CN106517636A - Waste emulsion treatment method and device - Google Patents
Waste emulsion treatment method and device Download PDFInfo
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- CN106517636A CN106517636A CN201510575215.0A CN201510575215A CN106517636A CN 106517636 A CN106517636 A CN 106517636A CN 201510575215 A CN201510575215 A CN 201510575215A CN 106517636 A CN106517636 A CN 106517636A
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Abstract
The invention discloses a waste emulsion treatment method and a waste emulsion treatment device. The treatment method comprises the following steps: treating a waste emulsion to be treated at a temperature of 18-60 DEG C by a solid-liquid separation high-frequency vibration membrane treater, and performing anaerobic treatment; performing aerobic contacting oxidation treatment; performing MBR filtration, performing ozonation treatment on the obtained liquid, and performing filtering to remove residual suspended solids, wherein the packing in an ozonation treatment device is a supported catalyst AODO. The treatment process disclosed by the invention is compact in flow, small in occupied area, low in operating cost and short in treatment time, the treated waste emulsion is nearly colorless and basically odorless, the effluent quality in the whole process can completely meet the secondary standard requirements in the Integrated Wastewater Discharge Standard (GB8978-1996), and the treatment process has extremely high popularization value in other high-difficulty organic wastewater treatment.
Description
Technical field
The present invention relates to field of industrial waste water treatment, and in particular to a kind of processing method of waste emulsified mixture and place
Reason device.
Background technology
As the big step development of China's industry, the usage amount of emulsion are more and more, at the same time, give up breast
The discharge capacity for changing liquid is also increasing.In mechanical processing industry, the cutting and grinding of metal need to be using a large amount of
Emulsion is used as lubrication, mainly contains machine oil and surfactant in emulsion, is with emulsification
Dilute with water adds what emulsifying agent was formulated to oil as needed, and the emulsification used in machine cut
In order to improve the rust-preventing characteristic of emulsion in liquid, natrium nitrosum etc. is also added into.But emulsion is through multiple
After Reusability, it may occur that different degrees of becomes sour, performance is reduced, and will regularly replace new emulsion,
So just generating a large amount of waste emulsified mixtures.Waste emulsified mixture in addition to the harm with general oily waste water, due to
The effect of surfactant, machinery oil are highly dispersed in water, and animals and plants, aquatile are more easy to absorb,
And surfactant itself also has harm to biology, can also make some water-fast noxious materials molten
Solution, while the rust-preventing characteristic for improving emulsion, the natrium nitrosum of addition is easily converted to carcinogenic nitrous
Base amine, does great damage to the ecosystem.As in waste emulsified mixture, pollutant levels are higher, composition is more
Plus complicated, therefore it is listed in danger wastes (HW09).
Emulsion mainly has oil base and water base two kinds, and most enterprises are all by oil base emulsion and water-based emulsion
Liquid is carried out mixed and is discharged simultaneously, due to oil (petroleum-type), nitrite, COD etc. in waste emulsified mixture
Pollutant levels are high, complicated component, therefore deal with improperly and will cause Heavy environmental pollution.Prior art
In, all must ability after acid adding or alkali breakdown of emulsion, air supporting and coagulating sedimentation in the processing procedure of waste emulsified mixture
Into the biochemical reaction stage, thus bring that occupation area of equipment is big, operating cost is high, process time is long
Etc. defect.The present situation is urgently solved.
The content of the invention
The technical problem to be solved is overcome in prior art in waste emulsified mixture processing procedure,
Must breakdown of emulsion, the biochemical reaction stage could be entered after coagulating sedimentation, thus bring occupation area of equipment it is big,
Operating cost is high, process time is long, and needs to heat emulsion in the method for breakdown of emulsion in prior art
To more than 80 DEG C, it is higher to there is temperature, wastes the defects such as energy, there is provided a kind of process of waste emulsified mixture
Method and processing meanss.In the handling process of the present invention, flow process is compact, and floor space is little, operating cost
Low, process time is short, and original waste emulsified mixture only need to be in the range of 18～60 DEG C.The present invention can be effective
Waste emulsified mixture is processed, can overall up to standard.Waste emulsified mixture water quality Jing after processing is close to colourless, substantially tasteless,
And realize that water outlet reaches pH for 6～9, COD≤120mg/L, oil content≤100mg/L, SS (water
Suspension in matter)≤30mg/L, whole set process effluent quality can be fully achieved《Integrated wastewater discharge mark
It is accurate》(GB8978-1996) secondary standard in is required.The handling process of the present invention highly difficult has to other
Machine wastewater treatment also has very high promotional value.
The present invention solves above-mentioned technical problem by the following technical programs.
The invention provides a kind of processing method of waste emulsified mixture, which comprises the steps：By 18～60 DEG C
Pending waste emulsified mixture elder generation Jing separation of solid and liquid high frequency diaphragms processor process, then Jing Anaerobic Treatments, so
By aerobic contact oxidation process, after Jing MBR filter after, the liquid for obtaining is again at Jing ozone oxidations
Reason, filters the suspension for removing residual；
Wherein, in the device of the ozone Oxidation Treatment, filler is loaded catalyst AODO, described negative
Supported catalyst AODO is obtained by following preparation methods：Aluminum oxide with 2～4mm enters as carrier
After row activation process, the predecessor of active component is supported on carrier using equi-volume impregnating, roasting,
Obtain final product the loaded catalyst AODO that mass fraction is 1%～8%；Described percentage refers to activearm
Divide the percentage for accounting for loaded catalyst gross mass；Wherein, the predecessor of described active component is
MaXb·cH2O, wherein, MaXbFor M and X-shaped into salt, M is Cd2+、Ni2+And Zn2+In
One or more；X is acid ion；A is 1,2 or 3；B is 1 or 2；C be 0,1,2,3,
4th, 5,6,7 or 8；The support-activated time is 2～15min；Support-activated temperature is 400 DEG C～500 DEG C；
The time of described roasting is 1～2 hour；The temperature of described roasting is 500～600 DEG C.
In the present invention, described waste emulsified mixture waste water is the conventional waste emulsified mixture waste water of field of machining,
General COD value is 100000～600000mg/L, and pH is 6～9, and oil content is 10000～60000mg/L,
SS (suspension in water quality) concentration is 10000～30000mg/L.
In the present invention, preferably 20～60 DEG C of the temperature of the pending waste emulsified mixture, more preferably for
40～60 DEG C, be most preferably 40～50 DEG C, is most preferably further 20 DEG C, 40 DEG C, 45 DEG C or 60 DEG C.
In the present invention, the separation of solid and liquid high frequency diaphragm processor is public affairs in patent CN103894069A
The separation of solid and liquid high frequency diaphragm processor opened, preferably model ZYF-10 separation of solid and liquid high frequency diaphragm
Processor, ZYF-10 are Suzhou Zhong Yu environmental science and technology Co., Ltd commercially available prod.
In the present invention, preferably, the waste emulsified mixture Jing intake pumps are entered at separation of solid and liquid high frequency diaphragm
Reason device.The frequency of the intake pump is preferably 20～40Hz, is more preferably 27.3Hz.
In the present invention, the intake pressure of the waste emulsified mixture is the conventional influent pressure of waste emulsified mixture process field
Power, preferably 1.8～2.0MPa, are more preferably 2.0MPa.
In the present invention, the concentrated water pressure during the separation of solid and liquid high frequency diaphragm processor is processed is
The conventional concentrated water pressure of separation of solid and liquid high frequency diaphragm processor process field, preferably 1.8～2.0MPa,
More preferably it is 2.0MPa.
In the present invention, during the separation of solid and liquid high frequency diaphragm processor is processed, vibrator frequency is preferably
For 40～60Hz, it is more preferably 46.3Hz.
In the present invention, described Anaerobic Treatment is the conventional Anaerobic Treatment of waste emulsified mixture process field, specifically
Each processing parameter can be by the field routine.Wherein, the hydraulic detention time of described Anaerobic Treatment is preferably
For 48～72 hours, it is more preferably 48 hours.
In the present invention, described aerobic contact oxidation is processed as aerobic the connecing of waste emulsified mixture process field routine
Tactile oxidation processes, concrete each processing parameter can be by the field routine.Wherein, described aerobic contact oxidation
The hydraulic detention time of process preferably 60～72 hours, is more preferably 72 hours.Described is aerobic
The dissolved oxygen control range of catalytic oxidation process is preferably 2～4mg/L, is more preferably 3mg/L.It is described
Aerobic contact oxidation process BOD volumetric loadings be preferably 1.0～1.5kg/m3D, more preferably for
1.0kg/m3·d。
In the present invention, the MBR, full name Membrane Bio-Reactor, Chinese are referred to as membrane bioreaction
Answer device.The operation that the MBR is filtered is the conventional operation of waste emulsified mixture process field, concrete each parameter
Can be by the field routine.The MBR process times preferably 15～25 hours, are more preferably 20
Hour.
In the present invention, in the MBR, film used is the conventional use of film of waste emulsified mixture process field, compared with
It is Flat Membrane goodly, more preferably for being purchased from the Sinap80-150 of Shanghai SINAP Membrane Science ＆ Technology Co., Ltd..
In the present invention, preferably, the aerobic contact oxidation is processed and the MBR membrane filtrations are adopted
Intermittent aerating.In the intermittent aerating, the time of aeration preferably 1～3 hour, is more preferably 2 hours.
Stop preferably 0.5～1.5 hour time of aeration in the intermittent aerating, be more preferably 1 hour.
In the present invention, the specific surface area of described loaded catalyst AODO is generally 230～250m2/ g,
Pore volume is generally 0.36～0.47mL/g, and aperture is generally 6.80～7.21nm.Above-mentioned characterize data adopts X
Ray fluorescence spectrometer is determined.
In the preparation method of the loaded catalyst AODO, described aluminum oxide can be prepared for ability
The conventional aluminum oxide of loaded catalyst, it is commercially available.
In the preparation method of the loaded catalyst AODO, X can for the conventional acid group in this area from
Son, is generally divided into inorganic acid radical ion or organic acid anions.Described inorganic acid radical ion is preferably
Sulfate ion (SO4 2-), salt acid ion (Cl-), nitrate ion (NO3 -), carbanion
(CO3 2-) and phosphate anion (PO4 3-) in one or more.Described organic acid anions compared with
It is acetate ion (Ac goodly-) and/or oxalate denominationby (C2O4 2-)。
In the preparation method of the loaded catalyst AODO, described MaXb·cH2O is preferably
Cd(NO3)2、Ni(NO3)2·6H2O、Zn(NO3)2、CdCl2、NiCl2·6H2O、ZnCl2、Cd3(PO4)2、
Ni3(PO4)2·8H2O、Zn3(PO4)2、CdAc2、NiAc2·4H2O and ZnAc2In one or more.
In the preparation method of the loaded catalyst AODO, after the activated process of carrier, preferably
Room temperature (10～30 DEG C) is cooled to, and equi-volume impregnating is then adopted again by the predecessor of active component
It is supported on carrier.
In the preparation method of the loaded catalyst AODO, described equi-volume impregnating is ability
The conventional method in domain, preferably by the carrier impregnation after activation process in MaXb·cH2In O solution, you can；
Wherein, described MaXb·cH2The volume of O solution is equal to pore volume.Described MaXb·cH2O
The mass fraction of solution is not especially limited, generally 2%～3% MaXb·cH2O solution, wherein,
Described percentage refers to MaXb·cH2The quality of O accounts for MaXb·cH2The percentage of O solution gross masses.
Work as MaXb·cH2When O is soluble in water, described MaXb·cH2Solvent in O solution is generally deionization
Water；Work as MaXb·cH2When O is insoluble in water, described MaXb·cH2Solvent in O solution generally has
Machine solvent, wherein, the species of described organic solvent is not especially limited, as long as can dissolve
MaXb·cH2O, does not affect the preparation of loaded catalyst, such as alcohols solvent or varsol.
Dip time, dipping temperature in described equi-volume impregnating etc. are not especially limited.
In the preparation method of described loaded catalyst AODO, after roasting terminates, can also be further
Including the operation of activating and reducing.The method of described activating and reducing can be the conventional method in this area, as long as
The predecessor of the active component being supported on carrier is reduced to into reduction-state, you can.
In the present invention, the ozone Oxidation Treatment is the conventional ozone Oxidation Treatment of waste emulsified mixture process field,
Concrete each processing parameter can be by the field routine.During the ozone Oxidation Treatment, the throwing amount of ozone
Preferably 60～80g/L, is more preferably 80g/L.During the ozone Oxidation Treatment, waterpower is stopped
Stay the time preferably 2～4 hours, be more preferably 3 hours.The bottom of the ozone oxidation tower is equipped with smelly
Oxygen disperser, forms tiny bubble, those bubbles, described loaded catalyst AODO and enters
Enter the waste emulsified mixture contact in tower, gas-solid-liquid phase reaction occurs.
The heretofore described operation for filtering the suspension for removing residual is waste emulsified mixture process field routine
Operation, concrete each processing parameter can be by the field routine.Preferably, being filtered using active carbon filter
Remove the suspension of residual.The active carbon filter is the conventional use of activated carbon mistake of field of waste water treatment
Filter, the preferably active carbon filter of Wuxi City the second station boiler subsidiary engine Co., Ltd.The work
Property charcoal be preferably 3～5 nanometers of particle diameter shell-shaped activated carbon.
Present invention also offers a kind of processing meanss of waste emulsified mixture, described processing meanss include connecting successively
A separation of solid and liquid high frequency diaphragm processor, a biochemical treatment equipment, an ozone Oxidation Treatment device and the work for connecing
Property carbon filter；Wherein, the biochemical treatment equipment includes the Anaerobic Treatment device being sequentially connected, aerobic connects
Tactile processor and MBR processors, it is described it is aerobic contact processor and the MBR processors with exposure
Device of air is connected；
Wherein, the filler in the ozone Oxidation Treatment device is foregoing loaded catalyst AODO.
In the present invention, the separation of solid and liquid high frequency diaphragm processor is as previously mentioned.
Preferably, the separation of solid and liquid high frequency diaphragm processor, the biochemical treatment equipment, the ozone
Oxidation processes device is connected by water pump with the active carbon filter.
Preferably, also including for heating waste emulsified mixture before the separation of solid and liquid high frequency diaphragm processor
Water tank.
Preferably, the aerator is the conventional aerator of field of waste water treatment, preferably air blast
Machine.
On the basis of common sense in the field is met, above-mentioned each optimum condition can be combined, obtain final product this
Bright each preferred embodiments.
Agents useful for same of the present invention and raw material are commercially available.
The present invention positive effect be：
1st, in the processing procedure of waste emulsified mixture of the present invention, at Anaerobic Treatment and aerobic contact oxidation
Before reason, without the need for waste emulsified mixture is heated to more than 80 DEG C, grasp without breakdown of emulsion, coagulant precipitation etc. is carried out
Make, only 18～60 DEG C of waste emulsified mixture Jing separation of solid and liquid high frequency diaphragms processor need to be processed.With
Prior art compares, and the handling process of the present invention drastically increases the biodegradability (B/C of waste emulsified mixture
More than 0.3), while removing substantial amounts of COD, oil and SS, clarification of water is used.And the place of the present invention
Reason technological process is compact, and floor space is little, and operating cost is low, and operational management is convenient, good stability, together
When shorten process time.
The loaded catalyst AODO of the present invention, when for catalytic ozonation advanced treatment of waste water,
The utilization rate of ozone can be improved, it is very good to the advanced treating effect of waste water.
2nd, all types of waste emulsified mixtures of present invention energy effective process, good stability can overall up to standard.
Waste emulsified mixture water quality Jing after processing is close to colourless, substantially tasteless, and realizes that water outlet reaches pH for 6～9,
COD≤120mg/L, oil content≤100mg/L, SS (suspension in water quality)≤30mg/L are whole
Set Process for Effluent water quality can be fully achieved《Integrated wastewater discharge standard》(GB8978-1996) two grades in
Standard is required.The handling process of the present invention also has very high popularization to other highly difficult treatment of Organic Wastewater
Value.
Description of the drawings
Processing meanss schematic diagrames of the Fig. 1 for the waste emulsified mixture of embodiment 1；Wherein, the direction of arrow is useless breast
Change trend of the liquid in technological process, 1 is the first water tank, and 2 is separation of solid and liquid high frequency diaphragm processor,
201 is centre of oscillation bar, and 202 is vibrator, and 3 is biochemical treatment equipment, and 301 is Anaerobic Treatment device, 302
For aerobic contact oxidation processor, 303 is MBR processors, and 4 is ozone Oxidation Treatment device, and 401 are
Filler, 5 is the second water tank, and 6 is active carbon filter, and 601 is active carbon filler, and 7 is three-tank,
801 be the first water pump, 802 be the second water pump, 803 be the 3rd water pump, 804 be the 4th water pump, 805
For the 5th water pump, 806 is the 6th water pump, and 9 is air blast.
Specific embodiment
The present invention is further illustrated below by the mode of embodiment, but is not therefore limited the present invention to
Among described scope of embodiments.The experimental technique of unreceipted actual conditions in the following example, according to normal
Rule method and condition, or select according to catalogue.
Integrated wastewater discharge standard (GB8978-1996) secondary standard：PH6～9, COD≤120mg/L,
SS (suspension in water quality)≤30mg/L, petroleum-type≤150mg/L.
In following embodiments, the detection method of pH, COD, SS and petroleum-type is performed by national standard：
PH examination criterias are GB 6920-86 (measure of water pH value, glass electrode method)
COD examination criterias are GB/T 11914-1989 (dichromate titration measure water chemical oxygen demand)；
It is HJ 637-2012 (water-quality petroleum and animals and plants oils that oil content examination criteria is examination criteria
Measure, infrared spectrophotometer)；
SS content detections standard is GB 11901-89 (measure of water quality suspension, gravimetric method).
In following embodiments 1～6, the loaded catalyst AODO for being adopted adopts following preparation sides
Method is obtained：
Aluminum oxide with 2～4mm as carrier, after activation process, with ZnCl2As the predecessor of Zn,
Mass fraction is configured to for after 2% aqueous solution, using equi-volume impregnating by ZnCl2It is supported on load
On body, roasting, after activating and reducing, obtains final product the loaded catalyst AODO that mass fraction is 4%；Institute
The percentage stated refers to that active component accounts for the percentage of loaded catalyst gross mass；Wherein, described load
The time of body activation is 15min；Described 500 DEG C support-activated of temperature；The time of described roasting
For 2 hours；The temperature of described roasting is 540 DEG C.Last obtained loaded catalyst AODO's
Specific surface area is 240m2/ g, pore volume are 0.38mL/g, and aperture is that 7.10nm (is composed using XRF
Instrument is determined).
Embodiment 1
Certain waste emulsified mixture water-quality constituents is as shown in table 1.
Processing meanss schematic diagrames of the Fig. 1 for the waste emulsified mixture of embodiment 1.Wherein, the direction of arrow is useless breast
Change trend of the liquid in technological process.
Said apparatus include the first water tank 1 being sequentially connected, the second water pump 802, separation of solid and liquid high frequency vibrating
Dynamic film process device 2, the 3rd water pump 803, biochemical treatment equipment 3, the 4th water pump 804, ozone Oxidation Treatment
Device 4, the 5th water pump 805, the second water tank 5, the 6th water pump 806, active carbon filter 6, the 3rd water
Case 7, the first water pump 801.
Centre of oscillation bar 201 is provided with separation of solid and liquid high frequency diaphragm processor 2, bottom is provided with vibrator
202。
It is sequentially provided with Anaerobic Treatment device 301 in biochemical treatment equipment 3, aerobic contact oxidation processor 302,
MBR processors 303；Aerobic contact processor 302 and the MBR processors 303 are and air blast
9 are connected, and are capable of achieving uniform aeration in bottom blast machine 9.
Filler 401 is provided with ozone Oxidation Treatment device 4.
Active carbon filler 601 is provided with active carbon filter 6.
Wherein, 2 model ZYF-10 of separation of solid and liquid high frequency diaphragm processor, is purchased from Suzhou crowd Yu Huan
Border Science and Technology Ltd., loaded catalyst AODO of the filler 401 for Shanghai Xi Ba limited companies,
The film adopted in MBR processors 303 is for being purchased from Shanghai SINAP Membrane Science ＆ Technology Co., Ltd.
Sinap80-150.Active carbon filter is purchased from the activated carbon of Wuxi City the second station boiler subsidiary engine Co., Ltd
Filter, shell-shaped activated carbon of the activated carbon for 3～5 nanometers of particle diameter.
Using above-mentioned processing meanss, the technique for processing waste emulsified mixture comprises the steps：
(1) 45 DEG C of waste emulsified mixture carries out the process of separation of solid and liquid high frequency diaphragm processor Jing after intake pump；
Wherein, intake pressure 2.0MPa, water inlet pump frequency are 27.3Hz；Vibrator frequency is 46.3Hz, dense
Water pressure is 2.0MPa；
(2) by separation of solid and liquid high frequency diaphragm processor produce water directly successively Jing Anaerobic Treatments, aerobic connect
Tactile oxidation processes, the process of MBR membrane filtrations；Wherein, Anaerobic Treatment time of staying 48h, Aerobic Process for Treatment stop
Stay time 72h, MBR film process time of staying 20h；Aerobic contact oxidation process and MBR membrane filtrations
Intermittent aerating is adopted, aeration time is 2h, stop aeration time for 1h；Aerobic contact oxidation process
Dissolved oxygen control range is 3mg/L.The BOD volumetric loadings that described aerobic contact oxidation is processed are
1.0kg/m3·d；
(3) the liquid Jing ozone oxidation towers obtained after MBR membrane filtrations are carried out into ozone Oxidation Treatment, it is smelly
Oxygen dosage is 80g/L, and hydraulic detention time is 3h；
(4) by the liquid Jing active carbon filter filter and remove suspended substances after ozone Oxidation Treatment, you can.
Start and show that the system run all right, treatment effect are fine with operation result.Jing coherent detections,
After its package unit is processed, effluent quality is as shown in table 1.
Embodiment 2
Certain waste emulsified mixture water-quality constituents as shown in table 1, using the processing meanss in embodiment 1, processes useless
The technique of emulsion comprises the steps：
(1) 45 DEG C of waste emulsified mixture carries out the process of separation of solid and liquid high frequency diaphragm processor Jing after intake pump；
Wherein, intake pressure 2.0MPa, water inlet pump frequency are 27.3Hz, and vibrator frequency is 46.3Hz, dense
Water pressure is 2.0MPa；
(2) by separation of solid and liquid high frequency diaphragm processor produce water directly successively Jing Anaerobic Treatments, aerobic connect
Tactile oxidation processes, the process of MBR membrane filtrations；Wherein, Anaerobic Treatment time of staying 48h, Aerobic Process for Treatment stop
Stay time 72h, MBR film process time of staying 20h；Aerobic contact oxidation process and MBR membrane filtrations
Intermittent aerating is adopted, aeration time is 2h, stop aeration time for 1h；Aerobic contact oxidation process
Dissolved oxygen control range is 3mg/L.The BOD volumetric loadings that described aerobic contact oxidation is processed are preferable
Ground is 1.0kg/m3·d；
(3) the liquid Jing ozone oxidation towers obtained after MBR membrane filtrations are carried out into ozone Oxidation Treatment, it is smelly
Oxygen dosage is 80g/L, hydraulic detention time 3h；
(4) by the liquid Jing active carbon filter filter and remove suspended substances after ozone Oxidation Treatment, you can.
Start and show that the system run all right, treatment effect are fine with operation result.Jing coherent detections,
After its package unit is processed, effluent quality is as shown in table 1.
Embodiment 3
Certain waste emulsified mixture water-quality constituents as shown in table 1, using the processing meanss in embodiment 1, processes useless
The technique of emulsion comprises the steps：
(1) 45 DEG C of waste emulsified mixture carries out the process of separation of solid and liquid high frequency diaphragm processor Jing after intake pump；
Wherein, intake pressure 2.0MPa, water inlet pump frequency are 27.3Hz；Vibrator frequency is 46.3Hz, dense
Water pressure is 2.0MPa；
(2) by separation of solid and liquid high frequency diaphragm processor produce water directly successively Jing Anaerobic Treatments, aerobic connect
Tactile oxidation processes, the process of MBR membrane filtrations；Wherein, Anaerobic Treatment time of staying 48h, Aerobic Process for Treatment stop
Stay time 72h, MBR film process time of staying 20h；Aerobic contact oxidation process and MBR membrane filtrations
Intermittent aerating is adopted, aeration time is 2h, stop aeration time for 1h；Aerobic contact oxidation process
Dissolved oxygen control range is 3mg/L.The BOD volumetric loadings that described aerobic contact oxidation is processed are preferable
Ground is 1.0kg/m3·d；
(3) the liquid Jing ozone oxidation towers obtained after MBR membrane filtrations are carried out into ozone Oxidation Treatment, it is smelly
Oxygen dosage is 80g/L, hydraulic detention time 3h；
(4) by the liquid Jing active carbon filter filter and remove suspended substances after ozone Oxidation Treatment, you can
Start and show that the system run all right, treatment effect are fine with operation result.Jing coherent detections,
After its package unit is processed, effluent quality is as shown in table 1.
Embodiment 4
Certain waste emulsified mixture water-quality constituents as shown in table 1, using the processing meanss in embodiment 1, processes useless
The technique of emulsion is that other control conditions are with embodiment 1 in addition to 40 DEG C except the temperature for entering waste emulsified mixture.Jing
Coherent detection, after its package unit is processed, effluent quality is as shown in table 1, its separation of solid and liquid high frequency diaphragm
After the process of processor processing meanss, effluent quality is as shown in table 2.
Embodiment 5
Certain waste emulsified mixture water-quality constituents as shown in table 1, using the processing meanss in embodiment 1, processes useless
The technique of emulsion is that other control conditions are with embodiment 1 in addition to 60 DEG C except the temperature for entering waste emulsified mixture.Jing
Coherent detection, after its package unit is processed, effluent quality is as shown in table 1, its separation of solid and liquid high frequency diaphragm
After processor process, effluent quality is as shown in table 2.
Although the present embodiment can reach the effect of the present invention, due to separation of solid and liquid dither film process
The maximum temperature that device members can bear is 60 DEG C, therefore it is not recommended that inflow temperature is more than 60 DEG C,
Apparatus assembly can be otherwise caused to damage.
Embodiment 6
Certain waste emulsified mixture water-quality constituents as shown in table 1, using the processing meanss in embodiment 1, processes useless
The technique of emulsion is that other control conditions are with embodiment 1 in addition to 20 DEG C except the temperature for entering waste emulsified mixture.
Water quality situation after waste emulsified mixture before processing in 1 embodiment 1～6 of table
Claims (10)
1. a kind of processing method of waste emulsified mixture, it is characterised in which comprises the steps：By 18～60 DEG C
Pending waste emulsified mixture elder generation Jing separation of solid and liquid high frequency diaphragms processor process, then Jing Anaerobic Treatments, so
By aerobic contact oxidation process, after Jing MBR filter after, the liquid for obtaining is again at Jing ozone oxidations
Reason, filters the suspension for removing residual；
Wherein, in the device of the ozone Oxidation Treatment, filler is loaded catalyst AODO, described negative
Supported catalyst AODO is obtained by following preparation methods：Aluminum oxide with 2～4mm enters as carrier
After row activation process, the predecessor of active component is supported on carrier using equi-volume impregnating, roasting,
Obtain final product the loaded catalyst AODO that mass fraction is 1%～8%；Described percentage refers to activearm
Divide the percentage for accounting for loaded catalyst gross mass；Wherein, the predecessor of described active component is
MaXb·cH2O, wherein, MaXbFor M and X-shaped into salt, M is Cd2+、Ni2+And Zn2+In
One or more；X is acid ion；A is 1,2 or 3；B is 1 or 2；C be 0,1,2,3,
4th, 5,6,7 or 8；The support-activated time is 2～15min；Support-activated temperature is 400 DEG C～500 DEG C；
The time of described roasting is 1～2 hour；The temperature of described roasting is 500～600 DEG C.
2. processing method as claimed in claim 1, it is characterised in that the pending waste emulsified mixture
Temperature be 20～60 DEG C, preferably 40～60 DEG C, be more preferably 40～50 DEG C, be most preferably 20 DEG C,
40 DEG C, 45 DEG C or 60 DEG C；
And/or, model ZYF-10 of the separation of solid and liquid high frequency diaphragm processor.
3. processing method as claimed in claim 1, it is characterised in that the waste emulsified mixture Jing water inlets
Pump enters separation of solid and liquid high frequency diaphragm processor, and the frequency of the intake pump is preferably 20～40Hz,
More preferably it is 27.3Hz；
And/or, the intake pressure of the waste emulsified mixture is 1.8～2.0MPa, preferably 2.0MPa；
And/or, the concentrated water pressure during the separation of solid and liquid high frequency diaphragm processor is processed is
1.8～2.0MPa, preferably 2.0MPa；
And/or, during the separation of solid and liquid high frequency diaphragm processor is processed, vibrator frequency is 40～60Hz,
Preferably 46.3Hz.
4. processing method as claimed in claim 1, it is characterised in that the water of described Anaerobic Treatment
The power time of staying is 48～72 hours, preferably 48 hours；
And/or, the hydraulic detention time that described aerobic contact oxidation is processed is 60～72 hours, preferably
Ground is 72 hours；
And/or, the dissolved oxygen control range that described aerobic contact oxidation is processed is 2～4mg/L, preferably
For 3mg/L；
And/or, the BOD volumetric loadings that described aerobic contact oxidation is processed are 1.0～1.5kg/m3D,
Preferably 1.0kg/m3·d。
5. processing method as claimed in claim 1, it is characterised in that the MBR process times are
15～25 hours, preferably 20 hours；
And/or, in the MBR, film used is Flat Membrane；
And/or, the aerobic contact oxidation is processed and the MBR membrane filtrations adopt intermittent aerating；Institute
Preferably 1～3 hour time of aeration in intermittent aerating is stated, is more preferably 2 hours；The interval exposes
Stop preferably 0.5～1.5 hour time of aeration in gas, be more preferably 1 hour.
6. processing method as claimed in claim 1, it is characterised in that described loaded catalyst
In the preparation method of AODO, X is inorganic acid radical ion or organic acid anions；Described inorganic acid radical
Ion is preferably sulfate ion, salt acid ion, nitrate ion, carbanion and phosphate radical
One or more in ion；Described organic acid anions are preferably acetate ion and/or oxalate
Ion；
And/or, in the preparation method of described loaded catalyst AODO, described MaXb·cH2O
For Cd (NO3)2、Ni(NO3)2·6H2O、Zn(NO3)2、CdCl2、NiCl2·6H2O、ZnCl2、Cd3(PO4)2、
Ni3(PO4)2·8H2O、Zn3(PO4)2、CdAc2、NiAc2·4H2O and ZnAc2In one or more.
7. processing method as claimed in claim 1, it is characterised in that described loaded catalyst
In the preparation method of AODO, after the activated process of carrier, 10～30 DEG C are cooled to, are then adopted again
The predecessor of active component is supported on carrier with equi-volume impregnating；
And/or, in the preparation method of described loaded catalyst AODO, described incipient impregnation
Method is in M by the carrier impregnation after activation processaXb·cH2In O solution, you can；
And/or, in the preparation method of described loaded catalyst AODO, after roasting terminates, may be used also
Further include the operation of activating and reducing.
8. processing method as claimed in claim 1, it is characterised in that the ozone Oxidation Treatment
During, the throwing amount of ozone is 60～80g/L, preferably 80g/L；
And/or, during the ozone Oxidation Treatment, hydraulic detention time is 2～4 hours, preferably
Ground is 3 hours；
And/or, the behaviour for filtering the suspension for removing residual is taken as active carbon filter and filters removal
The suspension of residual；The active carbon filter is preferably the limited public affairs of Wuxi City the second station boiler subsidiary engine
The active carbon filter of department, the activated carbon are preferably the shell-shaped activated carbon of 3～5 nanometers of particle diameter.
9. a kind of processing meanss of waste emulsified mixture, it is characterised in that described processing meanss are included successively
Connection a separation of solid and liquid high frequency diaphragm processor, a biochemical treatment equipment, an ozone Oxidation Treatment device and
Active carbon filter；Wherein, it is the biochemical treatment equipment includes being sequentially connected an Anaerobic Treatment device, aerobic
Contact processor and MBR processors, the aerobic contact processor and the MBR processors with
Aerator is connected；
Wherein, the filler in the ozone Oxidation Treatment device is support type as claimed in claims 6 or 7
Catalyst AODO.
10. processing meanss as claimed in claim 9, it is characterised in that the separation of solid and liquid high frequency vibrating
Dynamic film process device, the biochemical treatment equipment, the ozone Oxidation Treatment device and the active carbon filter are equal
It is connected by water pump；
And/or, also include the water for heating waste emulsified mixture before the separation of solid and liquid high frequency diaphragm processor
Case；
And/or, the aerator is air blast.
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