CN107721081A - A kind of innocuity disposal system and method for chlorophenols waste water - Google Patents
A kind of innocuity disposal system and method for chlorophenols waste water Download PDFInfo
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- CN107721081A CN107721081A CN201711172990.7A CN201711172990A CN107721081A CN 107721081 A CN107721081 A CN 107721081A CN 201711172990 A CN201711172990 A CN 201711172990A CN 107721081 A CN107721081 A CN 107721081A
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Abstract
The invention discloses a kind of Harmless and Comprehensive Disposal system and method for chlorophenols waste water, processing system includes pretreatment unit, wet oxidation reaction device, waste water deployment device, biochemical treatment apparatus and exhaust gas processing device etc., method using said system processing chlorophenols waste water includes corresponding processing step, wherein, preprocessing process mainly to remove the suspension in waste water, pH regulation, with biochemical treatment caused by excess sludge mixed；The mixture of chlorophenols waste water and biochemical sludge carries out wet oxidation processing, and through peroxide degradation, chlorophenol conversion ratio is more than 85%, and the biochemical index of waste water is improved to more than 0.4；Tail gas caused by wet oxidation enters biofilter and carries out vent gas treatment, purifying harmful gas；Wet oxidation water outlet enters membrane bioreactor after waste water is allocated and carries out biochemical treatment, removes organic pollution remaining in waste water.Through integrated artistic, the COD clearances of Chlorophenol are more than 95%；The problem of technique is easily operated, and water quality safety is high, stable effluent quality, and emission-free discharge and sludge produce.
Description
Technical field
The present invention relates to wastewater processing technology, and in particular to a kind of innocuity disposal system and method for chlorophenols waste water.
Background technology
With the industrialized continuous development in China, increasing compound is applied to various industries.Have as one kind
There is the material of the effect of broad-spectrum sterilization, desinsection, chlorophenols compound is widely used in preservative, antirust agent, insecticide, killed
In the industries such as microbial inoculum, herbicide.The use of a large amount of chlorophenols compounds causes it inevitably to enter in environment water.By
There is stronger bactericidal activity, bio-toxicity and carcinogenic, teratogenesis, mutagenesis etc. " three cause " effect in chlorophenols compound, and
It is difficult to degrade in the environment, can be constantly accumulated in vivo by food chain and food web, serious threat human health
And ecological environment.Therefore need to effectively being handled containing Chlorophenol.
Chlorophenols compound causes its biodegradability very low due to the presence of its specific aromatic ring structure and chloro atom,
Therefore, it is difficult to be removed using conventional biological treatment.Therefore existing biodegradable chlorophenols compound is needed using special
Property flora is degraded, and operating condition is harsh, such as CN103736241A.High-level oxidation technology is often used as chloride
The technique of phenol wastewater treatment.The effect of the wherein oxidation of ozone direct oxidation parachlorphenol class material is poor, and disposal ability is weak；Catalysis
Oxidation because a large amount of uses of catalyst cause it is seriously polluted and expensive；And although photocatalytic oxidation avoids catalyst
Pollution problem, but for the industrial wastewater of light transmittance difference, treatment effect is bad.Meanwhile although high-level oxidation technology to chlorine
Aldehydes matter has certain degradation efficiency, but intermediate product or by-product that a large amount of structures differ can be produced in oxidizing process
Thing, the toxicity of some of which intermediate product can also be far longer than parent pollutant, it is difficult to be truly realized the innoxious of chlorophenols waste water
Processing.Therefore, the purpose for removing chlorophenol pollutant in water body can not be fully achieved in treatment technology single at present.
The content of the invention
For wastewater biodegradability present in current chlorophenols wastewater treatment process is poor, intermediate product of processing procedure
It is more, remove the defects of not thorough, the present invention provides a kind of innocuity disposal system of chlorophenols waste water and corresponding processing side
Method.
The innocuity disposal system of chlorophenols waste water of the present invention, including the pretreatment being sequentially communicated by pipeline fill
Put, wet oxidation reaction device, waste water deployment device and biochemical treatment apparatus, wherein, the wet oxidation reaction device
Liquid product and solid residue outlet are connected with the entrance of waste water deployment device, the gas phase production of the wet oxidation reaction device
Directly by being discharged after pipeline communication to exhaust gas processing device processing, the water outlet after the biochemical treatment apparatus processing is straight for thing outlet
Run in, sludge caused by biochemical treatment apparatus processing is then introduced directly into wet oxidation reaction device by pipeline.
Wherein, a blender can also be set up between the pretreatment unit and wet oxidation reaction device, by biochemistry
Biochemical sludge derived from processing unit is first imported in blender and is well mixed with the filtrate after pretreatment unit pretreatment,
Then wet oxidation reaction device is imported again.
The biochemical treatment apparatus is membrane bioreactor.Membrane bioreactor sludge concentration be 5000-10000mg/L,
Aeration quantity is 20-40L/h, hydraulic detention time 1-5h.
The exhaust gas processing device is biofilter.Filler in the biofilter is peat, wood chip, porous ceramics,
One or more in granular activated carbon, treatment temperature is 25-35 DEG C, pH 7-8.
Preferably, a circulating pump is in series with the sludge outlet pipeline of the biochemical treatment apparatus.
Using the method for above-mentioned innocuity disposal system processing chlorophenols waste water, comprise the following steps：
(1) pre-process：Pending chlorophenols waste water is imported into pretreatment unit, flocculant is added, is filtered off after stirring
Oil removal and particulate matter, regulation filtrate pH is 7-9；Then filtrate is mixed with sludge caused by step (4) biochemical treatment, obtained
To mixture；
(2) wet oxidation：Mixture after being pre-processed via step (1) is transported to wet oxidation reaction device, added
Enter catalyst reaction, the organic pollution in mixture is degraded, and forms gas phase and liquid product and a small amount of solid residue；
After the completion of reaction, gas-phase product is discharged after being discharged into exhaust gas processing device purification, and liquid product and solid residue enter in next step
Reason；
(3) waste water is allocated：Liquid product and solid residue caused by step (2) wet oxidation reaction are delivered into waste water to adjust
With device, precipitation removes solid residue, then adjusts wastewater pH to 6-8, temperature to 20-35 DEG C, salt content and is less than 2%；
(4) biochemical treatment：Waste water after being allocated via step (3) imports biochemical treatment apparatus, and the water outlet after processing is straight
Run in and put, the filtrate that caused biochemical sludge then obtains with step (1) pretreatment after processing imports wet oxidation in the lump after mixing
Reaction unit.
In step (1), the flocculant is FeCl3、AlCl3, Sodium Polyacrylate and polyacrylamide it is therein a kind of or several
Kind, dosage is the 0.1%-0.3% of pending chlorophenols wastewater quality.
In step (1), according to actual conditions, it is 7-9 that acid or alkali regulation pH are added into filtrate.
In step (2), the catalyst is the one or more in the metal salt solutions such as Cu, Fe, Mn, Ce and Ti, is added
Measure the 0.1%-0.2% for pending chlorophenols waste water and biochemical sludge mixture quality.
In step (2), the wet oxidation reaction condition is：It is 250-320 DEG C of reaction temperature, reaction pressure 5-8MPa, anti-
0.5-2h between seasonable, oxidant used are oxygen, coefficient of oxidation 1.2-1.5.The wet oxidation reaction device is that continous way is anti-
Answer device, it is possible to achieve continuous feed and discharging.The wet oxidation reaction device uses oxygenerator to show by raw material of air
Field high purity oxygen, for wet oxidation reaction, oxygen purity>90%.The present invention realizes continuously to enter using continous way device
Discharging, is advantageous to industrial applications；Using oxygenerator formed in-situ high purity oxygen gas, be advantageous to improve pollution clearance and reduction
Energy consumption.
In step (2), the exhaust gas processing device is biofilter, is directly discharged after purifying harmful gas.Further,
Filler in the biofilter is peat, the one or more in wood chip, porous ceramics, granular activated carbon, and treatment temperature is
25-35 DEG C, pH 7-8.
In step (4), the biochemical treatment system is membrane bioreactor, the organic pollution further gone in water removal,
Wherein, membrane bioreactor sludge concentration be 5000-10000mg/L, aeration quantity 20-40L/h, hydraulic detention time 1-
5h。
In above-mentioned integrated conduct method, the reaction mass of wet oxidation is the mixture of chlorophenols waste water and biochemical sludge,
Water outlet biodegradability >=0.4 after wet oxidation is handled.After integrated artistic, conversion ratio >=99% of chlorophenol, Chlorophenol
COD clearance >=95%.
Summary is visible, the method for innocent treatment of chlorophenols waste water provided by the invention, is " pretreatment+wet type oxygen
The group technology of change+allotment+biochemistry+vent gas treatment ", oxidative degradation is carried out using wet oxidation process parachlorphenol waste water, by chlorophenol
Small organic molecule is oxidized to, improves its biodegradability；Gone out using the membrane bioreactor wet oxidation higher to biodegradability
Water is handled, and further removes the organic pollution in water body so that chlorophenols remove completely, are remained caused by biochemical process
Remaining sludge carries out wet oxidation processing after being mixed with Chlorophenol；Tail gas caused by wet oxidation is carried out using biofilter net
Change is handled.
Beneficial effect：Prior art is compared to, herein described integrated conduct method has the advantage that：
(1) usage amount of the advanced oxidation processes chemical agent such as traditional Fenton is big, and it is more to produce iron cement, it is difficult to clear up, and
The present invention carries out oxidative degradation using wet-type oxidation technology parachlorphenol class waste water, reduces the dosage of chemical agent and the production of sludge
It is raw；
(2) oxidation effectiveness of traditional advanced oxidation processes parachlorphenol class waste water is bad, and the wet type oxygen that the present invention uses
Conversion ratio >=85% of chemical industry skill parachlorphenol, chlorophenol are broken down into small carboxylic acid molecules and chlorion, and oxidation effectiveness is good, greatly carries
The high biodegradability of waste water, wet oxidation water outlet biodegradability >=0.4；Wet oxidation reaction device used is continuous reaction
Device, it is possible to achieve continuous feed and discharging, be easy to large-scale commercial application.
(3) present invention combines wet-type oxidation technology and membrane bioreactor, can greatly reduce what is remained in waste water
Organic pollution, conversion ratio >=99%, COD clearance >=95% of chlorophenol, reduce water body security risk；
(4) wet-type oxidation technology and membrane bioreactor provided by the invention are combined, and are reduced retention time of sewage, are easy to
Operation, and water standard is high, stable effluent quality；
(5) pretreated chlorophenols waste water is carried out mixing tune by the present invention with sludge caused by biochemical treatment process
Match somebody with somebody, it is common to carry out wet oxidation processing, reduce processing and the disposal costs of biochemical sludge；
(6) middle produce is reduced using the processing combination of different process to improve the degradation efficiency of chlorophenols in waste water
The generation of thing, reduce it and poison risk to reach innoxious purpose, meet environment protection requirement.
Brief description of the drawings
Fig. 1 is the innocuity disposal system schematic diagram of chlorophenols waste water.
Embodiment
In order that objects and advantages of the present invention are more clearly understood, the present invention is carried out specifically with reference to embodiments
It is bright.
Embodiment 1
The innocuity disposal system of chlorophenols waste water as shown in Figure 1, including the pretreatment being sequentially communicated by pipeline fill
Put, wet oxidation reaction device, waste water deployment device and biochemical treatment apparatus, wherein, the wet oxidation reaction device
Liquid product and solid residue outlet are connected with the entrance of waste water deployment device, the gas phase production of the wet oxidation reaction device
Directly by being discharged after pipeline communication to exhaust gas processing device processing, the water outlet after the biochemical treatment apparatus processing is straight for thing outlet
Run in, sludge caused by biochemical treatment apparatus processing is then introduced directly into wet oxidation reaction device by pipeline.Life therein
Change processing unit is membrane bioreactor, and exhaust gas processing device is biofilter.
Embodiment 2
The harmless treatment of chlorophenols waste water is carried out using the system described in embodiment 1.
Certain chemical industry factory production waste water, pH value 2.28, COD 9100mg/L, wherein contain 125.8mg/L2,4- dichloros
Phenol, 127.2mg/L2,4,6- trichlorophenols, 75.4mg/L2,3,5,6- tetra-chloro-phenols.Waste water imports pretreatment unit, adds 0.1%
Sodium Polyacrylate, flocculation stirring, then filter, remove water body in suspension, add 30% liquid caustic soda regulation water body pH
It is worth for 7；Waste water is mixed with excess sludge caused by biochemical reaction, wet oxidation reaction device is introduced, adds 0.1%
FeCl3As catalyst, for oxygen as oxidant, oxygen purity 93%, reaction temperature are 250 DEG C, reaction pressure 5MPa, anti-
It is 0.5h between seasonable, the conversion ratio of chlorophenols is 85.3% after wet oxidation system, and water outlet biodegradability is 0.4；It is wet
Formula oxidation water outlet enters waste water deployment device, adjusts the pH to 6 of waste water, temperature is 20 DEG C, salt content 1%, is then drawn
Enter membrane bioreactor, membrane bio-reaction system sludge concentration is 5000mg/L, aeration quantity 20L/h, hydraulic detention time are
1h；Excess sludge caused by membrane bio-reaction system, introduce wet oxidation reaction device and handled；The tail gas of wet oxidation draws
Enter biofilter and carry out vent gas treatment, bio-filter stuffing is peat, temperature is 25 DEG C, pH 7.After the PROCESS FOR TREATMENT,
The COD clearances of the chlorophenols waste water are 95.7%, the removal efficiency 99.5% of chlorophenols, are reached《Integrated wastewater discharges
Standard》GB8978-1996 grade III Standard, meet the adapter requirement of the sewage treatment plant of chemical industrial park.
Comparative example 1
The pending waste water of the comparative example is with embodiment 2, concrete operations and the difference of embodiment 2：Only carry out wet
Formula aoxidizes, and no longer carries out biochemical treatment.The conversion ratio of chlorophenols is 82.1% after wet oxidation system, and water outlet is biochemical
Property is 0.4, and COD clearances are only 75.5%, it is impossible to meet the adapter requirement of the sewage treatment plant of chemical industrial park.
Comparative example 2
The pending waste water of the comparative example is with embodiment 2, concrete operations and the difference of embodiment 2：Using air
As oxidant.After integrated artistic is handled, the COD clearances of the chlorophenols waste water are 91.2%, and chlorophenols are gone
Except the adapter requirement of efficiency 95.0%, the not up to sewage treatment plant of chemical industrial park.
Embodiment 3
Certain chemical industry factory production waste water, pH value 4.08, COD 21200mg/L, wherein contain 132.2mg/L2,4,6- tri-
Chlorophenol, the tetra-chloro-phenols of 327.4mg/L 2,3,5,6-, 260.3mg/L pentachlorophenols.Waste water imports pretreatment unit, adds 0.1%
Polyacrylamide flocculation stirring, is then filtered, and removes the suspension in water body, and the pH value for adding NaOH regulation water bodys is 8；Will be useless
Water mixes with excess sludge caused by biochemical reaction, introduces wet oxidation reaction device, adds 0.15% MnCl2As catalysis
Agent, oxygen is as oxidant, and oxygen purity 95%, reaction temperature are 280 DEG C, reaction pressure 7MPa, reaction time 1h, warp
The conversion ratio of chlorophenols is 89.8% after wet oxidation system, and water body biodegradability is 0.5；Wet oxidation water outlet enters useless
Water deployment device, adjusts the pH to 7 of waste water, temperature is 25 DEG C, salt content 1.5%, is then introduced into membrane bioreactor,
Membrane bio-reaction system sludge concentration is 7500mg/L, aeration quantity 30L/h, hydraulic detention time 3h；Membrane biological reaction system
Excess sludge caused by system, introduce wet oxidation reaction device and handled；The tail gas of wet oxidation introduces biofilter and carried out
Vent gas treatment, bio-filter stuffing are wood chip, and temperature is 30 DEG C, pH 8.After system processing, the chlorophenols waste water
COD clearances are 97.6%, the removal efficiency 99.8% of chlorophenols, are reached《Integrated wastewater discharge standard》GB8978-
1996 grade III Standard, meet the adapter requirement of the sewage treatment plant of chemical industrial park.
Embodiment 4
Certain chemical industry factory production waste water, pH value 6.67, COD 39700mg/L, wherein containing 250.5mg/L2- chlorophenols,
148.5mg/L 2,4- Dichlorophenol, 326mg/L 2,6- Dichlorophenols, 222.6mg/L pentachlorophenols.Waste water imports pretreatment unit, adds
Enter 0.3% AlCl3Flocculation stirring, then filter, remove the suspension in water body, the pH value for adding NaOH regulation water bodys is 9；
Waste water is mixed with excess sludge caused by biochemical reaction, introduces wet oxidation reaction device, adds 0.2% Cu (NO3)2Make
For catalyst, oxygen as oxidant, oxygen purity 91%, reaction temperature are 320 DEG C, reaction pressure 8MPa, the reaction time
For 2h, the conversion ratio of chlorophenols is 94.7% after wet oxidation system, and water body biodegradability is 0.6；Wet oxidation goes out
Water enters waste water deployment device, adjusts the pH to 8 of waste water, temperature is 30 DEG C, salt content 0.4%, is then introduced into film life
Thing reactor, membrane bio-reaction system sludge concentration is 10000mg/L, aeration quantity 40L/h, hydraulic detention time 5h.Film
Excess sludge caused by bio-reaction system, introduce wet oxidation reaction device and handled；The tail gas of wet oxidation introduces life
Thing filter tank carries out vent gas treatment, and bio-filter stuffing is porous ceramics, and temperature is 35 DEG C, pH 7.5.Handled by the system
Afterwards, the COD clearances of the chlorophenols waste water are 98.8%, the removal efficiency 99.9% of chlorophenols, are reached《Integrated wastewater is arranged
Put standard》GB8978-1996 grade III Standard, meet the adapter requirement of the sewage treatment plant of chemical industrial park.
Claims (7)
1. a kind of innocuity disposal system of chlorophenols waste water, it is characterised in that including the pretreatment being sequentially communicated by pipeline
Device, wet oxidation reaction device, waste water deployment device and biochemical treatment apparatus, wherein, the wet oxidation reaction device
Liquid product and solid residue outlet be connected with the entrance of waste water deployment device, the gas phase of the wet oxidation reaction device
Product exit after pipeline communication to exhaust gas processing device processing directly by discharging, the water outlet after the biochemical treatment apparatus processing
It is expelled directly out, sludge caused by biochemical treatment apparatus processing is then introduced directly into wet oxidation reaction device by pipeline.
2. utilize the method for system processing chlorophenols waste water described in claim 1, it is characterised in that comprise the following steps：
(1) pre-process：Pending chlorophenols waste water is imported into pretreatment unit, adds flocculant, is filtered off after stirring except outstanding
Float and particulate matter, regulation filtrate pH is 7-9, and then filtrate is mixed with sludge caused by step (4) biochemical treatment, is mixed
Compound；
(2) wet oxidation：Mixture after being pre-processed via step (1) is transported to wet oxidation reaction device, addition is urged
Agent is reacted, and the organic pollution in mixture is degraded, and forms gas phase and liquid product and a small amount of solid residue；Reaction
After the completion of, gas-phase product is discharged after being discharged into exhaust gas processing device purification, and liquid product and solid residue enter processing in next step；
(3) waste water is allocated：Liquid product and solid residue caused by step (2) wet oxidation reaction are delivered to waste water allotment dress
Put, precipitation removes solid residue, then adjusts wastewater pH to 6-8, temperature to 20-35 DEG C, salt content and is less than 2%；
(4) biochemical treatment：Waste water after being allocated via step (3) imports biochemical treatment apparatus, and the water outlet after processing is directly arranged
Put, the filtrate that caused biochemical sludge then obtains with step (1) pretreatment after processing imports wet oxidation reaction in the lump after mixing
Device.
3. chlorophenols method of wastewater treatment according to claim 2, it is characterised in that in step (1), the flocculant is
FeCl3、AlCl3, Sodium Polyacrylate and polyacrylamide one or more therein, dosage be pending chlorophenols waste water matter
The 0.1%-0.3% of amount.
4. chlorophenols method of wastewater treatment according to claim 2, it is characterised in that in step (2), the catalyst is
One or more in the metal salt solutions such as Cu, Fe, Mn, Ce and Ti, addition are pending waste water and biochemical sludge mixture
The 0.1%-0.2% of quality.
5. chlorophenols method of wastewater treatment according to claim 2, it is characterised in that in step (2), the wet oxidation
Reaction condition is：250-320 DEG C of reaction temperature, reaction pressure 5-8MPa, reaction time 0.5-2h, oxidant used are oxygen,
Oxygen purity>90%, coefficient of oxidation 1.2-1.5.
6. the integrated conduct method of chlorophenols waste water according to claim 2, it is characterised in that in step (2), the tail
Flash Gas Compression Skid System is biofilter, and the filler in biofilter is peat, one kind in wood chip, porous ceramics, granular activated carbon
Or it is several, treatment temperature is 25-35 DEG C, pH 7-8.
7. the integrated conduct method of chlorophenols waste water according to claim 2, it is characterised in that in step (4), the life
Change processing system is membrane bioreactor, the organic pollution further gone in water removal, wherein, membrane bioreactor sludge concentration
For 5000-10000mg/L, aeration quantity 20-40L/h, hydraulic detention time 1-5h.
Priority Applications (1)
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