CN111484195A - Harmless treatment method for high-concentration pesticide organic waste liquid - Google Patents
Harmless treatment method for high-concentration pesticide organic waste liquid Download PDFInfo
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- CN111484195A CN111484195A CN202010283228.1A CN202010283228A CN111484195A CN 111484195 A CN111484195 A CN 111484195A CN 202010283228 A CN202010283228 A CN 202010283228A CN 111484195 A CN111484195 A CN 111484195A
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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
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
- F23G7/00—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals
- F23G7/04—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste liquors, e.g. sulfite liquors
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/26—Treatment of water, waste water, or sewage by extraction
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/306—Pesticides
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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
- C02F3/00—Biological treatment of water, waste water, or sewage
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Abstract
The invention discloses a harmless treatment method of high-concentration pesticide organic waste liquid, which is divided into a channel a and a channel b for harmless treatment according to the components of the high-concentration pesticide organic waste liquid and comprises the following steps: (a1) introducing the high-concentration pesticide organic waste liquid into a distillation kettle; (a2) the waste liquid of (a1) enters an ozone oxidation section and then enters a biochemical facility; (b1) feeding the high-concentration pesticide organic waste liquid and an extracting agent into a static mixer according to a flow ratio, then feeding the mixture into a separation tower, and discharging an oil phase from the upper part and a water phase from the lower part; (b2) the oil phase enters a simple distillation kettle; (b3) the water phase enters an ozone oxidation section. The high-concentration pesticide organic waste liquid is effectively pretreated by extractive distillation before being subjected to ozone catalytic oxidation for advanced oxidation, so that a stable medium is ensured to enter ozone catalysis, the treatment pressure and the process burden of a working section are reduced by prolonging a process route, and the treatment efficiency and the running state of equipment and facilities are effectively improved.
Description
Technical Field
The invention belongs to the field of hazardous waste treatment, and particularly relates to a harmless treatment method of high-concentration pesticide organic waste liquid.
Background
The high-concentration ozone has unique effect on the organic high-concentration wastewater difficult to be biochemically generated under the alkali catalysis factor. The mechanism is that high-concentration ozone generates a large amount of OH with stronger chemical reaction capability, the structure of organic matters which are difficult to degrade can be changed into new substances, and an oxygenation functional group is introduced into the substances, so that the substances become biodegradable substances and are endowed with new chemical properties, and consequently, organic wastewater which is difficult to biochemically degrade can be decolored and deodorized, pollutants which are easy to biodegrade can be further removed by combining the traditional biochemical technology, the treatment cost is greatly reduced, the national environmental protection discharge standard is reached or the water quality requirement of sewage recycling is met, and the method has dual benefits of society and economy. The electrolysis technology can also well decompose organic matters in water, but the loss of the electrolyte of the anode is always a difficult problem, expensive rare metal alloy is used as the anode material abroad, but the processing technology is complex and has high cost, the popularization is difficult at present, and the practical application of the electrolysis technology in domestic environmental protection engineering is rarely seen. At present, advanced, practical, effective and economic wastewater treatment engineering technology is provided in the environmental protection technology of high-concentration organic wastewater difficult to be biochemically treated, and high-concentration advanced ozonization technology is highly concerned. The difficulty in the hazardous waste treatment process is that the source of the waste is unstable, the components are complex, even if the physicochemical properties of the waste liquid generated in different batches in the same workshop section of the same enterprise are different, the combined treatment of the waste of the comprehensive multi-production waste unit is more complex, and the problems of critical conditions and efficiency of the liquid material entering the ozone catalytic oxidation for advanced oxidation are specifically as follows:
1. hydroxyl free radicals released by ozone have certain selectivity and can not be effective to all organic components, and COD chemical oxygen demand borne by the ozone is not too high, otherwise, the expected removal rate and the task of degrading macromolecular complex organic matters can not be achieved.
2. The catalyst involved in advanced oxidation is the key of ozone catalysis, the good specific surface area and activity of the catalyst are the guarantee of ozone catalysis, and the prevention of the ozone catalysis from being blocked and inactivated too fast is a necessary work.
3. Ozone catalytic oxidation has large power consumption, and excessively high COD and excessive difficultly-degraded high-molecular organic matters will certainly influence the operation efficiency and efficiency of the ozone catalytic oxidation.
In the existing solid waste comprehensive disposal project, the number of the physicochemical disposal units is small, even if idle devices are arranged, the efficacy and the efficiency are low even if the device is operated reluctantly, the operation is difficult, the device is difficult to realize, the development of the industry to the real chemical industry in the directions of continuity, automation, intensification and stabilization is not facilitated, and the device becomes a defect in the solid waste comprehensive disposal.
Disclosure of Invention
The purpose of the invention is as follows: the invention aims to provide a harmless treatment method capable of effectively improving the treatment efficiency of high-concentration pesticide waste liquid.
The technical scheme is as follows: the invention relates to a harmless treatment method of high-concentration pesticide organic waste liquid, which is divided into a channel a and a channel b for harmless treatment according to the composition of the high-concentration pesticide organic waste liquid, wherein the channel a comprises the following steps:
(a1) introducing high-concentration pesticide organic waste liquid and packaging barrel washing water thereof into a distillation still, opening steam for heating, and directly introducing collected low boiling range substances into an incineration system;
(a2) carrying out water phase detection on COD of the characteristic pollutants in the waste liquid treated in the step (a1), when a COD detection value is higher than a COD standard value, continuing the treatment in the step (a1), when the COD detection value is not higher than the COD standard value, entering an ozone oxidation section, testing the salt content of soluble salt in the waste liquid after ozone oxidation is completed, when the test value of the salt content is higher than the salt content standard value, firstly entering single-effect evaporation, and when the test value of the salt content is not higher than the salt content standard value, directly entering a biochemical facility;
the channel b comprises the following steps:
(b1) treating insoluble substances in the high-concentration pesticide organic waste liquid by a pipeline filter, then enabling the high-concentration pesticide organic waste liquid and an extracting agent to enter a static mixer according to the flow ratio, then enabling the high-concentration pesticide organic waste liquid and the extracting agent to enter a separation tower, enabling an oil phase to flow out from the upper part and a water phase to flow out from the lower part;
(b2) the oil phase enters a simple distillation kettle, the extractant is separated out and recycled, and the extract enters an incinerator;
(b3) the water phase carries out the COD that the water phase detected the characteristic pollutant, and when the COD detected value was higher than the COD standard value, carries out the processing of a passageway, and when the COD detected value was not higher than the COD standard value, directly got into the ozone oxidation workshop section, through the salt content of ozone oxidation completion back test waste liquid soluble salt, when the test value of salt content was higher than the standard value, advanced single-effect evaporation that goes into, when not higher than the salt content standard value, directly got into biochemical facility.
Further, when the component concentration of the high-concentration pesticide organic waste liquid is less than or equal to 5 percent, the component composition of organic matters is less than 3, and the boiling point of distillate belongs to a low boiling range, directly carrying out a-channel treatment; when the component concentration of the high-concentration pesticide organic waste liquid is more than 5 percent and the component composition of the organic matter is not less than 3, the b-channel treatment is directly carried out.
Further, the COD standard value is 30000-50000 mg/L, and is selected according to the specific process and the stock solution composition.
Further, the standard value of the salt content is 1000-2500 mg/L, which is selected according to the specific process and the composition of the stock solution.
Further, the ozone oxidation section comprises: filtering floating materials and suspended solids in water by using a water collecting sedimentation tank, and then filtering the floating materials and the suspended solids by using a flow of 2m3And h, pressurizing by a pipeline booster pump with the head of 30m, metering the flow of a rotor, feeding the ozone and the waste liquid into a high-speed dynamic mixer for efficient gas-liquid mixing of the ozone and the waste liquid into a fog shape, improving the contact area and the reaction probability of the ozone and the sewage in the waste water, and favorably improving the dissolution rate and the utilization rate of the ozone, wherein the high-yield ozone with the concentration not lower than 40 mg/L is produced by a large ZT oxygen generator and a large ZT variable frequency ozone generator and is respectively injected into the high-speed dynamic mixer and an.
Furthermore, the oxidation tower is made of stainless steel, a micron-sized titanium plate porous gas diffuser formed by sintering detachable titanium powder is arranged in the oxidation tower, and the ozone gas can enter the liquid phase by adopting gas-liquid reverse contact.
Furthermore, the conditions of the size, density, color and the like of the reaction bubbles can be observed from the sight glass of the oxidation towerIn the case of waste liquid, after 5-10 min of quick and strong oxidation reaction, the waste liquid can reach the flocculation, decoloration and deodorization effects of the high-concentration organic matter waste water which is difficult to degrade and high in concentration, and can be degraded into new organic matters which can be directly biochemical and collected into a water collecting adjusting tank (meanwhile, partial reaction products can be directly changed into CO)2Gas evolution). The specific time can be set according to the COD value detected by the sampling port and the production experience.
Further, the extracting agent is diesel oil or carbon tetrachloride.
Has the advantages that: the treatment method of the invention utilizes distillation and extraction to enrich and concentrate part of high-concentration organic matter with lower water content, organic matter with low boiling point and higher calorific value to enter an incineration system, can partially remove complex organic matter, reduce the burden of advanced oxidation treatment and improve the ozone catalysis efficiency; the pollution characteristic of the water phase is better improved after the extraction, distillation and delamination, the process aim of homogenizing and equalizing the quantity of the same batch of materials is fulfilled, the problem of elastic operation is solved, the problem of continuous production of a batch of materials within a time period is solved, and the problem of accurately, qualitatively and quantitatively acquiring basic data of material balance is solved. The high-concentration pesticide organic waste liquid is effectively pretreated by extractive distillation before advanced oxidation of ozone catalytic oxidation, stable media are guaranteed to enter ozone catalysis, treatment pressure and process burden of a working section are relieved by prolonging a process route, and treatment efficiency and the running state of equipment and facilities are effectively improved.
Drawings
FIG. 1 is a process flow diagram of the treatment process of the present invention.
Detailed Description
For a further understanding of the present invention, reference will now be made in detail to the embodiments illustrated in the drawings.
Example 1
The high-concentration pesticide waste liquid is electricity-proof liquid, contains dimethyl carbonate and lithium hexafluorophosphate, has a total content of less than 5%, and is directly treated by using an a channel, as shown in fig. 1, and comprises the following steps:
(a1) introducing high-concentration pesticide organic waste liquid and packaging barrel washing water thereof into a distillation still, opening steam for heating, and directly introducing collected low-boiling-point substances into an incineration system;
(a2) carrying out water phase detection on the waste liquid treated in the step (a1) to obtain characteristic pollutant COD (chemical oxygen demand) of 13300 mg/L and lower than 30000 mg/L (COD standard value), introducing into an ozone oxidation section, filtering floating substances and suspended solids in water by using a water collecting sedimentation tank, and then passing through a flow rate of 2m3And h, pressurizing by a pipeline booster pump with the head of 30m, metering the flow of a rotor, feeding the ozone and the waste liquid into a high-speed dynamic mixer for efficient gas-liquid mixing of the ozone and the waste liquid into a fog shape, improving the contact area and the reaction probability of the ozone and the sewage in the waste water, and being favorable for improving the dissolution rate and the utilization rate of the ozone, wherein the ozone with the concentration of not less than 40 mg/L and high yield produced by a ZT large-scale oxygenerator and a large ZT variable frequency ozonizer is respectively injected into the high-speed dynamic mixer and an oxidation tower for reaction, and the salt content of soluble salt of the test waste liquid after the ozone oxidation is finished is 1700 mg/L and is less than the.
The wastewater indexes before and after the treatment by the process are compared in the table 1.
TABLE 1
Example 2
The high-concentration pesticide waste liquid is an evaporation waste liquid, contains polyhydric alcohols, fatty acids and lipids, has a total content higher than 5%, and is directly treated by using a b channel, as shown in fig. 1, and the method comprises the following steps:
(b1) treating insoluble substances in the high-concentration pesticide organic waste liquid by a pipeline filter, then enabling the high-concentration pesticide organic waste liquid and diesel oil to enter a static mixer according to the flow ratio, then enabling the high-concentration pesticide organic waste liquid and the diesel oil to enter a separation tower, enabling an oil phase to flow out from the upper part and a water phase to flow out from the lower part;
(b2) the oil phase enters a simple distillation kettle, the extractant is separated out and recycled, and the extract enters an incinerator;
(b3) the water phase is subjected to water phase detection to detect characteristic pollutants with COD of 45000 mg/L higher than COD standard value of 30000 mg/L, the treatment of the channel a is continued, the COD detected for the second time is 13400 mg/L and lower than 30000 mg/L, the water phase enters an ozone oxidation section, and the water phase is firstly usedFiltering floating materials and suspended solids in water by a water collecting sedimentation tank, and then carrying out flow rate of 2m3The method comprises the steps that a pipeline booster pump with the lift of 30m is pressurized, the flow of a rotor is metered into a high-speed dynamic mixer to perform efficient gas-liquid mixing of ozone and waste liquid to form mist, the contact area and the reaction probability of the ozone and sewage in the waste water are improved, the dissolution rate and the utilization rate of the ozone are improved, high-yield ozone with the concentration of not less than 40 mg/L is produced by a large ZT oxygen generator and a large ZT variable frequency ozone generator, the ozone is respectively injected into the high-speed dynamic mixer and an oxidation tower to perform reaction, the oxidation tower is made of stainless steel, a micron-sized titanium plate porous gas diffuser formed by sintering detachable titanium powder is arranged in the oxidation tower, the ozone enters a liquid phase by adopting reverse gas-liquid contact, the conditions of reaction size, density, color and the like can be observed from an oxidation tower sight glass, the waste liquid undergoes 10 minutes of rapid and strong oxidation reaction, and the waste liquid is flocculated, decolored and deodorized, the high-concentration organic wastewater with difficult degradation is degraded into new organic matters2Gas escape), the contrast condition before and after the reaction of waste water and ozone can be observed at any time from waste water sample connection 1 and sample connection 2 (wherein, sample connection 1 and sample connection 2 set up respectively in the different height of reaction tower, and the sample is in order to ensure the reaction is complete in different positions). The subsequent treatment process is a traditional biochemical process combining anaerobic treatment and aerobic treatment, organic pollutants in a colloid and dissolved state in the wastewater can be removed, the removal rate of COD and BOD can reach more than 90%, and the wastewater can be further discharged and recycled up to the standard through further ozone disinfection and sediment sand filtration processes, so that the purpose of recycling the wastewater is achieved.
The wastewater indexes before and after the treatment by the process are compared in the table 2.
TABLE 2
After the ozone oxidation is finished, the salt content of soluble salt of the test waste liquid is 1700 mg/L, which is less than the standard value of the salt content of 2000 mg/L, and the test waste liquid directly enters a biochemical facility.
Claims (9)
1. A harmless treatment method of high-concentration pesticide organic waste liquid is characterized in that harmless treatment is carried out by dividing the high-concentration pesticide organic waste liquid into a channel a and a channel b according to the composition of the high-concentration pesticide organic waste liquid, wherein the channel a comprises the following steps:
(a1) introducing high-concentration pesticide organic waste liquid and packaging barrel washing water thereof into a distillation still, opening steam for heating, and directly introducing collected low boiling range substances into an incineration system;
(a2) carrying out water phase detection on COD of the characteristic pollutants in the waste liquid treated in the step (a1), when a COD detection value is higher than a COD standard value, continuing the treatment in the step (a1), when the COD detection value is not higher than the COD standard value, entering an ozone oxidation section, testing the salt content of soluble salt in the waste liquid after ozone oxidation is completed, when the test value of the salt content is higher than the salt content standard value, firstly entering single-effect evaporation, and then entering a biochemical facility, and when the test value of the salt content is not higher than the salt content standard value, directly entering the biochemical facility;
the channel b comprises the following steps:
(b1) treating insoluble substances in the high-concentration pesticide organic waste liquid by a pipeline filter, then enabling the high-concentration pesticide organic waste liquid and an extracting agent to enter a static mixer according to the flow ratio, then enabling the high-concentration pesticide organic waste liquid and the extracting agent to enter a separation tower, enabling an oil phase to flow out from the upper part and a water phase to flow out from the lower part;
(b2) the oil phase enters a simple distillation kettle, the extractant is separated out and recycled, and the extract enters an incinerator;
(b3) the water phase carries out the COD that the water phase detected the characteristic pollutant, and when the COD detected value was higher than the COD standard value, carries out the processing of a passageway, and when the COD detected value was not higher than the COD standard value, directly got into the ozone oxidation workshop section, through the salt content of ozone oxidation completion back test waste liquid soluble salt, when the test value of salt content was higher than the standard value, advanced single-effect evaporation that goes into, when not higher than the salt content standard value, directly got into biochemical facility.
2. The method for harmless treatment of the high-concentration pesticide organic waste liquid as claimed in claim 1, wherein when the concentration of the components of the high-concentration pesticide organic waste liquid is less than or equal to 5%, the composition of the components of the organic substances is less than 3, and the boiling point of the distillate belongs to a low boiling range, the channel a treatment is directly performed; when the component concentration of the high-concentration pesticide organic waste liquid is more than 5 percent and the component composition of organic matters is not less than 3, the b-channel treatment is directly carried out.
3. The method for the harmless treatment of the high concentration pesticide organic waste liquid as claimed in claim 1, wherein the COD standard value is 30000-50000 mg/L.
4. The method as claimed in claim 1, wherein the standard value of the salt content is 1000-2500 mg/L.
5. The method for the harmless treatment of the high-concentration pesticide organic waste liquid according to claim 1, wherein the ozone oxidation section comprises a water collection sedimentation tank for filtering floating substances and suspended solids in water, and then the water collection sedimentation tank is pressurized by a pipeline booster pump and enters a high-speed dynamic mixer through rotor flow metering to perform efficient gas-liquid mixing of ozone and the waste liquid to form mist, wherein the high-yield ozone with the concentration of not less than 40 mg/L produced by a ZT large oxygen generator and a ZT variable frequency ozone generator is respectively injected into the high-speed dynamic mixer and an oxidation tower to perform reaction.
6. The method as claimed in claim 5, wherein the oxidation tower is made of stainless steel, and has a porous gas diffuser made of detachable sintered titanium powder and made of micron-sized titanium plate, and the gas diffuser is in gas-liquid contact with the porous gas diffuser.
7. The method for harmless treatment of the high-concentration pesticide organic waste liquid as claimed in claim 5 or 6, wherein the waste liquid is subjected to an ozone oxidation reaction in an oxidation tower for 5-10 minutes.
8. The method for the harmless treatment of the high-concentration pesticide organic waste liquid as claimed in claim 5, wherein the flow rate of the pipeline booster pump is 2m3H, lift30m。
9. The method of claim 1, wherein the extractant is diesel or carbon tetrachloride.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113390091A (en) * | 2021-05-29 | 2021-09-14 | 河南中环信环保科技股份有限公司 | Method for treating organic strong acid dangerous waste liquid |
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