CN110683700A - Recovery device and recycling method for metribuzin production waste acid water - Google Patents
Recovery device and recycling method for metribuzin production waste acid water Download PDFInfo
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- CN110683700A CN110683700A CN201911034112.8A CN201911034112A CN110683700A CN 110683700 A CN110683700 A CN 110683700A CN 201911034112 A CN201911034112 A CN 201911034112A CN 110683700 A CN110683700 A CN 110683700A
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- acid water
- waste acid
- metribuzin
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- aeration
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 85
- 239000002253 acid Substances 0.000 title claims abstract description 77
- 239000002699 waste material Substances 0.000 title claims abstract description 53
- 239000005583 Metribuzin Substances 0.000 title claims abstract description 36
- FOXFZRUHNHCZPX-UHFFFAOYSA-N metribuzin Chemical compound CSC1=NN=C(C(C)(C)C)C(=O)N1N FOXFZRUHNHCZPX-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 238000000034 method Methods 0.000 title claims abstract description 31
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 23
- 238000004064 recycling Methods 0.000 title claims abstract description 22
- 238000011084 recovery Methods 0.000 title claims description 11
- 239000011347 resin Substances 0.000 claims abstract description 48
- 229920005989 resin Polymers 0.000 claims abstract description 48
- 238000001179 sorption measurement Methods 0.000 claims abstract description 43
- 238000005273 aeration Methods 0.000 claims abstract description 35
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000000126 substance Substances 0.000 claims abstract description 9
- 238000004062 sedimentation Methods 0.000 claims description 27
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 26
- 238000000605 extraction Methods 0.000 claims description 18
- 239000003960 organic solvent Substances 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 4
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- 238000009835 boiling Methods 0.000 claims description 2
- 239000000428 dust Substances 0.000 claims description 2
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 239000004576 sand Substances 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 239000002351 wastewater Substances 0.000 abstract description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract description 9
- QMNWYGTWTXOQTP-UHFFFAOYSA-N 1h-triazin-6-one Chemical compound O=C1C=CN=NN1 QMNWYGTWTXOQTP-UHFFFAOYSA-N 0.000 abstract description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 3
- 239000001301 oxygen Substances 0.000 abstract description 3
- 229910052760 oxygen Inorganic materials 0.000 abstract description 3
- 238000007664 blowing Methods 0.000 abstract description 2
- 238000005265 energy consumption Methods 0.000 abstract description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 5
- 238000007069 methylation reaction Methods 0.000 description 5
- 238000003795 desorption Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000009965 odorless effect Effects 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000003513 alkali Substances 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 239000010802 sludge Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- 208000003643 Callosities Diseases 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 244000068988 Glycine max Species 0.000 description 1
- 235000010469 Glycine max Nutrition 0.000 description 1
- 206010020649 Hyperkeratosis Diseases 0.000 description 1
- 235000007688 Lycopersicon esculentum Nutrition 0.000 description 1
- 240000000111 Saccharum officinarum Species 0.000 description 1
- 235000007201 Saccharum officinarum Nutrition 0.000 description 1
- 240000003768 Solanum lycopersicum Species 0.000 description 1
- 244000061456 Solanum tuberosum Species 0.000 description 1
- 235000002595 Solanum tuberosum Nutrition 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000007806 chemical reaction intermediate Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 238000004332 deodorization Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 244000037666 field crops Species 0.000 description 1
- 230000002363 herbicidal effect Effects 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000011987 methylation Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- FWFGVMYFCODZRD-UHFFFAOYSA-N oxidanium;hydrogen sulfate Chemical compound O.OS(O)(=O)=O FWFGVMYFCODZRD-UHFFFAOYSA-N 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 235000012015 potatoes Nutrition 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
Images
Classifications
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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
- C02F1/02—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
- C02F1/26—Treatment of water, waste water, or sewage by extraction
-
- 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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
-
- 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
- C02F2001/007—Processes including a sedimentation step
-
- 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
- C02F2101/34—Organic compounds containing oxygen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F7/00—Aeration of stretches of water
Abstract
The invention relates to a recycling method of spent acid water in metribuzin production, which comprises the following steps: (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. The invention can process the waste acid water into the concentrated sulfuric acid which can be recycled, has simple processing equipment and low energy consumption, and has greater practicability and economical efficiency under the increasingly severe environment-friendly situation.
Description
Technical Field
The invention belongs to the technical field of pesticide wastewater treatment, and particularly relates to a recovery device and a recycling method for 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.
Disclosure of Invention
The invention aims to provide a recovery device and a recycling method for treating waste acid water into recyclable concentrated sulfuric acid.
In order to solve the technical problems, the invention adopts the following technical scheme:
one aspect of the invention provides a recycling method of spent acid water in metribuzin production, which comprises the following steps:
(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 indexes of the waste acid water in the invention are as follows:
in the invention, the concentration of the treated concentrated sulfuric acid is 80-98%, and the concentrated sulfuric acid is colorless and odorless.
The other aspect of the invention provides a recovery device of metribuzin production waste acid water, which comprises an extraction kettle, an aeration kettle communicated with the extraction kettle, a sedimentation tank communicated with the aeration kettle, a resin adsorption tower communicated with the sedimentation tank, and a concentration kettle communicated with the 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.
Due to the implementation of the technical scheme, compared with the prior art, the invention has the following advantages:
the invention can process the waste acid water into the concentrated sulfuric acid which can be recycled, has simple processing equipment and low energy consumption, and has greater practicability and economical efficiency under the increasingly severe environment-friendly situation.
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, essential 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 merely illustrative of the technical concept and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the content of the present invention and implement the invention, and not to limit the scope of the invention, and all equivalent changes or modifications made according to the spirit of the present invention should be covered by the scope of the present invention.
Claims (16)
1. A recycling method of metribuzin production waste acid water is characterized in that: the method comprises the following steps:
(1) extracting the waste acid water from metribuzin production;
(2) aerating and stripping the extracted waste acid water;
(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);
(5) and concentrating the acid water after resin adsorption to obtain concentrated sulfuric acid.
2. The recycling method of metribuzin production waste acid water according to claim 1, characterized in that: in the step (1), an organic solvent is adopted to extract the waste acid water.
3. The recycling method of metribuzin production waste acid water according to claim 2, characterized in that: the organic solvent is one or more of toluene, chlorobenzene, xylene, cyclohexane and methylcyclohexane.
4. The recycling method of metribuzin production waste acid water according to claim 1, characterized in that: controlling the extraction temperature in the step (1) to be 0-100 ℃.
5. The recycling method of metribuzin production waste acid water according to claim 1, characterized in that: and (3) adopting air and/or nitrogen as gas for aeration in the step (2).
6. The recycling method of metribuzin production waste acid water according to claim 1, characterized in that: controlling the stripping temperature in the step (2) to be 40-100 ℃.
7. The recycling method of metribuzin production waste acid water according to claim 1, characterized in that: and (3) removing the insoluble substances by adopting dust and sand treatment, controlling the horizontal flow velocity of water flow to be 0.01-0.3 m/s, and settling time to be 2-30 min.
8. The recycling method of metribuzin production waste acid water according to claim 1, characterized in that: in the step (4), the resin is macroporous adsorption resin.
9. The recycling method of metribuzin production waste acid water according to claim 1, characterized in that: and controlling the feeding speed of the resin adsorption to be 0.05-5 BV.
10. The recycling method of metribuzin production waste acid water according to claim 1, characterized in that: and the resin adsorption is carried out by adopting a lower feeding mode.
11. 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).
12. The recycling apparatus according to claim 11, 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).
13. The recycling apparatus according to claim 12, 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).
14. The recycling apparatus according to claim 11, 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.
15. The recycling apparatus according to claim 11, wherein: the sedimentation tank (6) is a horizontal flow type grit chamber.
16. The recycling apparatus according to claim 11, wherein: the resin adsorption towers (7) are arranged in parallel through switching valves.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101020586A (en) * | 2006-02-16 | 2007-08-22 | 大连市环境保护总公司 | Process of treating waste acid containing nitro compound in TNT production |
| CN102295380A (en) * | 2011-08-19 | 2011-12-28 | 杭州江南科学研究院有限公司 | Processing and recovering method of aromatic nitro-compound wastewater |
| EP2586519A1 (en) * | 2011-10-24 | 2013-05-01 | cobos Fluid Service GmbH | Processing of contaminated waste water from the production of plant protection agents |
| CN109912094A (en) * | 2019-03-04 | 2019-06-21 | 江苏南大华兴环保科技股份公司 | A kind for the treatment of process and its operation method of metribuzin discharged wastewater met the national standard collaboration salt recycling |
| CN210885671U (en) * | 2019-10-29 | 2020-06-30 | 江苏七洲绿色化工股份有限公司 | Recovery unit of metribuzin production waste acid water |
-
2019
- 2019-10-29 CN CN201911034112.8A patent/CN110683700A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101020586A (en) * | 2006-02-16 | 2007-08-22 | 大连市环境保护总公司 | Process of treating waste acid containing nitro compound in TNT production |
| CN102295380A (en) * | 2011-08-19 | 2011-12-28 | 杭州江南科学研究院有限公司 | Processing and recovering method of aromatic nitro-compound wastewater |
| EP2586519A1 (en) * | 2011-10-24 | 2013-05-01 | cobos Fluid Service GmbH | Processing of contaminated waste water from the production of plant protection agents |
| CN109912094A (en) * | 2019-03-04 | 2019-06-21 | 江苏南大华兴环保科技股份公司 | A kind for the treatment of process and its operation method of metribuzin discharged wastewater met the national standard collaboration salt recycling |
| CN210885671U (en) * | 2019-10-29 | 2020-06-30 | 江苏七洲绿色化工股份有限公司 | Recovery unit of metribuzin production waste acid water |
Non-Patent Citations (1)
| Title |
|---|
| 陈任华: "《危险废物环境管理与安全处理及污染控制标准实务全书 中》", 吉林电子出版社, pages: 627 * |
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