adding the production wastewater into an oxidation kettle, and adding alkali to adjust the pH value to be 6-11; 2) adding 0.5-1% of active carbon or active diatomite and 0.2-0.5% of defoaming agent; 3) opening an equipment waste gas treatment system, and maintaining the micro negative pressure in the oxidation kettle; 4) starting an ozone generator, and introducing ozone from the bottom of the oxidation kettle to perform oxidation reaction; 5) controlling the reaction temperature to be 15-45 ℃; periodically detecting the pH value, and adjusting the pH value to 6-11; 6) stopping ozone introduction when the pH value is stable, and adding Ca (OH)2Stirring and filtering; 7) evaporating the filtrate by three effects, and entrusting the filter residue to a qualification unit for treatment; 8) and (4) taking sodium chloride as a byproduct after evaporation for sale, and recycling the distilled water to the workshop hydrolysis process. The advantages are that: firstly, the ethyl chloride wastewater is treated by ozone oxidationThe effluent index meets the requirements of recycling to a workshop hydrolysis procedure or entering biochemical treatment; the effluent index is superior to that of the Fenton oxidation and the sodium hypochlorite method oxidation method for treating the wastewater.

Description

Method for treating ethyl chloride production wastewater by ozone oxidation method
Technical Field
The invention relates to a method for treating ethyl chloride production wastewater by ozone oxidation, belonging to the field of sewage treatment.
Background
Ethyl chloride is one of the basic organic synthetic raw materials and is an important intermediate for producing pesticides and medicines. The compound can be used for synthesizing organophosphorus insecticides such as phoxim, chlorpyrifos, triazophos, diazinon, profenofos and the like in pesticides, and has wide application range. At present, the ethyl chloride is generally prepared by a phosphorus pentasulfide method in China, namely phosphorus pentasulfide and absolute ethyl alcohol react under the catalysis of triethylamine to generate sulfide, and then chlorine is introduced for chlorination to obtain chloride; adding water into the chloride for hydrolysis, and removing disulfide dichloride to obtain crude ethyl chloride and sulfur; then rectifying the crude product to obtain the finished product of the ethyl chloride. The method for producing about 1.5T of acidic organic wastewater per ton of ethyl chloride has the disadvantages of complex wastewater components, high COD and difficult treatment.
At present, the ethyl chlorination production wastewater is mainly subjected to oxidation treatment by a Fenton oxidation method and a sodium hypochlorite method, but hydrogen peroxide used as a raw material in the Fenton oxidation is a class A material, the use process is safe and high in removal, the Fenton oxidation method also has incomplete oxidation, and the wastewater is separated out by sulfur in the distillation process, so that the quality of byproduct salt is influenced, evaporation equipment is blocked, and the normal operation of the equipment is influenced. The sodium hypochlorite oxidation process brings in a large amount of salt and wastewater, increasing the cost of wastewater treatment.
Ozone is a strong oxidant, has high degradation efficiency on some pollutants, is thorough in oxidative degradation, can convert complex organic pollutants into simple organic matters, and realizes functions of decoloring, deodorizing, reducing COD and the like. The residual ozone in the reaction can be catalytically decomposed into oxygen, and secondary pollution is not generated. The reaction of ozone and organic pollutant has fast speed, high effect, no secondary pollution, capacity of in-situ production, facile material, convenient use and safe and reliable technological apparatus.
Disclosure of Invention
The design purpose is as follows: the method avoids the defects in the background technology, designs a more economical, safe and effective method for treating the production wastewater of the ethyl chloride, adopts the process steps of neutralization, ozone oxidation, lime precipitation, filtration, triple-effect evaporation and the like, and efficiently and safely treats the production wastewater of the ethyl chloride.
The design scheme is as follows: in order to achieve the above design objectives. According to the invention, the acidic ethyl chloride production wastewater is treated through the process steps of neutralization, ozone oxidation, lime precipitation, filtration, triple-effect evaporation and the like, so that the standard requirement of workshop recycling is met, and the acidic ethyl chloride production wastewater is recycled to a workshop hydrolysis process, thereby realizing zero discharge of the wastewater.
The designed oxidation aims at oxidizing and degrading organic pollutants in the wastewater into simple organic matters, and achieving the purposes of decoloring, deodorizing, COD (chemical oxygen demand) reducing and the like.
The purpose of lime precipitation and filtration is to remove oxidized phosphate.
The technical scheme is as follows: an ozone oxidation treatment method for ethyl chloride production wastewater comprises the following process steps:
1) adding the production wastewater into an oxidation kettle, and adding alkali to adjust the pH value to 6-11;
2) adding 0.5-1% of active carbon or active diatomite and 0.2-0.5% of defoaming agent;
3) opening an ozone decomposer and an alkaline washing tower of the equipment waste gas treatment system, and maintaining the micro negative pressure in the oxidation kettle;
4) starting an ozone generator, and introducing ozone from the bottom of the oxidation kettle to perform oxidation reaction;
5) controlling the reaction temperature to be 15-45 ℃; periodically detecting the pH value, and adjusting the pH value to 6-11;
6) stopping ozone introduction when the pH value is stable, and adding Ca (OH)2Stirring and filtering;
7) evaporating the filtrate by three effects, and entrusting the filter residue to a qualification unit for treatment;
8) and (4) taking sodium chloride as a byproduct after evaporation for sale, and recycling the distilled water to the workshop hydrolysis process.
The production wastewater of the invention is wastewater generated in the production process of ethyl chloride. The main pollutants in the wastewater are hydrogen chloride, ethyl chloride and decomposers thereof, the pH is less than 2, the COD is 40000-.
Compared with the background technology, firstly, the ethyl chloride wastewater is treated by ozone oxidation, and the effluent index meets the requirements of recycling to a workshop hydrolysis procedure or entering biochemical treatment; effluent indexes are superior to those of wastewater treated by Fenton oxidation and sodium hypochlorite method oxidation, and effluent data comparison conditions are as follows:
fenton method for treating COD (mg/L) and ozone method for treating total phosphorus (mg/L) and total phosphorus (mg/L) by Fenton method and ozone method
3356 1204 30.7 6.9
4394 963.2 24.5 6.04
Secondly, the ethyl chloride wastewater is oxidized by ozone without adding FeSO4The Fenton reagent has no secondary pollution, the quality of the byproduct salt is excellent, and the index of the byproduct salt is met; thirdly, the ethyl chloride wastewater is subjected to ozone oxidation treatment, so that the sulfur-containing substances in the wastewater are thoroughly oxidized, no sulfur is separated out in the triple-effect evaporation process, and the stable operation of equipment is facilitated; fourthly, ozone oxidation is used, so that the operation cost is low; fifthly, ozone is used for oxidation, and is a clean oxidant, so that new pollution cannot be generated, and the environment is friendly; and sixthly, ozone oxidation is used, so that the storage and use of on-site hydrogen peroxide can be reduced, the safety risk is reduced, and the method is safe and reliable.
Detailed Description
Example 1: an ozone oxidation treatment method for ethyl chloride production wastewater,
1) adding 5000L of production wastewater into a 6300L enamel oxidation kettle, and adding liquid caustic soda to adjust the pH value to 7-8;
2) adding 0.5% of activated carbon and 0.2% of defoaming agent;
3) opening an equipment waste gas treatment system, and maintaining the micro negative pressure in the oxidation kettle;
4) starting an ozone generator, introducing ozone from the bottom of the reverse oxidation, controlling the concentration of the ozone to be 120-150 mg/L and controlling the ventilation volume to be 36-40 m3/hCarrying out an oxidation reaction;
5) controlling the reaction temperature to be 30-40 ℃; periodically detecting the pH value, and adjusting the pH value to 7-8;
6) stopping ozone introduction when the pH value is stabilized to 7, and adding Ca (OH)2Stirring and filtering;
7) the filtrate is evaporated by three effects, and the filter residue is entrusted to be processed by qualification unit.
8) And (4) taking sodium chloride as a byproduct after evaporation for sale, and recycling the distilled water to the workshop hydrolysis process. The wastewater indexes before and after treatment are as follows:
COD (mg/L) removal Rate (%) of COD (mg/L) before treatment Total phosphorus (mg/L) after treatment
58400 1204 97.94% 14440
Total phosphorus (mg/L) Total phosphorus removal (%)
6.9 99.95%
Example 2: an ozone oxidation treatment method for ethyl chloride production wastewater,
1) adding 5000L of production wastewater into a 6300L enamel oxidation kettle, and adding liquid caustic soda to adjust the pH value to 7-8;
2) adding activated carbon accounting for 0.75 percent of the amount of the wastewater to be treated and an antifoaming agent accounting for 0.35 percent of the amount of the wastewater to be treated;
3) opening an equipment waste gas treatment system, and maintaining the micro negative pressure in the oxidation kettle;
4) starting an ozone generator, introducing ozone from the bottom of the reverse oxidation, controlling the concentration of the ozone to be 120-150 mg/L and controlling the ventilation volume to be 36-40 m3Performing oxidation reaction;
5) controlling the reaction temperature to be 30-40 ℃; periodically detecting the pH value, and adjusting the pH value to 7-8;
6) stopping ozone introduction when the pH value is stabilized to 7, and adding Ca (OH)2Stirring and filtering;
7) the filtrate is evaporated by three effects, and the filter residue is entrusted to be processed by qualification unit.
8) And (4) taking sodium chloride as a byproduct after evaporation for sale, and recycling the distilled water to the workshop hydrolysis process. The wastewater indexes before and after treatment are as follows:
COD (mg/L) removal Rate (%) of COD (mg/L) before treatment Total phosphorus (mg/L) after treatment
58400 963.2 98.35% 14440
Total phosphorus (mg/L) Total phosphorus removal (%)
6.04 99.96%
Example 3: an ozone oxidation treatment method for ethyl chloride production wastewater,
1) adding 5000L of production wastewater into a 6300L enamel oxidation kettle, and adding liquid caustic soda to adjust the pH value to 7-8;
2) adding activated carbon accounting for 1 percent of the amount of the wastewater to be treated and an antifoaming agent accounting for 0.5 percent of the amount of the wastewater to be treated;
3) opening an equipment waste gas treatment system, and maintaining the micro negative pressure in the oxidation kettle;
4) starting an ozone generator, introducing ozone from the bottom of the reverse oxidation, controlling the concentration of the ozone to be 120-150 mg/L and controlling the ventilation volume to be 36-40 m3Performing oxidation reaction;
5) controlling the reaction temperature to be 30-40 ℃; periodically detecting the pH value, and adjusting the pH value to 7-8;
6) stopping ozone introduction when the pH value is stabilized to 7, and adding Ca (OH)2Stirring and filtering;
7) the filtrate is evaporated by three effects, and the filter residue is entrusted to be processed by qualification unit.
8) And (4) taking sodium chloride as a byproduct after evaporation for sale, and recycling the distilled water to the workshop hydrolysis process. The wastewater indexes before and after treatment are as follows:
COD (mg/L) removal Rate (%) of COD (mg/L) before treatment Total phosphorus (mg/L) after treatment
58400 993.3 98.3% 14440
Total phosphorus (mg/L) Total phosphorus removal (%)
2.55 99.98%
It is to be understood that: although the above embodiments have described the design idea of the present invention in more detail, these descriptions are only simple descriptions of the design idea of the present invention, and are not limitations of the design idea of the present invention, and any combination, addition, or modification without departing from the design idea of the present invention falls within the scope of the present invention.

Claims (6)

1. A method for treating ethyl chloride production wastewater by an ozone oxidation method is characterized by comprising the following steps:
1) adding the production wastewater into an oxidation kettle, and adding alkali to adjust the pH value to 6-11;
2) adding 0.5-1% of active carbon or active diatomite and 0.2-0.5% of defoaming agent;
3) opening an ozone decomposer and an alkaline washing tower of the equipment waste gas treatment system, and maintaining the micro negative pressure in the oxidation kettle;
4) starting an ozone generator, and introducing ozone from the bottom of the oxidation kettle to perform oxidation reaction;
5) controlling the reaction temperature to be 15-45 ℃; periodically detecting the pH value, and adjusting the pH value to 6-11;
6) stopping ozone introduction when the pH value is stable, and adding Ca (OH)2Stirring and filtering;
7) evaporating the filtrate by three effects, and entrusting the filter residue to a qualification unit for treatment;
8) and (4) taking sodium chloride as a byproduct after evaporation for sale, and recycling the distilled water to the workshop hydrolysis process.
2. The method for treating the wastewater from the production of ethyl chloride by the ozone oxidation method according to claim 1, which comprises the following steps: the oxidant is ozone, the concentration of the ozone is 80-150 mg/L, and the preferred concentration is 120-150 mg/L; the ozone introduction rate is 2-10 kg/h, preferably 4-5 kg/h.
3. The method for treating the wastewater from the production of ethyl chloride by the ozone oxidation method according to claim 1, which comprises the following steps: the pH value is preferably 7-8.
4. The method for treating the wastewater from the production of ethyl chloride by the ozone oxidation method according to claim 1, which comprises the following steps: the adding amount of the active carbon or the active diatomite is 0.5-1%.
5. The method for treating the wastewater from the production of ethyl chloride by the ozone oxidation method according to claim 1, which comprises the following steps: the addition amount of the defoaming agent is 0.2-0.5%.
6. The method for treating the wastewater from the production of ethyl chloride by the ozone oxidation method according to claim 1, which comprises the following steps: the oxidation control temperature is 15-45 ℃, and preferably 30-40 ℃.
CN201910844034.1A 2019-09-06 2019-09-06 Method for treating ethyl chloride production wastewater by ozone oxidation method Pending CN110683694A (en)

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CN201910844034.1A CN110683694A (en) 2019-09-06 2019-09-06 Method for treating ethyl chloride production wastewater by ozone oxidation method

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CN201910844034.1A CN110683694A (en) 2019-09-06 2019-09-06 Method for treating ethyl chloride production wastewater by ozone oxidation method

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106186556A (en) * 2016-08-26 2016-12-07 湖北犇星农化有限责任公司 A kind of ozone Oxidation Treatment chlopyrifos produces the method for waste water
CN108928979A (en) * 2018-06-22 2018-12-04 杭州深瑞水务有限公司 A kind of technique of the waste liquid of processing second chlorine production
CN109467058A (en) * 2018-12-21 2019-03-15 浙江埃森化学有限公司 A kind of melting and oxidative purification of diethylaluminum monochloride by-product sulphur
CN109851096A (en) * 2019-01-31 2019-06-07 扬州帮手科技有限公司 The chemical treatment method of hydrolysis process waste water in a kind of diethylaluminum monochloride production process that resourcebility utilizes

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106186556A (en) * 2016-08-26 2016-12-07 湖北犇星农化有限责任公司 A kind of ozone Oxidation Treatment chlopyrifos produces the method for waste water
CN108928979A (en) * 2018-06-22 2018-12-04 杭州深瑞水务有限公司 A kind of technique of the waste liquid of processing second chlorine production
CN109467058A (en) * 2018-12-21 2019-03-15 浙江埃森化学有限公司 A kind of melting and oxidative purification of diethylaluminum monochloride by-product sulphur
CN109851096A (en) * 2019-01-31 2019-06-07 扬州帮手科技有限公司 The chemical treatment method of hydrolysis process waste water in a kind of diethylaluminum monochloride production process that resourcebility utilizes

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Application publication date: 20200114