CN109912094A - A kind for the treatment of process and its operation method of metribuzin discharged wastewater met the national standard collaboration salt recycling - Google Patents
A kind for the treatment of process and its operation method of metribuzin discharged wastewater met the national standard collaboration salt recycling Download PDFInfo
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Abstract
The invention discloses the treatment process and its operation method of a kind of metribuzin discharged wastewater met the national standard collaboration salt recycling, belong to agricultural chemicals waste water processing technology field.Treatment process of the invention mainly includes precipitating filtering, resin adsorption, pH neutralization, MVR, pH are adjusted and Fenton advanced oxidation, and the salt recycling is to obtain highly industry sodium sulphate after centrifugation drying by evaporative crystallization.Metribuzin waste water is handled by resin adsorption can be greatly lowered its COD concentration, then further remove the salinity in waste water by MVR, and eventually by Fenton advanced oxidation advanced treating, water outlet meets garden pipe network adapter tube standard.The present invention realizes high COD, efficient stable with high salt, bio-refractory metribuzin waste water processing, so that the continuous qualified discharge of metribuzin waste water, while realizing sodium sulphate resource utilization in waste water.
Description
Technical field
The present invention relates to the treatment process and its operation method of a kind of metribuzin discharged wastewater met the national standard collaboration salt recycling, belong to
In agricultural chemicals waste water processing technology field.
Background technique
Metribuzin (chemical name 4- amino -6- (1,1- dimethyl ethyl) -3- methyl mercapto -1,2,4- triazine -5- tetrahydro
Ketone), also known as Garrick remove, first grass piperazine, Garagard, metribuzin, be selective herbicide, be mainly used for soybean, potato, tomato,
The field crops management of weeds such as sugarcane, corn.The novel process of metribuzin raw medicine production passes through mainly using triazinone as intermediate
The processes conjunctions such as methyl esters synthesis, sulfate synthesis, hydrolysis alkaline hydrolysis, precipitation crystallization are made, and can be produced in the production process of its technique
Raw a large amount of high concentration CODs, waste water with high salt and with bio-toxicity, major pollutants include triazinone, metribuzin, methanol, sulphur
Hydrochlorate etc..
Industrial wastewater generally uses the group technology of materialized pretreatment and biochemical degradation to be handled at present, but conventional object
Change treatment process to have some limitations, processing capacity is limited.Traditional pretreating process, such as iron-carbon micro-electrolysis, Fenton
Reagent oxidation, coagulating sedimentation etc., treatment effect to metribuzin waste water are simultaneously bad.Relatively low (the B/C < of the biodegradability of the waste water
0.1), while in waste water also contain a large amount of inorganic salts, exist to a certain degree for the growth of microorganism in subsequent biochemical system
Inhibiting effect.Main process of the biochemical processing process as field of industrial waste water treatment, operation operation low with cost of investment
The advantages that simple, is most widely used.But triazinone agricultural chemicals waste water itself contains certain Fungicidal substance, it is possible to department of biochemistry
The microorganism of system causes inhibiting effect, it is difficult to achieve the purpose that wastewater biological is degraded, it could even be possible to causing microorganism dead, lead
Entire biochemical system is caused to collapse.
Resin, especially some macroporous absorbent resins are especially fragrant to containing aromatic ring, the higher organic matter of molecular weight
Race's monocycle, polycyclic and condensed ring class organic intermediate have good adsorption treatment effect.Fenton (Fenton) is to utilize catalyst
And H2O2Reaction generates the high-level oxidation technology with the hydroxyl radical free radical of Strong oxdiative ability, and Fenton referred to herein is to borrow
The heterogeneous Fenton oxidation technology for helping effective catalyst to act on, is capable of the organic wastewater of efficient process difficult for biological degradation, can make
For wastewater deep treatment process.It, can using resin adsorption and Fenton advanced oxidation as the main process of metribuzin wastewater treatment
Water outlet COD is down to 500mg/L hereinafter, reaching garden adapter tube standard；Pass through middle process mechanical steam recompression skill simultaneously
Art (MVR) evaporation is capable of handling recycling sodium sulphate by-product salt, realizes the recycling treatment and utilization of metribuzin Pollutants in Wastewater.
For example, Chinese Patent Application No. is 201620878779.1, application publication date is the patent Shen on January 4th, 2017
Please file disclose a kind of processing unit of low concentration wastewater.The patent includes two-stage water tank, the oil removing that process is sequentially connected
Pond, MVR vapo(u)rization system, iron-carbon micro-electrolysis device, Fenton oxidation pond, flocculation sedimentation tank, industry water collecting-tank, aerobic and anaerobism are raw
Change system, secondary settling tank, intermediate pool, ultrafiltration membrane treatment device and clear water reserviors.The utility model is advanced with technology, handles
Effect is good, and after treatment, COD drops below 60mg/L by 7000mg/L or so, and BOD is less than 20mg/L；Simultaneously in waste water
Oil can be with recycling and reusing, the anhydrous sodium sulfate that evaporative desalination generates can be used as commodity selling, realize the increasing of by-product
Value utilizes, to reduce the operation cost of whole system, achieves many things at one stroke.But iron-carbon micro-electrolysis-sweet smell in the process flow
- neutralization precipitation treatment process to the metribuzin pesticide Wastewater Pretreatment effect in the present invention and bad, to subsequent biochemistry
System can have adverse effect on, and entire process flow is too tediously long, and subsequent ultrafiltration film process is even more that can additionally increase operation
Cost.In addition, preposition MVR technique can not guarantee to recycle the quality of salt well.
For another example, Chinese Patent Application No. 201610762200.X, application publication date are the patent Shen on January 4th, 2017
Please file disclose a kind of rubber chemicals waste water reclaiming processing system and method.Rubber chemicals waste water resource described in the patent
Changing processing system includes precipitation-air-flotation pond, MVR vapo(u)rization system, resin adsorption desorption system, Fenton oxidation system and discharge bay；
Inlet and outlet, the tree are provided on the precipitation-air-flotation pond, MVR vapo(u)rization system, Fenton oxidation system and discharge bay
Import, first outlet and second outlet are provided in rouge adsorption-desorption system；The outlet in the precipitation-air-flotation pond and MVR evaporation are
The import of system is connected, and the outlet of the MVR vapo(u)rization system is connected with the import of resin adsorption desorption system, and the resin is inhaled
The second outlet of attached desorption system is connected with the import of rectifying column.The invented technology process is simple, and energy and chemical consumption are few,
Solid waste is not generated, rubber chemicals retained material can be effectively recycled, is invested low with operating cost.But in the treatment process
For Fenton oxidation system using common Fenton reagent oxidizing process, oxidation effectiveness is general, in comparison, non-in the present invention
Homogeneous Fenton oxidation uses the transition metal oxide solid catalyst using active carbon as carrier, and depth degradation effect is obvious.
In addition, preposition MVR technique can not guarantee to recycle the quality of salt well.
Chinese Patent Application No. is 201611040360.X, the patent application text that application publication date is on 2 22nd, 2017
Part discloses a kind of yarn-dyed fabric yarn dyeing wastewater treatment and online recycling method and device.The patent specifically includes that self-cleaning filtering
Device, conditioning tank, heterogeneous Fenton oxidation pond, flotation tank, dual membrane system, MVR system are constituted using being sequentially connected；Its method
It is individually to handle yarn dyeing waste water, and resource utilization anhydrous sodium sulfate therein can effectively reduce difficult to degrade in comprehensive wastewater
The content of organic matter and salinity, and improve the utilization rate of raw material.Experimental result is shown: package unit recyclable 90% with
On yarn dyeing waste water, salinity can be effectively removed in waste water, the distillation that salt rejection rate > 99%, RO produces water and MVR system generates
Liquid can be back to each production link and use, and substitute new water consumption, the yield of pollutant is controlled from source, is fully demonstrated
The theory of clean manufacturing.But the heterogeneous Fenton oxidation in the treatment process is only used as pretreating process, only passes through double films
System is difficult to effectively remove the hard-degraded substance in waste water, and water outlet COD cannot be guaranteed.
Chinese Patent Application No. is 201711088952.3, the patent application text that data of publication of application is on 04 03rd, 2018
Part discloses a kind of method and technique by agricultural chemicals waste water resource utilization.The patent mainly uses the absorption of resin adsorption system
Organic matter therein is recycled with desorption, after filtrate is handled through evaporation and concentration, recycles sodium chloride and sodium thiosulfate therein；It should
The pollutants such as high COD in agricultural chemicals waste water, difficult to degrade, high bio-toxicity, still, the treatment process can be effectively treated in patent
Not preposition precipitating filtering of middle resin adsorption system etc. pre-processes measure, and some solid granules may will affect resin suction in waste water
The operational effect of attached system, and resin adsorption can effectively remove high boiling point organic compound, and the COD in waste water is greatly lowered, but
Limited to low-boiling-point organic compound removal ability, entire process flow end lacks technique of checking on, and water outlet COD cannot be guaranteed.
2 months 2011, the 165-168 pages of the phase of volume 34 the 2nd of " Environmental science and technology ", Li Jun, Han Yongzhong, Cheng Weijian,
Wu Xiaogen and Liu Zhifeng discloses the article of one entitled " research of metribuzin pesticide producing cyclization waste water physicochemical treatment process ", should
Research carries out materialized pretreatment to metribuzin pesticide producing cyclization waste water using flocculation-resin adsorption group technology, and experiment determines
Optimum process condition are as follows: (1) flocculation-flocculant be 10% aluminum sulfate solution, dosage 8%, wastewater pH be 6~9, quickly
It stirs 1min (150~180r/min), mixes slowly 15min (80~100r/min)；(2) resin adsorption-double-column series absorption:
Upper prop liquid pH=3.0 or so, adsorption temp are room temperature, adsorption flow rate 2.5BV/h；(3) resin desorption-desorbing agent 1BV H2O+
1BV 4%NaOH+1BV 2%NaOH+2BV H2O, flow velocity 1BV/h, temperature are 80 DEG C.The results showed that in optimised process
Under the conditions of the waste water is handled, COD is down to 3650mg/L hereinafter, removal rate reaches 85% or more；The BOD of waste water5/COD
It is increased to 0.43 by 0.23, provides good condition for subsequent biochemical processing.But the group technology is only useless as metribuzin
The pretreating process of water, inorganic salts resource utilization does not embody in waste water, and passes through the pretreated waste water of flocculation-resin adsorption
Although biodegradability increases, but still contain certain density fungicide, there are still certain prestige to subsequent biochemical system
The side of body, influent load are restricted.
Therefore, it for the processing of the waste water of metribuzin production, needs to develop a kind of metribuzin discharged wastewater met the national standard collaboration salt
The treatment process and its operation method of recycling, solve that its waste water COD concentration is high, be difficult to biodegrade and salinity is high asks
Topic.
Summary of the invention
1. to solve the problems, such as
For in the prior art including the pretreating process such as conventional iron-carbon micro-electrolysis, Fenton reagent oxidation, coagulating sedimentation,
It is limited to metribuzin production wastewater treatment degradation capability, and bioanalysis is not strong to the waste water adaptability, degradation rate is not high, stops
Overlong time is difficult to the problem of qualified discharge, and the present invention provides a kind of metribuzin discharged wastewater met the national standard collaboration salt recyclings
Treatment process and its operation method.After handling by MVR, then use heterogeneous Fenton oxidizing process that can efficiently reduce in waste water
COD concentration, carry out biodegrade, solve Traditional materialized to be difficult to ensure metribuzin discharged wastewater met the national standard with biochemistry combination process
Status；The by-product sodium sulphate in waste water can be recycled simultaneously, is economized on resources, and pollution is reduced.
2. technical solution
To solve the above-mentioned problems, the technical solution adopted in the present invention is as follows:
A kind for the treatment of process of metribuzin discharged wastewater met the national standard collaboration salt recycling, including waste water treatment process and salt resource
Chemical industry skill, the waste water treatment process successively includes precipitating, resin adsorption, MVR, pH are adjusted and Fenton oxidation, described
For salt process for reclaiming by carrying out freezing and crystallizing to concentrate in MVR workshop section, centrifugation drying obtains industrial refined sulfuric acid sodium.
Further, the setting pot that is precipitated as is handled, and setting pot uses horizontal flow type grit chamber, horizontal flow control
Two sections of funnel structures are used in the bottom of 0.1m/s~0.2m/s, residence time 2min~3min, setting pot, are arranged using gravity
Sand.
Further, the resin adsorption includes adsorption and desorption and regeneration treatment three phases.
Further, the resin adsorption stage use graininess superhigh cross-linking compound resin, partial size 0.1mm~
0.2mm, reaction unit use tower structure, and loadings are the 1/3-1/2 of tower dischargeable capacity, bottom water inlet, top water outlet, absorption
Flow velocity 1BV/h~2BV/h.
Further, desorption processing is carried out to absorption resin, the desorption stage is multiple using 2%~10% liquid alkaline
With mass concentration be 80%~90% organic solvent prepare mixed liquor as desorbing agent, wherein the preferred methanol of organic solvent or
Flow velocity 0.5BV/h~1BV/h is desorbed in ethyl alcohol.
Further, the regeneration treatment stage is by the organic solvent in rectifying recycling desorption liquid to compound
Desorbing agent, remaining raffinate pass through incineration disposal.
Further, it is carried out in the pH and in pH neutralization pond, pH neutralization pond is alkali conditioning tank, passes through metering pump
The 30%NaOH solution being stored in industrial lye tank is added drop-wise in resin adsorption efflux, is stirred using micro-pore aeration, surely
Its fixed pH value guarantees that water outlet pH value is neutrality, prevents the water quality under acid condition from causing corrosion to make subsequent MVR 7~8
With.
Further, the MVR evaporator, evaporating temperature is at 85 DEG C~95 DEG C.
Further, pH adjusting carries out in pH conditioning tank, and pH conditioning tank is Fenton oxidation pre-treatment pond,
98% concentrated sulfuric acid being stored in industrial sulphuric acid tank is added drop-wise in evaporation condensate by metering pump, is stirred using micro-pore aeration
It mixes, stablizes its pH value 3~4, that is, create the optimal pH of the water inlet of subsequent heterogeneous Fenton technique.
Further, the Fenton oxidation is aoxidized using heterogeneous Fenton, and reactor uses tower knot
Structure, top water inlet, bottom U-tube overflow water outlet；Inside filling is excellent using granular activated carbon as the noble metal active catalyst of carrier
PdO, Pt or Pd are selected, content is 0.1%~5%, and the loadings of catalyst are the 1/2~2/3 of tower dischargeable capacity；Using 30%
H2O2Main water inlet tube road is injected by metering pump, flow is 0.5 ‰~the 1 ‰ of inflow；The Fenton reaction system bottom
If disc type aeration head provides a certain amount of uniform aeration, wherein QGas/QWaterFor (20~30): 1.
Further, the freezing and crystallizing is to be freezed to the MVR concentration material for being pumped into crystallization kettle using jacket type, cold
The calcium chloride water that jelly liquid is 20%~25%, -20 DEG C~-5 DEG C of cryogenic temperature.
Further, centrifugation drying is to carry out centrifugal dehydration to crystallization kettle material using vertical centrifugal machine, then
Drying and processing is carried out to centrifugal material using single cone vacuum dryer, 103 DEG C~105 DEG C of drying temperature.
A kind of operation method of metribuzin discharged wastewater met the national standard collaboration salt recycling, using above-mentioned treatment process, including
Following processing step:
1) waste water is through the bulky grain solid impurity in horizontal flow type grit chamber removal waste water, horizontal flow control 0.1~
0.2m/s, 2~3min of residence time, periodically turn on bucket gravity deslagging, and sludge discharging period is 1~2d.
2) setting pot water outlet flow to intermediate pond body and collects, synchronous to open intermediate pond body elevator pump, by pipeline by waste water from
Resin adsorption tower bottom is pumped into, top outflow, 1~2BV/h of adsorption flow rate.
3) two groups of resin adsorption towers are set, alternately, switching valve, one group of adsorption saturation is arranged in inlet pipeline to adsorption-desorption
After close valve, switch to another group of resin adsorption tower；Using liquid alkaline compounding organic solvent as desorbing agent, wherein organic solvent
For methanol or ethanol solution, opens metering pump and be pumped into desorbing agent from resin adsorption top of tower by pipeline, flow velocity 0.5 is desorbed
~1BV/h；Tower bottom is equipped with automatic control flowing water Valve, and desorption liquid is flowed out from bottom.
4) desorption liquid collected recycles organic solvent through rectifier unit, prepares solution as desorbing agent, remaining rectifying is residual
Liquid enters incinerator disposition.
5) liquid alkaline (synchronous with water inlet) is added dropwise by metering pump from pH neutralization pond, water inlet is flow in resin adsorption tower water outlet,
Pond body is diagonally equipped with submersible agitator, guarantees that water body soda acid reconciles uniformly, water outlet pH value is 7~8.
6) water outlet of pH neutralization pond is delivered to the processing of MVR system, evaporation temperature by pump from MVR stock solution collection tank, stoste is flow to
85~95 DEG C of degree, the condensate liquid of generation is collected to condensate liquid collecting tank, and the concentrate of generation is pumped by transfer tank to crystallization kettle.
7) after concentrate is pumped into crystallization kettle, it is pumped into chilled brine into kettle external jacket and carries out freezing and crystallizing, cryogenic temperature -20
~-5 DEG C, 2~5h of cooling time.
8) crystallized stock in crystallization kettle, which is put into vertical centrifugal machine, carries out centrifugal dehydration, and dewatered material transfers to
Drying and processing in single cone vacuum dryer of drying chamber, 103~105 DEG C of drying temperature.Material after drying is by-product industry sulphur
Sour sodium.
9) treated that condensate liquid is pumped from collecting tank to pH conditioning tank by MVR, and the concentrated sulfuric acid is added dropwise by metering pump in water inlet；And
And the synchronous water inlet of the concentrated sulfuric acid and MVR treated condensate liquid, pond body are diagonally equipped with submersible agitator, it is equal to guarantee that water body pH reconciles
Even, water outlet pH value is 3~4.
10) water outlet of pH conditioning tank opens elevator pump for stoste and is pumped into Fenton oxidation from Fenton water inlet collecting tank is flow to
Tower, top water inlet, bottom U-tube overflow water outlet, 2~3h of residence time.It is synchronous to open H2O2Metering pump is by H2O2Inject waste pipe
It is uniformly mixed in road, and opens blower and provide aeration for tower body, the air quantity and flow of inlet water of blower are than control in (20~30):
1。
11) water outlet of Fenton oxidation tower is pumped into garden pipe network from discharge pond, standard water discharge is flow to.
3. beneficial effect
Compared with the prior art, the invention has the benefit that
(1) present invention can be completed by group technologies such as resin adsorption, evaporative crystallization, Fenton advanced oxidations to height
COD, metribuzin technique waste water with high salt, bio-refractory are effectively treated, while by-product sulphur is realized in the purification passed through to water quality
The resource utilization of sour sodium.Resin adsorption in the technique can effectively adsorb high boiling point organic compound in waste water, by waste water COD by
4000mg/L~6000mg/L is effectively down to 1000mg/L~1500mg/L, the sodium sulphate colorless and odorless of recycling, solid sodium sulfate
Middle TOC≤0.6mg/g, sodium sulphate quality reach Nacl standard.Condensate liquid is after the processing of Fenton advanced oxidation, COD energy
It is enough to stablize in 500mg/L hereinafter, reaching garden sewage treatment adapter tube standard, and reduce waste water to subsequent biochemical processing system
Bio-toxicity.Effective combine of the group technology not only realizes high COD, at efficient stable with high salt, bio-refractory waste water
Reason, while the resource utilization of sodium sulphate is realized, achieve certain economic well-being of workers and staff；
(2) technique of present invention processing metribuzin waste water can be while high with the by-product sodium sulphate in resource utilization waste water
Effect, stably reaching standard handle the waste water of this feature.
Detailed description of the invention
Fig. 1 is process flow chart of the invention.
Specific embodiment
The present invention is further described below combined with specific embodiments below.
Embodiment 1
Jiangsu Coastal agricultural chemicals enterprise workshop generate metribuzin waste water quality it is as shown in table 1, belong to high salt, high COD and
Waste water difficult for biological degradation.
The instrument and equipment of the present embodiment wastewater treatment include: horizontal flow type grit chamber；Intermediate pool；Resin adsorption-desorption column；
PH neutralization pond；MVR evaporator；PH conditioning tank；Fenton oxidation tower；Discharge pond；Freezing and crystallizing kettle；Vertical centrifugal machine；Single cone is true
Empty dryer；Rectifying column.
1 metribuzin waste water quality of table and garden adapter tube standard
As shown in Figure 1, the wastewater treatment concrete technology flow process of the present embodiment is as follows:
With high salt, high COD, difficult for biological degradation metribuzin waste water is miscellaneous by granular solids in horizontal flow type grit chamber removal waste water
Matter flows into intermediate pool again, wherein horizontal flow type grit chamber flow control opens primary weight in 0.1m/s, residence time 3min daily
Power sediment outflow carries out sludge discharge work；Intermediate pool water outlet is pumped into resin adsorption-desorption column, wherein loads in resin adsorption-desorption column
Resin partial size is 0.1mm~0.2mm, and resin loadings are the 1/3 of tower dischargeable capacity, and adsorption flow rate 2BV/h is high boiling in waste water
Point organic matter is removed by large aperture resin adsorption, and COD is greatly lowered, and the biodegradability of waste water improves；Resin adsorption water outlet
It adsorbs efflux and enters MVR evaporator after pH neutralization pond adjusting pH value to 7, setting evaporating temperature is 90 DEG C；On the one hand, MVR
The concentrate that evaporator generates is pumped into freezing and crystallizing kettle, passes through jacket type freezing and crystallizing, wherein freezing liquid uses 25% chlorination
Calcium solution, cryogenic temperature are -15 DEG C, cooling time 2h；Crystallized stock is put into centrifuge and carries out centrifugal dehydration, dewatered object
Expect to obtain by-product sodium sulphate by single cone vacuum dryer drying (105 DEG C of drying temperature) again, realizes salt resource utilization；Meanwhile
On the other hand, the condensate liquid that MVR evaporator generates enters pH conditioning tank and adjusts pH value to after 3, makes it into Fenton using pump
Oxidizing tower, by using granular activated carbon as the PdO solid catalyst of carrier, catalysis oxidation H2O2What is generated has Strong oxdiative ability
The further degrading waste water of OH in organic matter, strengthen the removal of COD and hard-degraded substance, finally flow into discharge pond, wherein
The activity for the PdO and 90%~95% that the content (mass fraction) of catalyst main component is 1~10% in Fenton oxidation tower
Charcoal, loaded catalyst are the 1/2, H of tower dischargeable capacity2O2For the H of mass fraction 30%2O2, H2O2Flow be inflow
0.7 ‰, and aeration is set, gas-water ratio 30:1；After resin adsorption tower adsorption saturation, desorption processing is carried out, flow velocity 1BV/ is desorbed
H, desorbing agent compound 90% methanol solution using 5% liquid alkaline；The desorption liquid of generation enters rectifying column rectifying methanol reuse, and compounding is de-
Attached dose, remaining distillation residual liquid enters incinerator disposition.
Metribuzin waste water treatment process the following steps are included:
1) waste water is promoted to horizontal flow type grit chamber intake chamber from the boosted pump of wastewater collection tank, removes through horizontal flow type grit chamber
Granule foreign is collected subsequently into intermediate pool；Horizontal flow type grit chamber flow control is periodically opened in 0.1m/s, residence time 3min
Gravity sediment outflow is opened, sludge discharging period is 1 day.
2) intermediate pool waste water enters resin adsorption-desorption column progress adsorption treatment, and removing higher boiling macromolecular in waste water has
Machine object, waste water from bottom to top, adsorption flow rate 2BV/h；After adsorption saturation, inlet valve is closed, is pumped by metering pump from top
Liquid alkaline compounds 90% methanol solution and carries out desorption processing, and flow velocity 1BV/h is desorbed.It is synchronous to open another group of resin adsorption-desorption column
Inlet valve carry out adsorption treatment, two groups of resin adsorption towers carry out adsorption-desorption switchings.The desorption liquid that resin tower generates enters essence
Tower rectifying recycling methanol is evaporated, desorbing agent is compounded, remaining distillation residual liquid enters incinerator disposition.
3) from pH neutralization pond is flowed into, liquid alkaline is added dropwise in synchronous metering pump of opening, and opens submersible agitator for resin adsorption water outlet,
Even regulation water outlet pH value is to 7, effluent collection to MVR stock solution collection tank.
4) waste water in MVR stock solution collection tank is pumped into MVR evaporator and is evaporated processing, 90 DEG C of evaporating temperature.It generates
Condensate liquid and concentrate are separately stored in respective collecting tank.
5) MVR condensate liquid is pumped from collecting tank to pH conditioning tank, sulfuric acid is added dropwise in synchronous metering pump of opening, and opens diving
Blender, even regulation water outlet pH value to 3, effluent collection to Fenton water inlet collecting tank.
6) raw water in Fenton water inlet collecting tank is pumped into Fenton oxidation tower, top water inlet, bottom U-tube overflow goes out
Water.It is synchronous to open H2O2Metering pump is by H2O2It is pumped into inlet pipeline, H2O2For the H of mass fraction 30%2O2, H2O2Flow be into
The 0.7 ‰ of water, and aeration is opened, gas-water ratio 30:1.The hydraulic detention time of Fenton oxidation tower is 2h, and water outlet is flow to certainly
Pond is discharged, standard water discharge is discharged into garden pipe network.
7) on the other hand, MVR concentrate is pumped into freezing and crystallizing kettle from collecting tank, and calcium chloride freezing liquid is pumped into crystallization kettle folder
Set carries out freezing and crystallizing, and cryogenic temperature is -15 DEG C, cooling time 2h.After freezing, material is put into centrifuge from bottom
Centrifugal dehydration is carried out in material trough, dewatered material transfers to drying chamber, carries out drying and processing using single cone vacuum dryer
By-product sodium sulphate, 105 DEG C of drying temperature.
Treated that effluent quality situation is shown in Table 2 by the present invention.
Each workshop section's effluent quality of 2 group technology of table processing
As shown in Table 2, after resin adsorption, COD concentration is obviously greatly lowered metribuzin raw wastewater, using
The COD concentration of MVR evaporator treated condensate liquid has certain reduction, and more it is worth noting that, total salt concentration significantly subtracts
Few, COD≤500mg/L, the total salt≤5000mg/L of last Fenton oxidation water outlet can be discharged into garden sewage network.
Embodiment 2
Substantially the same manner as Example 1, the metribuzin waste water of the present embodiment also chooses the production of Jiangsu Coastal agricultural chemicals enterprise workshop
Raw metribuzin waste water, water quality indicator are as shown in table 1.The difference is that technological parameter is changed.
Specifically, the wastewater treatment concrete technology flow process of the present embodiment is as follows:
With high salt, high COD, difficult for biological degradation metribuzin waste water remove granular solids impurity in waste water by horizontal flow type grit chamber
Intermediate pool is flowed into again, wherein horizontal flow type grit chamber flow control opens primary weight for every 2 days in 0.15m/s, residence time 2min
Power sediment outflow carries out sludge discharge work；Intermediate pool water outlet is pumped into resin adsorption-desorption column, wherein loads in resin adsorption-desorption column
Resin partial size is 0.1mm~0.2mm, and resin loadings are the 1/3 of tower dischargeable capacity, and adsorption flow rate 1BV/h is high boiling in waste water
Point organic matter is removed by large aperture resin adsorption, and COD is greatly lowered, and the biodegradability of waste water improves；Resin adsorption water outlet
It adsorbs efflux and enters MVR evaporator after pH neutralization pond adjusting pH value to 8, setting evaporating temperature is 85 DEG C；On the one hand, MVR
The concentrate that evaporator generates is pumped into freezing and crystallizing kettle, passes through jacket type freezing and crystallizing, wherein freezing liquid uses 20% chlorination
Calcium solution, cryogenic temperature are -20 DEG C, cooling time 5h；Crystallized stock is put into centrifuge and carries out centrifugal dehydration, dewatered object
Expect to obtain by-product sodium sulphate by single cone vacuum dryer drying (104 DEG C of drying temperature) again, realizes salt resource utilization；Meanwhile
On the other hand, the condensate liquid that MVR evaporator generates enters pH conditioning tank and adjusts pH value to after 4, makes it into Fenton using pump
Oxidizing tower, by using granular activated carbon as carrier, catalyst that active material is Pt, catalysis oxidation H2O2Having for generating is strong
Organic matter in the further degrading waste water of the OH of oxidability strengthens the removal of COD and hard-degraded substance, finally flows into discharge
Pond, wherein the content of catalyst is 0.1% in Fenton oxidation tower, and loaded catalyst is the 1/2, H of tower dischargeable capacity2O2For
The H of mass fraction 30%2O2, H2O2Flow be the 0.5 ‰ of inflow, and aeration is set, gas-water ratio 20:1；Resin adsorption
After tower adsorption saturation, desorption processing is carried out, flow velocity 0.5BV/h is desorbed, desorbing agent compounds 80% ethanol solution using 2% liquid alkaline；
The desorption liquid of generation enters rectifying column rectifying ethyl alcohol reuse, compounds desorbing agent, and remaining distillation residual liquid enters incinerator disposition.
Metribuzin waste water treatment process the following steps are included:
1) waste water is promoted to horizontal flow type grit chamber intake chamber from the boosted pump of wastewater collection tank, removes through horizontal flow type grit chamber
Granule foreign is collected subsequently into intermediate pool；Horizontal flow type grit chamber flow control is periodically opened in 0.15m/s, residence time 2min
Gravity sediment outflow is opened, sludge discharging period is 2 days.
2) intermediate pool waste water enters resin adsorption-desorption column progress adsorption treatment, and removing higher boiling macromolecular in waste water has
Machine object, waste water from bottom to top, adsorption flow rate 1BV/h；After adsorption saturation, inlet valve is closed, is pumped by metering pump from top
2% liquid alkaline compounds 80% ethanol solution and carries out desorption processing, and flow velocity 0.5BV/h is desorbed.Synchronous another group of resin adsorption-of unlatching is de-
The inlet valve of attached tower carries out adsorption treatment, and two groups of resin adsorption towers carry out adsorption-desorption switching.Resin tower generate desorption liquid into
Enter rectifying column rectifying recycling ethyl alcohol, compound desorbing agent, remaining distillation residual liquid enters incinerator disposition.
3) from pH neutralization pond is flowed into, liquid alkaline is added dropwise in synchronous metering pump of opening, and opens submersible agitator for resin adsorption water outlet,
Even regulation water outlet pH value is to 8, effluent collection to MVR stock solution collection tank.
4) waste water in MVR stock solution collection tank is pumped into MVR evaporator and is evaporated processing, 85 DEG C of evaporating temperature.It generates
Condensate liquid and concentrate are separately stored in respective collecting tank.
5) MVR condensate liquid is pumped from collecting tank to pH conditioning tank, sulfuric acid is added dropwise in synchronous metering pump of opening, and opens diving
Blender, even regulation water outlet pH value to 4, effluent collection to Fenton water inlet collecting tank.
6) raw water in Fenton water inlet collecting tank is pumped into Fenton oxidation tower, top water inlet, bottom U-tube overflow goes out
Water.It is synchronous to open H2O2Metering pump is by H2O2It is pumped into inlet pipeline, wherein H2O2Flow is the 0.5 ‰ of inflow, and opens aeration,
Gas-water ratio is 20:1.The hydraulic detention time of Fenton oxidation tower is 3h, and water outlet is discharged into garden from discharge pond, standard water discharge is flow to
Pipe network.
7) on the other hand, MVR concentrate is pumped into freezing and crystallizing kettle from collecting tank, and calcium chloride freezing liquid is pumped into crystallization kettle folder
Set carries out freezing and crystallizing, and cryogenic temperature is at -20 DEG C, cooling time 5h.After freezing, material is put into centrifuge from bottom
Centrifugal dehydration is carried out in material trough, dewatered material transfers to drying chamber, carries out drying and processing using single cone vacuum dryer
By-product sodium sulphate, 104 DEG C of drying temperature.
Treated that effluent quality situation is shown in Table 3 by the present invention.
Each workshop section's effluent quality of 3 group technology of table processing
As shown in Table 3, after resin adsorption, COD concentration is obviously greatly lowered metribuzin raw wastewater, using
The COD concentration of MVR evaporator treated condensate liquid has certain reduction, and more it is worth noting that, total salt concentration significantly subtracts
Few, COD≤500mg/L, the total salt≤5000mg/L of last Fenton oxidation water outlet can be discharged into garden sewage network.
Embodiment 3
Substantially the same manner as Example 1, the metribuzin waste water of the present embodiment also chooses the production of Jiangsu Coastal agricultural chemicals enterprise workshop
Raw metribuzin waste water, water quality indicator are as shown in table 1.The difference is that technological parameter is changed.
Specifically, the wastewater treatment concrete technology flow process of the present embodiment is as follows:
With high salt, high COD, difficult for biological degradation metribuzin waste water remove granular solids impurity in waste water by horizontal flow type grit chamber
Intermediate pool is flowed into again, wherein horizontal flow type grit chamber flow control opens primary weight in 0.2m/s, residence time 1.5min daily
Power sediment outflow carries out sludge discharge work；Intermediate pool water outlet is pumped into resin adsorption-desorption column, wherein loads in resin adsorption-desorption column
Resin partial size is 0.1mm~0.2mm, and resin loadings are the 1/2 of tower dischargeable capacity, adsorption flow rate 1.5BV/h, the height in waste water
Boiling organics are removed by large aperture resin adsorption, and COD is greatly lowered, and the biodegradability of waste water improves；Resin adsorption water outlet
Absorption efflux to adjust pH value to MVR evaporator, setting evaporating temperature is entered after 7 through pH neutralization pond be 95 DEG C；On the one hand,
The concentrate that MVR evaporator generates is pumped into freezing and crystallizing kettle, passes through jacket type freezing and crystallizing, wherein freezing liquid uses 22.5%
Calcium chloride solution, cryogenic temperature be -12.5 DEG C, cooling time 3.5h；Crystallized stock is put into centrifuge and carries out centrifugal dehydration,
Dewatered material passes through single cone vacuum dryer drying (103 DEG C of drying temperature) again and obtains by-product sodium sulphate, realizes salt recycling
It utilizes；Meanwhile on the other hand, the condensate liquid that MVR evaporator generates enters pH conditioning tank and adjusts pH value to after 3, makes it using pump
Into Fenton oxidation tower, by using granular activated carbon as carrier, catalyst that active material is Pd, catalysis oxidation H2O2It produces
Organic matter in the raw further degrading waste water of OH with Strong oxdiative ability strengthens the removal of COD and hard-degraded substance, most
Discharge pond is flowed into eventually, and wherein the content of catalyst is 2.55% in Fenton oxidation tower, and loaded catalyst is tower dischargeable capacity
2/3, H2O2For the H of mass fraction 30%2O2, H2O2Flow be the 0.75 ‰ of inflow, and open aeration, gas-water ratio is
25:1；After resin adsorption tower adsorption saturation, desorption processing is carried out, flow velocity 0.75BV/h is desorbed, desorbing agent is compounded using 2% liquid alkaline
80% methanol solution；The desorption liquid of generation enters rectifying column rectifying methanol reuse, compounds desorbing agent, and remaining distillation residual liquid enters
Incinerator disposition.
Metribuzin waste water treatment process the following steps are included:
1) waste water is promoted to horizontal flow type grit chamber intake chamber from the boosted pump of wastewater collection tank, removes through horizontal flow type grit chamber
Granule foreign is collected subsequently into intermediate pool；Horizontal flow type grit chamber flow control is in 0.2m/s, residence time 1.5min, periodically
Gravity sediment outflow is opened, sludge discharging period is 1 day.
2) intermediate pool waste water enters resin adsorption-desorption column progress adsorption treatment, and removing higher boiling macromolecular in waste water has
Machine object, waste water from bottom to top, adsorption flow rate 1.5BV/h；After adsorption saturation, inlet valve is closed, is pumped by metering pump from top
Enter 10% liquid alkaline, 90% methanol solution of compounding and carry out desorption processing, flow velocity 0.75BV/h is desorbed.It is synchronous to open another group of resin suction
The inlet valve of attached-desorption column carries out adsorption treatment, and two groups of resin adsorption towers carry out adsorption-desorption switching.Resin tower generates de-
Attached liquid enters rectifying column rectifying recycling methanol, compounds desorbing agent, and remaining distillation residual liquid enters incinerator disposition.
3) from pH neutralization pond is flowed into, liquid alkaline is added dropwise in synchronous metering pump of opening, and opens submersible agitator for resin adsorption water outlet,
Even regulation water outlet pH value is to 7, effluent collection to MVR stock solution collection tank.
4) waste water in MVR stock solution collection tank is pumped into MVR evaporator and is evaporated processing, 95 DEG C of evaporating temperature.It generates
Condensate liquid and concentrate are separately stored in respective collecting tank.
5) MVR condensate liquid is pumped from collecting tank to pH conditioning tank, sulfuric acid is added dropwise in synchronous metering pump of opening, and opens diving
Blender, even regulation water outlet pH value to 3, effluent collection to Fenton water inlet collecting tank.
6) raw water in Fenton water inlet collecting tank is pumped into Fenton oxidation tower, top water inlet, bottom U-tube overflow goes out
Water.It is synchronous to open H2O2Metering pump is by H2O2It is pumped into inlet pipeline, wherein H2O2Flow is the 0.75 ‰ of inflow, and opens exposure
Gas, gas-water ratio 25:1.The hydraulic detention time of Fenton oxidation tower is 1.5h, and water outlet is arranged from discharge pond, standard water discharge is flow to
Enter garden pipe network.
7) on the other hand, MVR concentrate is pumped into freezing and crystallizing kettle from collecting tank, and calcium chloride freezing liquid is pumped into crystallization kettle folder
Set carries out freezing and crystallizing, and cryogenic temperature is at -12.5 DEG C, cooling time 3.5h.After freezing, material is put into centrifugation from bottom
Centrifugal dehydration is carried out in the material trough of machine, dewatered material transfers to drying chamber, is dried using single cone vacuum dryer
Handle to obtain by-product sodium sulphate, 103 DEG C of drying temperature.
Treated that effluent quality situation is shown in Table 4 by the present invention.
Each workshop section's effluent quality of 4 group technology of table processing
As shown in Table 4, after resin adsorption, COD concentration is obviously greatly lowered metribuzin raw wastewater, using
The COD concentration of MVR evaporator treated condensate liquid has certain reduction, and more it is worth noting that, total salt concentration significantly subtracts
Few, COD≤500mg/L, the total salt≤5000mg/L of last Fenton oxidation water outlet can be discharged into garden sewage network.
Embodiment 4
Substantially the same manner as Example 3, the metribuzin waste water of the present embodiment also chooses the production of Jiangsu Coastal agricultural chemicals enterprise workshop
Raw metribuzin waste water, water quality indicator are as shown in table 1.The difference is that technological parameter is changed.
Specifically, the wastewater treatment concrete technology flow process of the present embodiment is as follows:
With high salt, high COD, difficult for biological degradation metribuzin waste water remove granular solids impurity in waste water by horizontal flow type grit chamber
Intermediate pool is flowed into again, wherein horizontal flow type grit chamber flow control opens primary weight in 0.2m/s, residence time 1.5min daily
Power sediment outflow carries out sludge discharge work；Intermediate pool water outlet is pumped into resin adsorption-desorption column (3), wherein fills out in resin adsorption-desorption column
The resin partial size of dress is 0.1mm~0.2mm, and resin loadings are the 5/12 of tower dischargeable capacity, adsorption flow rate 1.5BV/h, waste water
In high boiling point organic compound removed by large aperture resin adsorption, COD is greatly lowered, and the biodegradability of waste water improves；Resin is inhaled
The absorption efflux of attached water outlet enters MVR evaporator after pH neutralization pond adjusting pH value to 7, and setting evaporating temperature is 95 DEG C；One
Aspect, the concentrate that MVR evaporator generates are pumped into freezing and crystallizing kettle, pass through jacket type freezing and crystallizing, wherein freezing liquid uses
22.5% calcium chloride solution, cryogenic temperature are -5 DEG C, cooling time 3.5h；Crystallized stock, which is put into centrifuge and be centrifuged, to be taken off
Water, dewatered material pass through single cone vacuum dryer drying (103 DEG C of drying temperature) again and obtain by-product sodium sulphate, realize salt resource
Change and utilizes；Meanwhile on the other hand, the condensate liquid that MVR evaporator generates enters pH conditioning tank and adjusts pH value to after 3, is made using pump
It enters Fenton oxidation tower, by using granular activated carbon as carrier, catalyst that active material is Pd, catalysis oxidation H2O2
The organic matter in the further degrading waste water of OH with Strong oxdiative ability generated, strengthens the removal of COD and hard-degraded substance,
Discharge pond is finally flowed into, wherein the content of catalyst is 5% in Fenton oxidation tower, and loaded catalyst is tower dischargeable capacity
7/12, H2O2For the H of mass fraction 30%2O2, H2O2Flow be the 1 ‰ of inflow, and open aeration, gas-water ratio 25:1；
After resin adsorption tower adsorption saturation, desorption processing is carried out, flow velocity 0.75BV/h is desorbed, desorbing agent is using 6% liquid alkaline compounding 85%
Methanol solution；The desorption liquid of generation enters rectifying column rectifying methanol reuse, compounds desorbing agent, and remaining distillation residual liquid enters burning
Furnace disposition.
Metribuzin waste water treatment process the following steps are included:
1) waste water is promoted to horizontal flow type grit chamber intake chamber from the boosted pump of wastewater collection tank, removes through horizontal flow type grit chamber
Granule foreign is collected subsequently into intermediate pool；Horizontal flow type grit chamber flow control is in 0.2m/s, residence time 1.5min, periodically
Gravity sediment outflow is opened, sludge discharging period is 1 day.
2) intermediate pool waste water enters resin adsorption-desorption column progress adsorption treatment, and removing higher boiling macromolecular in waste water has
Machine object, waste water from bottom to top, adsorption flow rate 1.5BV/h；After adsorption saturation, inlet valve is closed, is pumped by metering pump from top
Enter 6% liquid alkaline, 85% methanol solution of compounding and carry out desorption processing, flow velocity 0.75BV/h is desorbed.It is synchronous to open another group of resin suction
The inlet valve of attached-desorption column carries out adsorption treatment, and two groups of resin adsorption towers carry out adsorption-desorption switching.Resin tower generates de-
Attached liquid enters rectifying column rectifying recycling methanol, compounds desorbing agent, and remaining distillation residual liquid enters incinerator disposition.
3) from pH neutralization pond is flowed into, liquid alkaline is added dropwise in synchronous metering pump of opening, and opens submersible agitator for resin adsorption water outlet,
Even regulation water outlet pH value is to 7, effluent collection to MVR stock solution collection tank.
4) waste water in MVR stock solution collection tank is pumped into MVR evaporator and is evaporated processing, 95 DEG C of evaporating temperature.It generates
Condensate liquid and concentrate are separately stored in respective collecting tank.
5) MVR condensate liquid is pumped from collecting tank to pH conditioning tank, sulfuric acid is added dropwise in synchronous metering pump of opening, and opens diving
Blender, even regulation water outlet pH value to 3, effluent collection to Fenton water inlet collecting tank.
6) raw water in Fenton water inlet collecting tank is pumped into Fenton oxidation tower, top water inlet, bottom U-tube overflow goes out
Water.It is synchronous to open H2O2Metering pump is by H2O2It is pumped into inlet pipeline, wherein H2O2Flow is the 1 ‰ of inflow, and opens aeration, gas
Water ratio is 25:1.The hydraulic detention time of Fenton oxidation tower is 1.5h, and water outlet is discharged into garden from discharge pond, standard water discharge is flow to
Pipe network.
7) on the other hand, MVR concentrate is pumped into freezing and crystallizing kettle from collecting tank, and calcium chloride freezing liquid is pumped into crystallization kettle folder
Set carries out freezing and crystallizing, and cryogenic temperature is at -5 DEG C, cooling time 3.5h.After freezing, material is put into centrifuge from bottom
Centrifugal dehydration is carried out in material trough, dewatered material transfers to drying chamber, carries out drying and processing using single cone vacuum dryer
By-product sodium sulphate, 103 DEG C of drying temperature.
Treated that effluent quality situation is shown in Table 5 by the present invention.
Each workshop section's effluent quality of 5 group technology of table processing
As shown in Table 5, after resin adsorption, COD concentration is obviously greatly lowered metribuzin raw wastewater, using
The COD concentration of MVR evaporator treated condensate liquid has certain reduction, and more it is worth noting that, total salt concentration significantly subtracts
Few, COD≤500mg/L, the total salt≤5000mg/L of last Fenton oxidation water outlet can be discharged into garden sewage network.
Comparative example 1
This comparative example is substantially same as Example 1, the difference is that: what is loaded in Fenton oxidation tower is that ternary is negative
Load type activated-carbon catalyst CuO-MnO2- ZnO/AC, the indices of final outflow water water quality are as shown in table 6:
Each workshop section's effluent quality of 6 group technology of table processing
As shown in Table 6, after resin adsorption, COD concentration is obviously greatly lowered metribuzin raw wastewater, using
The COD concentration of MVR evaporator treated condensate liquid has certain reduction, and more it is worth noting that, total salt concentration significantly subtracts
It is few, but COD >=500mg/L of last Fenton oxidation water outlet, it is not able to satisfy garden sewage network adapter tube standard.
Comparative example 2
MVR evaporator in wastewater treatment concrete technology flow process compared with Example 1, is advanceed to resin and inhaled by this comparative example
Before attached-desorption column, specific wastewater treatment concrete technology flow process is as follows:
With high salt, high COD, difficult for biological degradation metribuzin waste water is miscellaneous by granular solids in horizontal flow type grit chamber removal waste water
Matter flows into intermediate pool again, wherein horizontal flow type grit chamber flow control opens primary weight in 0.1m/s, residence time 3min daily
Power sediment outflow carries out sludge discharge work；Intermediate pool water outlet enters MVR evaporator, setting evaporation temperature after pH neutralization pond adjusting pH value to 7
Degree is 90 DEG C；On the one hand, the concentrate that MVR evaporator generates is pumped into freezing and crystallizing kettle, passes through jacket type freezing and crystallizing, wherein
Freezing liquid uses 25% calcium chloride solution, and cryogenic temperature is -15 DEG C, cooling time 2h；Crystallized stock be put into centrifuge into
Row centrifugal dehydration, dewatered material passes through single cone vacuum dryer drying (105 DEG C of drying temperature) again and obtains by-product sodium sulphate, real
Existing salt resource utilization；Meanwhile on the other hand, the condensate liquid that MVR evaporator generates is pumped into resin adsorption-desorption column, wherein tree
The resin partial size loaded in rouge adsorption-desorption tower is 0.1mm~0.2mm, and resin loadings are the 1/3 of tower dischargeable capacity, absorption
Flow velocity 2BV/h, the high boiling point organic compound in waste water are removed by large aperture resin adsorption, and COD is greatly lowered, waste water it is biochemical
Property improve；The absorption efflux of resin adsorption water outlet enters pH conditioning tank and adjusts pH value to after 3, makes it into Fenton using pump
Oxidizing tower (7), by using granular activated carbon as the PdO solid catalyst of carrier, catalysis oxidation H2O2What is generated has Strong oxdiative energy
Organic matter in the further degrading waste water of the OH of power strengthens the removal of COD and hard-degraded substance, finally flows into discharge pond,
The work for the PdO and 90%~95% that the content (mass fraction) of catalyst main component is 1~10% in middle Fenton oxidation tower
Property charcoal, loaded catalyst be tower dischargeable capacity 1/2, H2O2For the H of mass fraction 30%2O2, H2O2Flow be inflow
0.7 ‰, and aeration is set, gas-water ratio 30:1；After resin adsorption tower adsorption saturation, desorption processing is carried out, flow velocity is desorbed
1BV/h, desorbing agent compound methanol solution using 5% liquid alkaline；The desorption liquid of generation enters rectifying column rectifying methanol reuse, and compounding is de-
Attached dose, remaining distillation residual liquid enters incinerator disposition.
Metribuzin waste water treatment process the following steps are included:
1) waste water is promoted to horizontal flow type grit chamber intake chamber from the boosted pump of wastewater collection tank, removes through horizontal flow type grit chamber
Granule foreign is collected subsequently into intermediate pool；Horizontal flow type grit chamber flow control is periodically opened in 0.1m/s, residence time 3min
Gravity sediment outflow is opened, sludge discharging period is 1 day.
2) intermediate pool waste water enters pH neutralization pond, and liquid alkaline is added dropwise in synchronous metering pump of opening, and opens submersible agitator, uniformly
Water outlet pH value is adjusted to 7, effluent collection to MVR stock solution collection tank.
3) waste water in MVR stock solution collection tank is pumped into MVR evaporator and is evaporated processing, 90 DEG C of evaporating temperature.It generates
Condensate liquid and concentrate are separately stored in respective collecting tank.
4) MVR condensate liquid is pumped to resin adsorption-desorption column from collecting tank and carries out adsorption treatment, removed high boiling in waste water
Point larger molecular organics, waste water from bottom to top, adsorption flow rate 2BV/h；After adsorption saturation, inlet valve is closed, metering pump is passed through
Liquid alkaline 90% methanol solution of compounding is pumped into from top and carries out desorption processing, and flow velocity 1BV/h is desorbed.It is synchronous to open another group of resin suction
The inlet valve of attached-desorption column (3) carries out adsorption treatment, and two groups of resin adsorption towers carry out adsorption-desorption switching.What resin tower generated
Desorption liquid enters rectifying column (12) rectifying recycling methanol, compounds desorbing agent, and remaining distillation residual liquid enters incinerator disposition.
5) from pH conditioning tank (6) are flowed into, sulfuric acid is added dropwise in synchronous metering pump of opening, and opens submersible agitating for resin adsorption water outlet
Device, even regulation water outlet pH value to 3, effluent collection to Fenton water inlet collecting tank.
6) raw water in Fenton water inlet collecting tank is pumped into Fenton oxidation tower (7), top water inlet, bottom U-tube is overflow
Outflow water.It is synchronous to open H2O2Metering pump is by H2O2It is pumped into inlet pipeline, H2O2For the H of mass fraction 30%2O2, H2O2Flow
It is the 0.7 ‰ of inflow, and opens aeration, gas-water ratio 30:1.The hydraulic detention time of Fenton oxidation tower is 2h, and water outlet is certainly
It is flow to discharge pond (8), standard water discharge is discharged into garden pipe network.
7) on the other hand, MVR concentrate is pumped into freezing and crystallizing kettle (8) from collecting tank, calcium chloride freezing liquid is pumped into crystallization
Kettle collet carries out freezing and crystallizing, and cryogenic temperature is -15 DEG C, cooling time 2h.After freezing, material is put into centrifugation from bottom
Centrifugal dehydration is carried out in the material trough of machine (9), dewatered material transfers to drying chamber, using single cone vacuum dryer (10) into
Row drying and processing obtains by-product sodium sulphate, and 105 DEG C of drying temperature.
Treated that effluent quality situation is shown in Table 7 by the present invention.
Each workshop section's effluent quality of 7 group technology of table processing
By table 7 and table 2 it is found that in metribuzin raw wastewater treatment process, MVR evaporator is advanced to before resin adsorption, is given up
Water is after MVR evaporation process, and COD decreases and total salt is greatly lowered, then after resin adsorption and Fenton oxidation, finally
It is discharged COD≤500mg/L, total salt≤5000mg/L, meets garden adapter tube standard, but in the preposition one side waste water of MVR evaporator
High boiling point organic compound can stay in by-product salt, influence the quality of by-product salt, on the other hand fail to make full use of resin adsorption
Efficient COD removal effect.In addition, the salinity in effluent quality is higher compared to present invention process, the salt rate of recovery is declined slightly.
Thus, group technology of the present invention has synergistic effect to metribuzin discharged wastewater met the national standard and salt recycling treatment therein.
Claims (10)
1. a kind for the treatment of process of metribuzin discharged wastewater met the national standard collaboration salt recycling, it is characterised in that: including wastewater treatment work
Skill and salt process for reclaiming, the waste water treatment process successively includes precipitating, resin adsorption, MVR, pH are adjusted and Fenton oxygen
Change, for the salt process for reclaiming by carrying out freezing and crystallizing to concentrate in MVR workshop section, centrifugation drying obtains industry purification sulphur
Sour sodium.
2. a kind for the treatment of process of metribuzin discharged wastewater met the national standard collaboration salt recycling according to claim 1, feature
Be: described is precipitated as sand setting processing, and setting pot uses horizontal flow type grit chamber, and horizontal flow velocity 0.1m/s~0.2m/s is stopped
Time 2min~3min.
3. a kind for the treatment of process of metribuzin discharged wastewater met the national standard collaboration salt recycling according to claim 1, feature
Be: the resin adsorption includes adsorption and desorption and regeneration treatment three phases.
4. a kind for the treatment of process of metribuzin discharged wastewater met the national standard collaboration salt recycling according to claim 3, feature
Be: the absorption phase uses graininess superhigh cross-linking compound resin, partial size 0.1mm~0.2mm, adsorption flow rate 1BV/h
~2BV/h；The desorbing agent that the desorption stage uses adds the mixed liquor that organic solvent is prepared for 2%~10% liquid alkaline,
Wherein, organic solvent is methanol or ethyl alcohol, and the mass concentration of organic solvent is 80%~90%, desorption flow velocity 0.5BV/h~
1BV/h；The regeneration treatment stage is by the organic solvent in rectifying recycling desorption liquid to compound desorbing agent.
5. a kind of according to claim 1, place of metribuzin discharged wastewater met the national standard collaboration salt recycling described in 3 or 4 any one
Science and engineering skill, it is characterised in that: the waste water obtained after the resin adsorption first carries out pH neutralisation treatment and flows into MVR, the pH again
Neutralization is that the pH of waste water is adjusted to 7~8, the pH adjusting agent used for 30% NaOH solution.
6. a kind for the treatment of process of metribuzin discharged wastewater met the national standard collaboration salt recycling according to claim 5, feature
Be: the MVR evaporator, evaporating temperature are 85 DEG C~95 DEG C.
7. a kind for the treatment of process of metribuzin discharged wastewater met the national standard collaboration salt recycling according to claim 1, feature
Be: the pH adjusting is that condensate liquid pH value is adjusted to 3~4, and the pH adjusting agent used is 98% dense H2SO4。
8. a kind for the treatment of process of metribuzin discharged wastewater met the national standard collaboration salt recycling according to claim 1, feature
Be: the Fenton oxidation is heterogeneous Fenton oxidation, and the catalyst of Fenton oxidation is used is with granular activated carbon
The transition metal oxide solid catalyst of carrier, preferably PdO, Pt or Pd, content 0.1%~5%, catalyst volume account for reaction
The 1/2~2/3 of container dischargeable capacity；Using 30% H2O2, H2O2Dosage be flow of inlet water 0.5 ‰~1 ‰；It is described
Fenton oxidation reaction process in a certain amount of uniform aeration is provided, wherein QGas/QWaterFor (20~30): 1.
9. a kind for the treatment of process of metribuzin discharged wastewater met the national standard collaboration salt recycling according to claim 1, feature
Be: the freezing and crystallizing is freezed using jacket type, the calcium chloride water that freezing liquid is 20%~25%, cryogenic temperature
It is -20 DEG C~-5 DEG C；The centrifugation drying is to carry out centrifugal dehydration to crystallization kettle material using vertical centrifugal machine, then using single
Bore vacuum dryer to centrifugal material carry out drying and processing, 103 DEG C~105 DEG C of drying temperature.
10. a kind of operation method of metribuzin discharged wastewater met the national standard collaboration salt recycling, including following processing step:
1) waste water is through the bulky grain solid impurity in horizontal flow type grit chamber removal waste water, horizontal flow control in 0.1~0.2m/s,
2~3min of residence time；
2) setting pot water outlet flow to intermediate pond body and collects, synchronous to open intermediate pond body elevator pump, by pipeline by waste water from resin
Adsorption tower bottom is pumped into, top outflow, 1~2BV/h of adsorption flow rate；
3) two groups of resin adsorption towers are set, alternately, switching valve is arranged in inlet pipeline to adsorption-desorption, closes after one group of adsorption saturation
Valve closing door switches to another group of resin adsorption tower；Using liquid alkaline compounding organic solvent as desorbing agent, wherein organic solvent is first
Alcohol or ethanol solution open metering pump, desorbing agent are pumped into from resin adsorption top of tower, and 0.5~1BV/h of flow velocity is desorbed；Tower bottom
Portion is equipped with automatic control flowing water Valve, and desorption liquid is flowed out from bottom；
4) collect desorption liquid recycle organic solvent through rectifier unit, as desorbing agent prepare solution, remaining distillation residual liquid into
Enter incinerator disposition；
5) resin adsorption tower water outlet is from pH neutralization pond is flow to, and liquid alkaline is added dropwise by metering pump in water inlet, and lye and resin are inhaled
The synchronous water inlet of attached tower water outlet, pond body are diagonally equipped with submersible agitator, guarantee that water body soda acid reconciles uniformly, water outlet pH value 7~
8；
6) water outlet of pH neutralization pond is delivered to the processing of MVR system, evaporating temperature 85 by pump from MVR stock solution collection tank, stoste is flow to
~95 DEG C, the condensate liquid of generation is collected to condensate liquid collecting tank, and the concentrate of generation is pumped by transfer tank to crystallization kettle；
7) after concentrate is pumped into crystallization kettle, it is pumped into chilled brine into kettle external jacket and carries out freezing and crystallizing, cryogenic temperature -20~-5
DEG C, 2~5h of cooling time；
8) crystallized stock in crystallization kettle, which is put into vertical centrifugal machine, carries out centrifugal dehydration, and dewatered material transfers to drying chamber
Single cone vacuum dryer in drying and processing, 103 DEG C~105 DEG C of drying temperature；Material after drying is by-product industrial sulphuric acid
Sodium；
9) treated that condensate liquid is pumped from collecting tank to pH conditioning tank by MVR, and the concentrated sulfuric acid is added dropwise by metering pump in water inlet；And it is dense
The synchronous water inlet of sulfuric acid and MVR treated condensate liquid, pond body are diagonally equipped with submersible agitator, guarantee that water body pH reconciles uniformly, out
Mouth of a river pH value is 3~4；
10) water outlet of pH conditioning tank opens elevator pump for stoste and is pumped into Fenton oxidation tower, push up from Fenton water inlet collecting tank is flow to
Portion's water inlet, bottom U-tube overflow water outlet, 2~3h of residence time；It is synchronous to open H2O2Metering pump is by H2O2It injects in waste line
It is uniformly mixed, and opens blower and provide aeration for tower body, the air quantity and flow of inlet water of blower are than control in (20~30): 1；
11) water outlet of Fenton oxidation tower is pumped into garden pipe network from discharge pond, standard water discharge is flow to.
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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 |
| CN112607947A (en) * | 2020-12-17 | 2021-04-06 | 江苏南大华兴环保科技股份公司 | Systematization method for applying resin to high-concentration organic wastewater treatment |
| CN112678984A (en) * | 2019-10-17 | 2021-04-20 | 中国石油化工股份有限公司 | Treatment method of cleaning wastewater of butylbenzene emulsion device |
| CN113698016A (en) * | 2021-06-21 | 2021-11-26 | 江苏中科双鑫环保设备有限公司 | Chemical pesticide technology waste water resourceful treatment energy-saving equipment |
| CN114477611A (en) * | 2021-09-29 | 2022-05-13 | 福州市聚泰环境科技有限公司 | Method for preparing biological organic nutrient solution and cement grinding aid base material by using acidified oil production wastewater |
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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 |
| CN112607947A (en) * | 2020-12-17 | 2021-04-06 | 江苏南大华兴环保科技股份公司 | Systematization method for applying resin to high-concentration organic wastewater treatment |
| CN113698016A (en) * | 2021-06-21 | 2021-11-26 | 江苏中科双鑫环保设备有限公司 | Chemical pesticide technology waste water resourceful treatment energy-saving equipment |
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