CN210885671U - Recovery unit of metribuzin production waste acid water - Google Patents
Recovery unit of metribuzin production waste acid water Download PDFInfo
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- CN210885671U CN210885671U CN201921829111.8U CN201921829111U CN210885671U CN 210885671 U CN210885671 U CN 210885671U CN 201921829111 U CN201921829111 U CN 201921829111U CN 210885671 U CN210885671 U CN 210885671U
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Abstract
The utility model relates to a recovery unit of metribuzin production waste acid water, including the extraction cauldron, with the extraction cauldron aeration cauldron that is linked together, with the aeration cauldron be linked together the sedimentation tank, with the resin adsorption tower that is linked together of sedimentation tank, with the concentrated cauldron that is linked together of resin adsorption tower. The utility model discloses can be with the concentrated sulfuric acid of spent acid water treatment for can recycling, and treatment facility is simple, and the energy consumption is low, under the increasingly severe environmental protection situation, has great practicality and economic nature.
Description
Technical Field
The utility model belongs to the technical field of pesticide waste water treatment, concretely relates to recovery unit of metribuzin production waste acid water.
Background
Metribuzin is a selective herbicide and is mainly used for preventing and removing weeds in field crops such as soybeans, potatoes, tomatoes, sugarcanes, corns and the like. The novel process for producing metribuzin technical mainly uses triazinone as a reaction intermediate, concentrated sulfuric acid (the content is more than or equal to 96 percent, and COD (chemical oxygen demand) is less than or equal to 1000mg/L) is used as a reaction solvent in the methyl esterification and sulfate synthesis processes in the synthesis route, and a large amount of waste sulfuric acid water is generated in the post-treatment process after water is added and washed after the reaction is finished. The waste acid has the concentration of about 30-60%, and contains 0.1-0.3% of triazone, 0.1-0.3% of metribuzin, a small amount of methanol, sulfate and other organic matters.
The existing method for treating the waste acid water generally adopts a process route of adding alkali for neutralization and extracting sulfate. For example, CN109912094 discloses a method for treating metribuzin integrated process wastewater, which needs a large amount of alkali to neutralize waste acid, and obtains industrial anhydrous sodium sulphate by a series of operations of reducing organic matters and extracting salt through multiple-effect evaporation.
CN102173525 describes a pretreatment method for treating metribuzin wastewater, which has a removal effect of more than 70% on COD of the wastewater by adjusting pH, liquid membrane separation, complex extraction and the like.
CN101445304 introduces a method for treating metribuzin production methylation wastewater, which adopts a deodorization and color removal-rectification-evaporation-oxidation-extraction process.
The above wastewater treatment methods are all to adjust the pH of the acidic wastewater to be neutral or alkaline, then remove the organic matters in the wastewater, and extract a large amount of sulfate generated by neutralization through an evaporation salt extraction mode. The treatment process not only consumes a large amount of alkali, but also produces a large amount of sulfate with low added value, thereby causing the waste of raw materials, resources and energy.
SUMMERY OF THE UTILITY MODEL
The utility model aims at providing a can be with the recovery unit of concentrated sulfuric acid of spent acid water treatment for can recycling.
For solving the technical problem, the utility model discloses a following technical scheme:
one aspect of the utility model is to provide a recovery unit of metribuzin production waste acid water, including the extraction cauldron, with the extraction cauldron aeration cauldron that is linked together, with the sedimentation tank that is linked together of aeration cauldron, with the sedimentation tank be linked together resin adsorption tower, with the concentrated cauldron that is linked together of resin adsorption tower.
Preferably, the recovery device further comprises a first storage tank communicated with the extraction kettle and used for storing waste acid water, a second storage tank respectively communicated with the aeration kettle and the sedimentation tank and used for storing waste acid water from the aeration kettle, and a third storage tank respectively connected with the resin adsorption tower and the concentration kettle and commonly used for storing acid water from the resin adsorption tower.
Further preferably, the first storage tank is installed at a position higher than the extraction tank, the second storage tank is installed at a position higher than the aeration tank and the sedimentation tank, and the third storage tank is installed at a position higher than the resin adsorption tower and the concentration tank.
Preferably, the recovery device further comprises a first condenser communicated with the aeration kettle and used for collecting the low-boiling-point solvent, and a second condenser connected with the concentration kettle and used for collecting water.
Preferably, the sedimentation tank is a horizontal flow type grit chamber.
Preferably, the resin adsorption towers are arranged in parallel by switching valves, and preferably 3-20 resin adsorption towers are arranged, so that part of the resin adsorption towers can be subjected to adsorption treatment, and part of the resin adsorption towers can be subjected to desorption and regeneration treatment.
Another aspect of the utility model is to provide a cyclic utilization method of metribuzin production waste acid water, including following step:
(1) extracting waste acid water from metribuzin production to recover part of triazinone and metribuzin and reduce organic matters in the waste water;
(2) aerating and blowing off the extracted waste acid water to remove low-boiling-point substances such as methanol and the like;
(3) removing insoluble substances in the waste acid water after aeration stripping;
(4) performing resin adsorption on the waste acid water treated in the step (3) to remove residual organic matters, and reducing COD (chemical oxygen demand) of the waste water from 4000-5000mg/L to below 1000mg/L, wherein the original waste water is changed from yellow to light yellow, and the odor of the waste water is basically eliminated;
(5) and concentrating the acid water after resin adsorption to obtain concentrated sulfuric acid.
Preferably, in the step (1), the waste acid water is extracted by using an organic solvent.
Further preferably, the organic solvent is one or more of toluene, chlorobenzene, xylene, cyclohexane and methylcyclohexane.
Most preferably, the organic solvent is toluene.
Further preferably, the feeding volume ratio of the waste acid water to the organic solvent is 1.5-5: 1.
Specifically, the waste acid water and the organic solvent are fully stirred and mixed, then the mixture is kept stand for layering, and the water layer is subjected to the step (2).
Preferably, the organic phase after standing and layering is concentrated and then sheathed into the methylation reaction stage of the metribuzin production process.
More specifically, the stirring time is controlled to be 0.5-1 h.
Preferably, the temperature for extraction in the step (1) is controlled to be 0-100 ℃, preferably 30-80 ℃, and most preferably 60-70 ℃.
Preferably, the gas used for aeration in step (2) is air and/or nitrogen.
Preferably, the volume of the gas introduced is controlled to be 10-100 times/h of the volume of the acid water.
Preferably, the temperature of the stripping in the step (2) is controlled to be 40-100 ℃, and further preferably 60-90 ℃.
Preferably, the time of aeration stripping is controlled to be 2-5 h.
Preferably, after the aeration is controlled to be finished, the temperature is reduced to 40-50 ℃ to carry out the step (3).
Preferably, the insoluble matter is removed in step (3) by treatment with dust and sand.
Preferably, the horizontal flow rate of the water flow in the step (3) is controlled to be 0.01-0.3 m/s, and the settling time is controlled to be 2-30 min.
Preferably, in step (4), the resin is a macroporous adsorbent resin, such as DH-1, DH-2, D001, etc.
Preferably, the feeding speed of the resin adsorption is controlled to be 0.05-5 BV, and further preferably 0.2-0.5 BV.
Wherein BV is feed volume per hour per resin volume.
Preferably, the resin adsorption is carried out in a downfeed mode.
Preferably, hot water at 90-95 ℃ is used as a desorption agent of the resin.
Preferably, the concentration in the step (5) is carried out at a temperature of 90-130 ℃, and the concentration is carried out under a reduced pressure condition.
The utility model discloses the index of well spent acid water is as follows:
the utility model discloses in, the concentration of concentrated sulfuric acid after the processing is 80 ~ 98%, colorless odorless.
Due to the implementation of the above technical scheme, compared with the prior art, the utility model has the following advantages:
the utility model discloses can be with the concentrated sulfuric acid of spent acid water treatment for can recycling, and treatment facility is simple, and the energy consumption is low, under the increasingly severe environmental protection situation, has great practicality and economic nature.
Drawings
FIG. 1 is a schematic view of an embodiment of a recycling apparatus;
wherein, 1, a first storage tank; 2. an extraction kettle; 3. an aeration kettle; 4. a first condenser; 5. a second reservoir; 6. a sedimentation tank; 7. a resin adsorption tower; 8. a third reservoir; 9. a concentration kettle; 10. a second condenser.
Detailed Description
The present invention will be described in further detail with reference to specific examples. It is to be understood that these embodiments are provided to illustrate the basic principles, main features and advantages of the present invention, and the present invention is not limited by the following embodiments. The implementation conditions used in the examples can be further adjusted according to specific requirements, and the implementation conditions not indicated are generally the conditions in routine experiments. The contents are all mass contents.
The recovery device for metribuzin production waste acid water comprises a first storage tank 1 for storing waste acid water, an extraction kettle 2 with the upper part communicated with the lower part of the first storage tank 1, an aeration kettle 3 with the upper part communicated with the bottom of the extraction kettle 2, a first condenser 4 communicated with the upper part of the aeration kettle 3 and used for collecting low boiling point solvent, a second storage tank 5 communicated with the bottom of the aeration kettle 3 and used for storing waste acid water from the aeration kettle 3, a sedimentation tank 6 communicated with the lower part of the second storage tank 5, a resin adsorption tower 7 with the bottom communicated with the sedimentation tank 6, a third storage tank 8 communicated with the top of the resin adsorption tower 7 and used for storing acid water from the resin adsorption tower 7, a concentration kettle 9 communicated with the lower part of the third storage tank 8, and a second condenser 10 communicated with the upper part of the concentration kettle 9 and used for collecting water.
The first storage tank 1 is arranged higher than the extraction kettle 2, the second storage tank 5 is arranged higher than the aeration kettle 3 and the sedimentation tank 6, and the third storage tank 8 is arranged higher than the resin adsorption tower 7 and the concentration kettle 9. The water layer in the extraction kettle 2 is pumped into the first storage tank 1 by a pump, the acid liquid in the aeration kettle 3 is pumped into the second storage tank 5 by a pump, and the liquid in the sedimentation tank 6 is pumped into the resin adsorption tower 7 by a pump.
The sedimentation tank 6 is the advection formula grit chamber, resin adsorption tower 7 is a plurality of and through the parallelly connected setting of switching valve, preferably 3 ~ 20, be 3 in the picture, a resin adsorption tower 7 adsorbs to the saturation back, switches to another resin system through the switching valve and adsorbs the processing, this resin adsorption tower 7 that adsorbs the saturation adopts 90 ~ 95 ℃ of hot water as desorption agent, open the measuring pump, pump hot water into from the top of the tower of resin adsorption tower 7 through the pipeline, desorption liquid flows into concentrated cauldron 9 from the bottom.
Example 1
The specific indexes of the waste acid water generated by the metribuzin process are as follows:
| index (I) | Sulfuric acid% | COD mg/L | Appearance of the product | Smell(s) | Triazinone% | Metribuzin% |
| Spent acid water | 43 | 12080 | Yellow colour | Bad smell | 0.21 | 0.18 |
Adding toluene into the waste acid water for 8t, heating to 60-70 ℃, keeping the temperature, stirring for 1h, standing for 0.5h, layering, and feeding the lower layer acid water into an aeration kettle 3. The toluene phase is condensed and then is sleeved into a methylation reaction section. The temperature of the aeration kettle 3 is 80-90 ℃, the compressed air is introduced at the speed of 5 cubic/min, the aeration time is 2 hours, and the temperature is reduced to 40-50 ℃ and then the mixture enters a sedimentation tank. The flow velocity of the sedimentation tank is 0.1m/s, the sedimentation time is 30min, and the settled solid is treated according to the sludge. After sedimentation, the COD value of the acid water is 6810mg/L, the acid water enters a resin tower filled with DH-1 macroporous adsorption resin from the lower end for adsorption, and the material is discharged from the upper end at the feeding speed of 0.5 BV. After discharging, the COD data is measured to be 620mg/L, the acid water enters a concentration kettle 9 for concentration, the concentration temperature is 90-130 ℃, the pressure is-0.095 MPa, and the concentration and dehydration are carried out until the sulfuric acid content is 98%. The obtained concentrated sulfuric acid is colorless and odorless, and can be directly used.
Example 2
The specific indexes of the waste acid water generated by the metribuzin process are as follows:
| index (I) | Sulfuric acid% | COD mg/L | Appearance of the product | Smell(s) | Triazinone% | Metribuzin% |
| Spent acid water | 50 | 10800 | Deep yellow | Bad smell | 0.15 | 0.10 |
Adding toluene into the waste acid water for 8t, heating to 60-70 ℃, keeping the temperature, stirring for 1h, standing for 0.5h, layering, and feeding the lower layer acid water into an aeration kettle 3. The toluene phase is condensed and then is sleeved into a methylation reaction section. The temperature of the aeration kettle 3 is 60-70 ℃, the compressed air is introduced at the speed of 6 cubic/min, the aeration time is 2 hours, and the mixture enters a sedimentation tank after being cooled to 40-50 ℃. The flow velocity of the sedimentation tank is 0.1m/s, the sedimentation time is 30min, and the settled solid is treated according to the sludge. After sedimentation, the COD value of the acid water is 5110mg/L, the acid water enters a resin tower filled with DH-1 macroporous adsorption resin from the lower end for adsorption, and the material is discharged from the upper end at the feeding speed of 0.5 BV. After discharging, measuring the COD data to be 720mg/L, feeding the acid water into a concentration kettle 9 for concentration, wherein the concentration temperature is 90-130 ℃, the pressure is-0.095 MPa, and the concentration and dehydration are carried out until the sulfuric acid content is 98%. The obtained concentrated sulfuric acid is colorless and odorless, and can be directly used.
Example 3
The specific indexes of the waste acid water generated by the metribuzin process are as follows:
| index (I) | Sulfuric acid% | COD mg/L | Appearance of the product | Smell(s) | Triazinone% | Metribuzin% |
| Spent acid water | 40 | 23000 | Deep yellow | Bad smell | 0.25 | 0.21 |
Adding toluene into the waste acid water for 8t, heating to 60-70 ℃, keeping the temperature, stirring for 1h, standing for 0.5h, layering, and feeding the lower layer acid water into an aeration kettle 3. The toluene phase is condensed and then is sleeved into a methylation reaction section. The temperature of the aeration kettle 3 is 60-70 ℃, the compressed air is introduced at the speed of 2 cubic/min, the aeration time is 5 hours, and the mixture enters a sedimentation tank after being cooled to 40-50 ℃. The flow velocity of the sedimentation tank is 0.1m/s, the sedimentation time is 30min, and the settled solid is treated according to the sludge. The COD value of the settled acid water is 6130mg/L, the settled acid water enters a resin tower filled with DH-1 macroporous adsorption resin from the lower end for adsorption, and the acid water is discharged from the upper end at the feeding speed of 0.3 BV. After discharging, the COD data is 630mg/L, the acid water enters a concentration kettle 9 for concentration, the concentration temperature is 90-130 ℃, the pressure is-0.095 MPa, and the concentration and dehydration are carried out until the sulfuric acid content is 98%. The obtained concentrated sulfuric acid is colorless and odorless, and can be directly used.
The above embodiments are only for illustrating the technical concept and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the contents of the present invention and to implement the present invention, so as not to limit the protection scope of the present invention, and all equivalent changes or modifications made according to the spirit of the present invention should be covered by the protection scope of the present invention.
Claims (6)
1. The utility model provides a recovery unit of metribuzin production waste acid water which characterized in that: comprises an extraction kettle (2), an aeration kettle (3) communicated with the extraction kettle (2), a sedimentation tank (6) communicated with the aeration kettle (3), a resin adsorption tower (7) communicated with the sedimentation tank (6), and a concentration kettle (9) communicated with the resin adsorption tower (7).
2. The recycling apparatus according to claim 1, wherein: the recovery unit still include with extraction cauldron (2) link to each other general first storage tank (1) that is used for storing waste acid water, respectively with aeration cauldron (3) with sedimentation tank (6) link to each other general second storage tank (5) that are used for storing the waste acid water that comes from aeration cauldron (3), respectively with resin adsorption tower (7) with concentrated cauldron (9) be linked together and be used for storing the third storage tank (8) that come from the acid water of resin adsorption tower (7).
3. The recycling apparatus according to claim 2, wherein: the first storage tank (1) is arranged higher than the extraction kettle (2), the second storage tank (5) is arranged higher than the aeration kettle (3) and the sedimentation tank (6), and the third storage tank (8) is arranged higher than the resin adsorption tower (7) and the concentration kettle (9).
4. The recycling apparatus according to claim 1, wherein: the recovery device also comprises a first condenser (4) which is connected with the aeration kettle (3) and is used for collecting the low boiling point solvent, and a second condenser (10) which is connected with the concentration kettle (9) and is used for collecting water.
5. The recycling apparatus according to claim 1, wherein: the sedimentation tank (6) is a horizontal flow type grit chamber.
6. The recycling apparatus according to claim 1, wherein: the resin adsorption towers (7) are arranged in parallel through switching valves.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110683700A (en) * | 2019-10-29 | 2020-01-14 | 江苏七洲绿色化工股份有限公司 | Recovery device and recycling method for metribuzin production waste acid water |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110683700A (en) * | 2019-10-29 | 2020-01-14 | 江苏七洲绿色化工股份有限公司 | Recovery device and recycling method for metribuzin production waste acid water |
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