CN106630306A - Treating and recycling method for pesticide intermediate wastewater - Google Patents
Treating and recycling method for pesticide intermediate wastewater Download PDFInfo
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- CN106630306A CN106630306A CN201510735543.2A CN201510735543A CN106630306A CN 106630306 A CN106630306 A CN 106630306A CN 201510735543 A CN201510735543 A CN 201510735543A CN 106630306 A CN106630306 A CN 106630306A
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Abstract
The invention belongs to the technical field of sewage treatment, and particularly relates to a treating and recycling method for pesticide intermediate wastewater. By process design of pretreatment, electroosmosis concentration, triple-effect evaporation and recycling and the like, wastewater zero discharging is implemented basically, and water resources can be recycled. The treating and recycling method for the pesticide intermediate wastewater has the advantages of small occupied area, high recycling rate of water resources, low running costs and good economic and social effects. The treating and recycling method can be widely used in pesticide intermediate enterprises.
Description
Technical field：
The invention belongs to technical field of sewage, and in particular to a kind of process of pesticide intermediate waste water and reuse method.It is logical
Cross the coupling of the technologies such as flocculating sedimentation, electrodialysis concentration and triple effect evaporation, in effective process medicine intermediate production process pickling with
The waste water of the high COD of high salt produced by the alkali washing process stage.
Background technology：
The development of China in Recent Years pesticide industry is very rapid, and in the time of 10 years or so, pesticide yield has almost turned over one
Kind, pesticide species are doubled and redoubled.There are 774 by the chemical pesticide manufacturing enterprises more than end of the year 2011, China's scale, can
Produce more than 300 kinds of active compound；The pesticide intermediate kind for having produced is up to kind more than 800, and yield is nearly 3,000,000 tons.China's pesticide industry
Set up from active compound production, intermediate to match somebody with somebody and be set to preparation processing in interior more complete industrial system.However, due to synthesizing agriculture
Medicine intermediate reaction needs to add various medicaments, and product yield is low, the technique such as the substantial amounts of pickling of intermediate demand, alkali cleaning, so
Cause containing more chemical combination material (such as raw material, salt, by-product) in pesticide intermediate waste water, it is useless that these materials make
Water have high COD, difficult degradation, salinity is high, toxicity is big, the features such as be difficult biochemical treatment.At present, in the middle of little pesticide
Body enterprise can accomplish sewage qualified discharge, even and if qualified discharge, some of which high poison or the chemical combination with potential risk
Thing is still impacted to the health of ecological environment and the mankind.Therefore, agricultural chemicals waste water in a large number ask by the caused environmental pollution of discharge
Topic has become one of current China's urgent problem.
Looked into newly by technology, at present the domestic method to such wastewater treatment be mainly Jing after multiple-effect evaporation, dilution it is biochemical at
Reason etc..But due to traditional multiple-effect evaporation process energy consumption it is higher so that the profit margin of product is reduced.And the method such as biochemical materialization is difficult
To process the waste water of high salt, high COD, while some by-products are difficult to degrade in pesticide intermediate so that final outflow water is difficult to reach
To discharging standards.In order to solve the above problems, this patent is mixed by a certain percentage by pickling, alkali-wash waste water, Ran Houtong
The pretreatment such as flocculation are crossed, COD contents are reduced to into 18000mg/L or so.Simultaneously by the regulation of pH, it is ensured that in waste water
Organic substance, then by electrodialysis and the combination of triple effect evaporation, the process of profound level is carried out to waste water in the form of organic salt,
Realize the target of resource recycling and zero-emission.
With the enhancing of the increasingly serious and environmental consciousness of domestic shortage of water resources, country will increasingly weigh to energy-saving and emission-reduction
Depending on.Waste water produced by China's pesticide intermediate production technology is faced with high intractable problem, if to production technology and do not given up
Broken through on the recovery and utilization technology of water, China's environment will be caused continuous worsening with water resource, therefore to pesticide intermediate waste water
Process and recycling have great importance and necessity.
The content of the invention：
The present invention be directed in pesticide intermediate production process produced by alkali cleaning and acid cleaning process stage with high salinity, peracid
The alkali cleaning of the features such as basicity and high COD and pickling waste waterss, have designed and developed a kind of pesticide intermediate waste water integrated approach, organic
The method of thing and Water circulation.To set with the technique such as sand filtration pretreatment, electrodialysis concentration, triple effect evaporation with flocculation in the method
Meter, reaches that wastewater zero discharge, water resource can be recycled, floor space is little, integrated operation expense is low, economy and society effect
The good purpose of benefit.
The present invention is achieved by following technical proposals：
A kind of process of pesticide intermediate waste water and reuse method, it is characterised in that comprise the steps：
(1) will the middle pickling waste waterss (COD for producing of production pesticide intermediate 4- dibutylamino keto acids (BBA)：30000mg/L)
With alkali-wash waste water (COD：220000mg/L) mix, the pH of regulating water quality is 8-9, separates out insoluble Organic substance；
(2) into after flocculation basin, flocculant, flocculation aid are added in due order；
The flocculant for wherein adding is aluminium polychlorid, and consumption is 30-80 g ton waste water, and flocculation aid is polyacrylamide,
Consumption is 1-6 g ton waste water, and the sedimentation time is 1-4 hours, and COD is down to 18000mg/L；
(3) and then by above-mentioned pretreated waste water Jing sand filtrations filter, during in described sandfiltration pot Punica granatum L. sand grains footpath exist
100-300um, reaction time maintains 20-40min, produces water flow velocity and controls in 1-3m3/h；
(4) waste water Jing after sand filtration filtration carries out concentration into electrodialysis plant：Electric current density in electrodialysis plant
For 200-600A/m2, Jing circulation concentrations, until electrodialysis plant enriched chamber outlet salinity is lifted to 12%wt-18%wt, and it is light
The salinity of room outlet is reduced to 0.05%wt-0.15%wt, and light room outlet COD is reduced to 2800mg/L-2000mg/L, and water is returned
Yield is 70%-80%；
The electrodialysis plant for wherein using is homogeneous ion-exchange membrane, and membrane resistance is 1-4 Ω/cm2, the degree of cross linking is 75%-90%,
Soda acid tolerance pH is 2-13；
(5) the dense room outlet dope of electrodialysis plant delivers to triple effect evaporation tower vaporizing solid Organic substance and water resource, and evaporating column goes out
Used as industrial water, light room water outlet enters alkali cleaning and acid washing water operation stage reuse to the distilled water for coming.
The innovative point and beneficial effect of the present invention：
1. mix tune pH with alkali-wash waste water using pickling, be 7-9 by pH regulator, separate out the Organic substances such as a large amount of pesticide intermediates,
Then utilizing Flocculating Settling Technology, make COD in composite waste be down to 18000mg/L, and can ensure in waste water that part is solvable has
Machine thing exists with organic salt form；
2. the present invention is concentrated using the strong homogeneous EDBM of low resistance, high-crosslinking-degree, permselective property, can be by alkali
Wash and be concentrated to more than 12% with the salinity of pickling composite waste, the COD of fresh water outlet is reduced to 2000mg/L by 18000mg/L,
The response rate of water resource reaches more than 70%, and the expense for making triple effect evaporation is greatly lowered, and has been greatly reduced the process of whole technique
Cost；
3. due to this technique be for pesticide intermediate waste water various features and develop, finally can reclaim Organic substance consolidate
Body, the water outlet of triple effect evaporation can be used as industrial water, the light room water outlet of electrodialysis can also pickling, alkali scouring water use,
The zero-emission effect of waste water is basically reached, and realizes preferable economic and social profit.
Specific embodiment：
Embodiment 1：
With each processing meanss design and installation and debugging of 6 tons per hour for the treatment of capacity to whole technique, finally tried on the spot
Test, pilot experiment is carried out with alkali-wash waste water to the pickling that certain pesticide intermediate factory produces：
1st, the pH of its factory's alkali-wash waste water is 13.6, CODcrFor 220000mg/L, the pH of pickling waste waterss is 1.4, CODcr
For 30000mg/L；
2nd, pickling and alkali-wash waste water send into flocculation basin and carry out flocculation treatment by centrifugal pump respectively, and wherein flocculant is polymerization chlorine
Change aluminum, consumption is 50 g ton waste water, and flocculation aid is the polyacrylamide that molecular weight is 18,000,000, and consumption is 3 g ton waste water,
Sedimentation time is 1 hour；
3rd, the supernatant Jing centrifugal pumps after flocculating sedimentation is processed are passed through sand filtration tank arrangement, and Punica granatum L. sand grains footpath exists wherein in sandfiltration pot
100um, reaction time maintains 20min, produces water flow velocity and controls in 1m3/h；
4th, pretreated waste water quality is relatively preferable, and wherein pH is that 7.8, COD is down to below 18000mg/L, saliferous
Measure as 3.5%wt；
5th, preprocessed waste water out enters electrodialysis concentration, the membrane stack of 250 couples of 4,00*,800 1, electrodialysis
Electric current density be 400A/m2, Jing circulation concentrations, the electrodialytic membraness for using are homogeneous ion-exchange membrane, and wherein membrane resistance is 2
Ω/cm2, the degree of cross linking is 80%, and the salinity for making electrodialysis enriched chamber BBA waste water is promoted to 14%wt, and the salinity of fresh water
It is reduced to 0.15%wt, the COD of light room water outletcrFor 2000mg/L, Water Sproading rate is 73%, and electrodialysis energy consumption is 37kWh/t.
Concentrated water water quality：Salt content is 14%wt, CODcrFor 68000mg/L；Fresh water water quality：Salt content is 0.15%wt, CODcrFor
2000mg/L；
The water outlet of electrodialysis plant enriched chamber enters the evaporation of triple effect evaporation tower and reclaims Organic substance and distilled water, final by triple effect evaporation
Solid organic matters and distilled water are obtained, distilled water returns to BBA workshops does industrial water carries out reuse.Electrodialytic light room goes out
The pickling that water is entered in BBA production processes and alkali washing process stage, as the solvent of soda acid utilization is circulated；
The reusing rate of last BBA waste water reaches 98%, and Organic substance is 95% with the response rate of salt, and overall energy consumption is 48kWh/t,
60% is reduced with cost using triple effect evaporation process BBA waste water than simple, while reaching wastewater zero discharge purpose.
Embodiment 2：
With each processing meanss design and installation and debugging of 4 tons per hour for the treatment of capacity to whole technique, finally tried on the spot
Test, pilot experiment is carried out with alkali-wash waste water to the pickling that certain pesticide intermediate factory produces：
1st, the pH of its factory's alkali-wash waste water is 13.6, CODcrFor 226000mg/L, the pH of pickling waste waterss is 1.2, CODcr
For 31000mg/L；
2nd, pickling and alkali-wash waste water send into flocculation basin by centrifugal pump respectively carries out flocculation treatment, and wherein flocculant is polymerization chlorine
Change aluminum, consumption is 60 g ton waste water, and flocculation aid is the polyacrylamide that molecular weight is 18,000,000, and consumption is 4 g ton waste water,
Sedimentation time is 1.5 hours；
3rd, the supernatant Jing centrifugal pumps after flocculating sedimentation is processed are passed through sand filtration tank arrangement, and Punica granatum L. sand grains footpath exists wherein in sandfiltration pot
200um, reaction time maintains 25min, produces water flow velocity and controls in 2m3/h；
4th, pretreated waste water quality is relatively preferable, and wherein pH is that 8.1, COD is down to below 18000mg/L, saliferous
Measure as 4.2%wt；
5th, preprocessed waste water out enters electrodialysis concentration, the membrane stack of 200 couples of 4,00*,800 1, electrodialysis
Electric current density be 450A/m2, Jing circulation concentrations, the electrodialytic membraness for using are homogeneous ion-exchange membrane, and wherein membrane resistance is 2.5
Ω/cm2, the degree of cross linking is 85%, and the salinity for making electrodialysis enriched chamber BBA waste water is promoted to 15.5%wt, and the saliferous of fresh water
Amount is reduced to 0.1%wt, the COD of light room water outletcrFor 1900mg/L, Water Sproading rate is 75%, and electrodialysis energy consumption is 39kWh/t.
Concentrated water water quality：Salt content is 15.5%wt, CODcrFor 69000mg/L；Fresh water water quality：Salt content is 0.1%wt, CODcrFor
1900mg/L；
The water outlet of electrodialysis plant enriched chamber enters the evaporation of triple effect evaporation tower and reclaims Organic substance and distilled water, final by triple effect evaporation
Solid organic matters and distilled water are obtained, distilled water returns to BBA workshops does industrial water carries out reuse.Electrodialytic light room goes out
The pickling that water is entered in BBA production processes and alkali washing process stage, as the solvent of soda acid utilization is circulated；
The reusing rate of last BBA waste water reaches 98.5%, and Organic substance is 95.6% with the response rate of salt, and overall energy consumption is
49kWh/t, reduces 62%, while reaching wastewater zero discharge using triple effect evaporation process BBA waste water than simple with cost
Purpose.
Embodiment 3：
With each processing meanss design and installation and debugging of 2 tons per hour for the treatment of capacity to whole technique, finally carry out on the spot
Test, pilot experiment is carried out to the pickling that certain pesticide intermediate factory produces with alkali-wash waste water：
1st, the pH of its factory's alkali-wash waste water is 13.8, CODcrFor 228000mg/L, the pH of pickling waste waterss is 1.1, CODcr
For 32000mg/L；
2nd, pickling and alkali-wash waste water send into flocculation basin by centrifugal pump respectively carries out flocculation treatment, and wherein flocculant is polymerization chlorine
Change aluminum, consumption is 70 g ton waste water, and flocculation aid is the polyacrylamide that molecular weight is 18,000,000, and consumption is 5 g ton waste water,
Sedimentation time is 2 hours；
3rd, the supernatant Jing centrifugal pumps after flocculating sedimentation is processed are passed through sand filtration tank arrangement, and Punica granatum L. sand grains footpath exists wherein in sandfiltration pot
300um, reaction time maintains 30min, produces water flow velocity and controls in 3m3/h；
4th, pretreated waste water quality is relatively preferable, and wherein pH is that 8.8, COD is down to below 18000mg/L, saliferous
Measure as 4.6%wt；
5th, preprocessed waste water out enters electrodialysis concentration, the membrane stack of 150 couples of 4,00*,800 1, electrodialysis
Electric current density be 500A/m2, Jing circulation concentrations, the electrodialytic membraness for using are homogeneous ion-exchange membrane, and wherein membrane resistance is 3
Ω/cm2, the degree of cross linking is 90%, and the salinity for making electrodialysis enriched chamber BBA waste water is promoted to 16%wt, and the salinity of fresh water
It is reduced to 0.05%wt, the COD of light room water outletcrFor 1800mg/L, Water Sproading rate is 77%, and electrodialysis energy consumption is 40kWh/t.
Concentrated water water quality：Salt content is 16%wt, CODcrFor 70000mg/L；Fresh water water quality：Salt content is 0.05%wt, CODcrFor
1800mg/L；
The water outlet of electrodialysis plant enriched chamber enters the evaporation of triple effect evaporation tower and reclaims Organic substance and distilled water, final by triple effect evaporation
Solid organic matters and distilled water are obtained, distilled water returns to BBA workshops does industrial water carries out reuse.Electrodialytic light room goes out
The pickling that water is entered in BBA production processes and alkali washing process stage, as the solvent of soda acid utilization is circulated；
The reusing rate of last BBA waste water reaches 98.9%, and Organic substance is 95.7% with the response rate of salt, and overall energy consumption is
50kWh/t, reduces 61%, while reaching wastewater zero discharge using triple effect evaporation process BBA waste water than simple with cost
Purpose.
Claims (2)
1. a kind of process of pesticide intermediate waste water and reuse method, are primarily characterized in that, comprise the following steps：
(1) will the middle pickling waste waterss (COD for producing of production pesticide intermediate 4- dibutylamino keto acids (BBA)：30000mg/L) and
Alkali-wash waste water (COD：220000mg/L) mix, the pH of regulating water quality is 8-9, separates out insoluble Organic substance；
(2) into after flocculation basin, flocculant, flocculation aid are added in due order：
The flocculant for wherein adding is aluminium polychlorid, and consumption is 30-80 g ton waste water, and flocculation aid is polyacrylamide, and consumption is
1-6 g ton waste water, the sedimentation time is 1-4 hours, and COD is down to 18000mg/L；
(3) and then by above-mentioned pretreated waste water Jing sand filtrations filter, during in described sandfiltration pot Punica granatum L. sand grains footpath exist
100-300um, reaction time maintains 20-40min, produces water flow velocity and controls in 1-3m3/h；
(4) waste water Jing after sand filtration filtration carries out concentration into electrodialysis plant：Electric current density in electrodialysis plant is
200-600A/m2, Jing circulation concentrations, until water salinity is produced in the outlet of electrodialysis plant enriched chamber lifted to 12%wt-18%wt, and
The salinity that water is produced in light room outlet is reduced to 0.05%wt-0.15%wt, and the COD that water is produced in light room outlet is reduced to
2000mg/L-3000mg/L, Water Sproading rate is 70%-80%；
The film for wherein using in electrodialysis plant is homogeneous ion-exchange membrane, and membrane resistance is 1-4 Ω/cm2, the degree of cross linking is 75%-90%,
Soda acid tolerance pH is 2-13；
(5) the dense room outlet dope of electrodialysis plant delivers to triple effect evaporation tower vaporizing solid Organic substance and water resource, evaporating column steaming out
Used as industrial water, light room water outlet enters alkali cleaning and acid washing water operation stage reuse to distilled water.
2. the novel process wastewater from chemical industry device according in claims 1, it is characterised in that step (2) and (4), step
(2) simultaneously using flocculation aid and flocculant, light room water outlet COD is down to flocculation process by 18000mg/L in step (4) in
2000mg/L, salinity is down to 0.15%wt by 4%wt, and electrodialysis plant Water Sproading rate reaches 75% or so, and energy consumption is 40kWh/t.
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| CN201510735543.2A CN106630306A (en) | 2015-10-30 | 2015-10-30 | Treating and recycling method for pesticide intermediate wastewater |
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| CN201510735543.2A CN106630306A (en) | 2015-10-30 | 2015-10-30 | Treating and recycling method for pesticide intermediate wastewater |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113698043A (en) * | 2021-09-08 | 2021-11-26 | 南京东大能源工程设计院有限公司 | Resource utilization and advanced treatment method for raw material medicine production process wastewater |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101734821A (en) * | 2008-11-24 | 2010-06-16 | 中国石油天然气股份有限公司 | Method for treating atrazine-containing pesticide wastewater |
| CN101955282A (en) * | 2010-10-18 | 2011-01-26 | 江苏省环境科学研究院 | Method for realizing zero emission of dyeing wastewater with high salinity in printing and dyeing enterprises |
| CN102295392A (en) * | 2011-08-08 | 2011-12-28 | 杭州水处理技术研究开发中心有限公司 | Method for treating and reusing calcium chloride wastewater |
-
2015
- 2015-10-30 CN CN201510735543.2A patent/CN106630306A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101734821A (en) * | 2008-11-24 | 2010-06-16 | 中国石油天然气股份有限公司 | Method for treating atrazine-containing pesticide wastewater |
| CN101955282A (en) * | 2010-10-18 | 2011-01-26 | 江苏省环境科学研究院 | Method for realizing zero emission of dyeing wastewater with high salinity in printing and dyeing enterprises |
| CN102295392A (en) * | 2011-08-08 | 2011-12-28 | 杭州水处理技术研究开发中心有限公司 | Method for treating and reusing calcium chloride wastewater |
Non-Patent Citations (1)
| Title |
|---|
| 黄海苏 等: ""热敏染料废水处理技术"", 《净水技术》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113698043A (en) * | 2021-09-08 | 2021-11-26 | 南京东大能源工程设计院有限公司 | Resource utilization and advanced treatment method for raw material medicine production process wastewater |
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