CN109851097A - A method of using organic matter in ultrasound-electrocatalytic oxidation-ultrafiltration group technology processing reverse osmosis concentrated water - Google Patents
A method of using organic matter in ultrasound-electrocatalytic oxidation-ultrafiltration group technology processing reverse osmosis concentrated water Download PDFInfo
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- CN109851097A CN109851097A CN201910118009.5A CN201910118009A CN109851097A CN 109851097 A CN109851097 A CN 109851097A CN 201910118009 A CN201910118009 A CN 201910118009A CN 109851097 A CN109851097 A CN 109851097A
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- reverse osmosis
- electrocatalytic oxidation
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Abstract
The present invention provides a kind of methods using organic matter in ultrasound-electrocatalytic oxidation-ultrafiltration group technology processing reverse osmosis concentrated water, and this method includes ultrasound unit, electrocatalytic oxidation unit and ultra filtration unit.In the treatment process, reverse osmosis water initially enters ultrasound unit and is ultrasonically treated, and initial breakdown organic matter, concentrated water enters electrocatalytic oxidation unit later, makes reverse osmosis concentrated organic pollutants mineralising, achievees the purpose that COD is removed；Finally pass through hyperfiltration treatment, remove the small wadding body generated in reaction process, remove turbidity and further removes organic matter.The characteristics of salt content of the process makes full use coking wastewater RO concentrated water is high, good conductivity, based on electrocatalytic oxidation, the dense organic pollutants of RO are removed using ultrasound-electrocatalytic oxidation-ultrafiltration technology, the technique occupied area is small, reaction condition is simple, and treatment effeciency is high, is not necessarily to outer adding medicine, unharmful substance generates, it can be achieved that really environmental-friendly.
Description
Technical field
The invention belongs to Treatment of Industrial Water technical fields, are related to a kind of reasonable sanding of reverse osmosis concentrated organic pollutants
Method.
Background technique
Increasingly stringent with national clean manufacturing and environmental requirement, reverse osmosis (RO) technology is increasingly becoming many industries,
Especially coking wastewater industry, sewage treatment and the one preferred technique for recycling water depth Treatment for Reuse.But usual reverse osmosis process
The generation of 20%-50% concentrated water is had, this kind of water COD content is high, and macromolecular organic pollutant mostly difficult to degrade, biodegradability
It is very poor.In addition RO concentrated water salt content is high, is difficult to cause to imitate using conventional biochemistry and physical chemistry method, and it is dense that high-level oxidation technology becomes RO
The removal of organic pollutants is preferred.
CN107540175A discloses the method for hardly degraded organic substance advanced treating in a kind of pair of Industrial reverse osmosis concentrated water,
It is characterized in that, advanced oxidation and humus microbial activity charcoal is organically combined together, it is ultraviolet first with ozone cooperative
The advanced oxidization method of the photochemical catalytic oxidation of Fenton improves the biodegradability of RO concentrated water, then under anaerobic, passes through culture
Domestication is that main biocenose carries out activated carbon adsorption carbon column biofilm with humus microorganism, forms humus microbial activity
Charcoal, organic matter difficult to degrade in concentrated water of further degrading.
CN108658299A discloses a kind of for reverse osmosis concentrated water organic matter removal technique, which is characterized in that first carries out
Oxidation reaction removes partial organic substances mineralising, then further removes organic matter by activated carbon adsorption, and final outflow water COD is lower than
80mg/L.The oxidation reaction is carried out using combined oxidation mode, and the combined oxidation mode is to utilize ozone and dioxygen water phase
In conjunction with by the dense water part mineralization of organic material removing of RO.
Two above processing the dense organic pollutants of RO patent in be required to adjust pH before treatment, in the process plus
Enter a large amount of medicaments, greatly increases processing cost.In contrast, electrocatalytic oxidation is without adjusting pH, without outer adding medicine, and
The general 8000 inherently a kind of excellent electrolyte solution of μ S/cm, RO concentrated water of > of coking wastewater factory RO concentrated water conductivity.Sufficiently
The characteristics of using RO concentrated water salt content height, good conductivity, becomes selection process using electro-catalytic oxidation technology processing RO concentrated water.
Summary of the invention
It is a kind of reverse osmosis using ultrasound-electrocatalytic oxidation-ultrafiltration group technology processing it is an object of the invention to design
The method of organic matter, solves the above problems in concentrated water.
To achieve the goals above, The technical solution adopted by the invention is as follows:
A method of using organic matter in ultrasound-electrocatalytic oxidation-ultrafiltration group technology processing reverse osmosis concentrated water, packet
Include following steps:
Step (1), ultrasonic treatment: reverse osmosis concentrated water enters ultrasound unit through pump from tank, and the ultrasound unit is super
Phonoresponse device, under acoustic cavitation effect, so that advanced oxidation, pyrolysis and/or supercritical oxidation occur for organic pollutant in turn
Obtain initial breakdown；
Step (2), electrocatalytic oxidation: entering electrocatalytic oxidation unit through the processed concentrated water of the supersonic reaction device,
Oxidation reaction occurs in anode and generates the intermediate product with oxidisability, the intermediate product of generation destroys the organic contamination
The molecular structure of object finally makes organic pollutant mineralising；
Step (3), hyperfiltration treatment: the concentrated water crossed through electrocatalytic oxidation cell processing enters ultra filtration unit, through ultra filtration unit
It removes the wadding body generated in reaction process and further removes the organic pollutant, process concentrated water later and arranged through ultra filtration unit
Out.
It preferably, further include step (4), ultrafiltration cleaning unit: the sewage after cleaning ultra filtration unit is discharged into equipped with reverse osmosis
In the tank of concentrated water.
Preferably, in step (1), the hydraulic detention time of the supersonic reaction device is 5-20min, the ultrasonic reaction
Device is equipped with supersonic generator, and the supersonic frequency that the supersonic generator generates is 1-10MHz.
Preferably, in rapid (2), the electrocatalytic oxidation unit includes electrochemical reactor, the electrochemical reactor water
Power residence time 30-120min, the water inlet end of the electrochemical reactor are connected with the supersonic reaction device, the electrochemistry
The water outlet of reactor is connected with ultra filtration unit.
Preferably, the electrochemical reactor includes electrolytic cell, constant voltage dc source, cathode plate and anode plate；The sun
Pole plate is parallel to each other with cathode plate and intersects, and is vertically arranged in electrolytic cell, and the anode plate and the constant voltage dc source
Anode be connected, the cathode plate is connected with the cathode of the constant voltage dc source.
Preferably, the anode plate uses metal oxide electrode, the metal oxidation that pole plate coating selects oxygen evolution potential high
Object or ion doping type metal oxide；The cathode plate uses graphite plate, titanium plate or stainless steel plate.
Preferably, the logarithm of cathode-anode plate is 10-50 pairs in the electrochemical reactor, and the anode plate and the yin
The spacing of pole plate is 2-10cm.
Preferably, the constant voltage dc source output electric current is 2000-6000A.
Preferably, the ultra filtration unit is ultrafiltration apparatus, uses external pressure type hollow fiber membrane component in the ultrafiltration apparatus,
Membrane aperture is 0.01-0.1 μm, and membrane material is Kynoar, and membrane flux is 15-25L/ (m2·h)。
Preferably, the ultrafiltration apparatus uses single hop intermittent duty mode, runing time 5-10min, dwell time 1-
3min, transmembrane pressure 0-50kpa.
Beneficial effect of the present invention can be summarized as follows:
The present invention is a kind of using organic matter in ultrasound-electrocatalytic oxidation-ultrafiltration group technology processing reverse osmosis concentrated water
Method, the characteristics of this method makes full use of the salt content of coking wastewater RO concentrated water high, good conductivity, turned to electrocatalytic oxidation
It is main, the dense organic pollutants of RO are removed using " ultrasound-electrocatalytic oxidation-ultrafiltration " technique, the technique occupied area is small, reaction
Condition is simple, and treatment effeciency is high, is not necessarily to outer adding medicine, and unharmful substance generates, it can be achieved that really environmental-friendly.
Detailed description of the invention
Fig. 1 is process flow chart of the invention.
Specific embodiment
In order to which the technical problems, technical solutions and beneficial effects solved by the present invention is more clearly understood, below in conjunction with
Accompanying drawings and embodiments, the present invention will be described in further detail.It should be appreciated that specific embodiment described herein only to
It explains the present invention, is not intended to limit the present invention.
As shown in Figure 1 is a kind of using organic in ultrasound-electrocatalytic oxidation-ultrafiltration group technology processing reverse osmosis concentrated water
The method of matter, comprising the following steps:
Step (1), ultrasonic treatment: reverse osmosis concentrated water enters ultrasound unit through pump from tank, and the ultrasound unit is super
Phonoresponse device, under acoustic cavitation effect, so that advanced oxidation, pyrolysis and/or supercritical oxidation occur for organic pollutant in turn
Obtain initial breakdown；
Step (2), electrocatalytic oxidation: entering electrocatalytic oxidation unit through the processed concentrated water of the supersonic reaction device,
Oxidation reaction occurs in anode and generates the intermediate product with strong oxidizing property, the intermediate product of generation destroys organic dirt
The molecular structure for contaminating object, finally makes organic pollutant mineralising；
Step (3), hyperfiltration treatment: the concentrated water crossed through electrocatalytic oxidation cell processing enters ultra filtration unit, through ultra filtration unit
It removes the wadding body generated in reaction process and further removes the organic pollutant, process concentrated water later and arranged through ultra filtration unit
Out.
It in a more preferred embodiment, further include step (4), ultrafiltration cleaning unit: the sewage row after cleaning ultra filtration unit
Enter in the tank equipped with reverse osmosis concentrated water.
In a more preferred embodiment, in step (1), the hydraulic detention time of the supersonic reaction device is 5-20min,
The supersonic reaction device is equipped with supersonic generator, and the supersonic frequency that the supersonic generator generates is 1-10MHz.
In a more preferred embodiment, in rapid (2), the electrocatalytic oxidation unit includes electrochemical reactor, the electricity
Chemical reactor hydraulic detention time 30-120min, the water inlet end of the electrochemical reactor and the supersonic reaction device phase
Even, the water outlet of the electrochemical reactor is connected with ultra filtration unit.
In a more preferred embodiment, the electrochemical reactor includes electrolytic cell, constant voltage dc source, cathode plate and sun
Pole plate；The anode plate is parallel to each other with cathode plate to intersect, and is vertically arranged in electrolytic cell, and the anode plate and described steady
The anode of DC power supply is pressed to be connected, the cathode plate is connected with the cathode of the constant voltage dc source.
In a more preferred embodiment, the anode plate uses metal oxide electrode, and pole plate coating selects oxygen evolution potential
High metal oxide or ion doping type metal oxide；The cathode plate uses graphite plate, titanium plate or stainless steel plate.
In a more preferred embodiment, the logarithm of cathode-anode plate is 10-50 pairs in the electrochemical reactor, and the sun
The spacing of pole plate and the cathode plate is 2-10cm.
In a more preferred embodiment, the constant voltage dc source output electric current is 2000-6000A.
In a more preferred embodiment, the ultra filtration unit is ultrafiltration apparatus, is used in external-compression type in the ultrafiltration apparatus
Empty fiber membrane component, membrane aperture are 0.01-0.1 μm, and membrane material is Kynoar, and membrane flux is 15-25L/ (m2·h)。
In a more preferred embodiment, the ultrafiltration apparatus use single hop intermittent duty mode, runing time 5-10min,
Dwell time 1-3min, transmembrane pressure 0-50kpa.
A method of using organic matter in ultrasound-electrocatalytic oxidation-ultrafiltration group technology processing reverse osmosis concentrated water, packet
Include following steps:
Step (1), ultrasonic treatment: reverse osmosis concentrated water flows into ultrasound unit through tank, and ultrasound unit is sent out using ultrasonic wave
Raw device cleans the concentrated water of entrance, efficient ultrasonic is handled, under acoustic cavitation effect, so that advanced oxygen occurs for organic pollutant
Change, pyrolysis and/or supercritical oxidation obtain initial breakdown, promotion subsequent processing efficiency in turn；
Step (2) electrocatalytic oxidation: enters electrocatalytic oxidation unit through the processed waste water of supersonic reaction device, electricity is urged
Change oxidation unit and use electrochemical reactor, water occurs oxidation reaction in the anode of electrochemical reactor and generates OH, HO2
Or O2 etc. has the intermediary of strong oxidizing property, the molecular structure of organic pollutant is destroyed by the intermediary of strong oxidizing property, most
Make organic pollutant mineralising eventually, achievees the purpose that remove COD；
Step (3), hyperfiltration treatment: the concentrated water crossed through electrocatalytic oxidation cell processing enters ultra filtration unit, and ultra filtration unit is adopted
The wadding body generated in reaction process is removed with ultrafiltration apparatus and further removes the organic pollutant, processes concentrated water warp later
Ultra filtration unit discharge.Ultrafiltration apparatus uses single hop intermittent duty mode, runing time 5-10min, dwell time 1-3min, cross-film
Pressure difference 0-50kpa.
Step (4), ultrafiltration cleaning unit: the sewage after cleaning ultra filtration unit is discharged into the tank equipped with reverse osmosis concentrated water
In.
The supersonic frequency that supersonic generator generates is 1-10MHz, hydraulic detention time 5-20min.
Electrochemical reactor hydraulic detention time 30-120min, and the water inlet end of electrochemical reactor and the ultrasound are anti-
Device is answered to be connected, water outlet is connected with ultra filtration unit.
Electrochemical reactor includes electrolytic cell, constant voltage dc source, cathode plate and anode plate；The anode plate and cathode plate
It is parallel to each other and intersects, be vertically arranged in electrolytic cell, and the anode plate is connected with the anode of the constant voltage dc source, institute
Cathode plate is stated to be connected with the cathode of the constant voltage dc source.The logarithm of cathode-anode plate is 10-50 pairs in electrochemical reactor, and
The spacing of anode plate and cathode plate is 2-10cm；Anode plate uses metal oxide electrode (DSA electrode), and pole plate coating selects analysis
The high metal oxide of oxygen current potential or ion doping type oxide, such as Ti/Ti4O7 electrode, Ti/SnO2-Sb electrode etc.；Yin
Pole plate is one kind of graphite plate, titanium plate, stainless steel plate etc..The constant voltage dc source output electric current is 2000-6000A.
External pressure type hollow fiber membrane component is used in ultrafiltration apparatus, membrane aperture is 0.01-0.1 μm, and membrane material is to gather inclined fluorine
Ethylene, membrane flux are 15-25L/ (m2·h)。
Concrete case: by certain Treatment of Coking Effluent factory after biochemical treatment for advanced treating reverse osmosis concentrated water, in concentrated water
COD content is 280-320mg/L, and conductivity of waste water is 18000-24000 μ S/cm.
Embodiment 1:
Reverse osmosis concentrated water enters ultrasound unit by diaphragm pump, supersonic frequency 2MHz, initial breakdown organic pollutant and
Promote water temperature, ultrasonic time 20min, effluent COD concentration 275-315mg/L.
Ultrasound unit water outlet enters electrochemical reactor.With Ti/Ti4O7Electrode is anode, and stainless steel plate is cathode, respectively
It is connected with constant voltage dc source positive and negative anodes, adjusting direct current of voltage regulation ource electric current is 2000A, and pole plate logarithm 10 is right, pole plate spacing
10cm, hydraulic detention time 120min.After reaction, into ultrafiltration apparatus.External-compression type doughnut is used in ultrafiltration apparatus
Membrane module, membrane aperture are 0.1 μm, membrane material PVDF, and membrane flux is 20L/ (m2H), using single hop intermittent duty mode, fortune
Row time 8min, dwell time 2min, transmembrane pressure 0-25kpa.It is 115-135mg/L that COD content is discharged after ultrafiltration, reaches dirty
The requirement of water comprehensive discharge standard secondary standard.
Embodiment 2:
Reverse osmosis concentrated water enters ultrasound unit by diaphragm pump, supersonic frequency 6MHz, initial breakdown organic pollutant and
Promote water temperature, ultrasonic time 10min, effluent COD concentration 270-310mg/L.
Ultrasound unit water outlet enters electrochemical reactor.With Ti/Ti4O7Electrode is anode, and stainless steel plate is cathode, respectively
It is connected with constant voltage dc source positive and negative anodes, adjusting direct current of voltage regulation ource electric current is 4000A, and pole plate logarithm 20 is right, pole plate spacing
5cm, hydraulic detention time 60min.After reaction, into ultrafiltration apparatus.External pressing type hollow fibrous membrane is used in ultrafiltration apparatus
Component, membrane aperture are 0.1 μm, membrane material PVDF, and membrane flux is 20L/ (m2H), using single hop intermittent duty mode, operation
Time 8min, dwell time 2min, transmembrane pressure 0-25kpa.It is 105-125mg/L that COD content is discharged after ultrafiltration, reaches sewage
The requirement of comprehensive discharge standard secondary standard.
Embodiment 3:
Reverse osmosis concentrated water enters ultrasound unit by diaphragm pump, supersonic frequency 10MHz, initial breakdown organic pollutant and
Promote water temperature, ultrasonic time 5min, effluent COD concentration 265-305mg/L.
Ultrasound unit water outlet enters electrochemical reactor.With Ti/Ti4O7Electrode is anode, and stainless steel plate is cathode, respectively
It is connected with constant voltage dc source positive and negative anodes, adjusting direct current of voltage regulation ource electric current is 6000A, and pole plate logarithm 50 is right, pole plate spacing
2cm, hydraulic detention time 30min.After reaction, into ultrafiltration apparatus.External pressing type hollow fibrous membrane is used in ultrafiltration apparatus
Component, membrane aperture are 0.1 μm, membrane material PVDF, and membrane flux is 20L/ (m2H), using single hop intermittent duty mode, operation
Time 8min, dwell time 2min, transmembrane pressure 0-25kpa.It is 110-130mg/L that COD content is discharged after ultrafiltration, reaches sewage
The requirement of comprehensive discharge standard secondary standard.
Comparative example:
Reverse osmosis concentrated water is directly entered electrochemical reactor by diaphragm pump.With Ti/Ti4O7Electrode is anode, stainless steel plate
For cathode, it is connected respectively with constant voltage dc source positive and negative anodes, adjusting direct current of voltage regulation ource electric current is 4000A, pole plate logarithm 20
It is right, pole plate spacing 5cm, hydraulic detention time 60min.After reaction, into ultrafiltration apparatus.External-compression type is used in ultrafiltration apparatus
Hollow fiber film assembly, membrane aperture are 0.1 μm, membrane material PVDF, and membrane flux is 20L/ (m2H), it is transported using single hop interval
Line mode, runing time 8min, dwell time 2min, transmembrane pressure 0-25kpa.It is 215- that COD content is discharged after ultrafiltration
255mg/L。
The present invention is described in detail above by specific and preferred embodiment, but those skilled in the art should be bright
White, the present invention is not limit to that embodiments describe above, all within the spirits and principles of the present invention, made any modification,
Equivalent replacement etc., should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of method using organic matter in ultrasound-electrocatalytic oxidation-ultrafiltration group technology processing reverse osmosis concentrated water, special
Sign is, the following steps are included:
Step (1), ultrasonic treatment: reverse osmosis concentrated water enters ultrasound unit through pump from tank, and the ultrasound unit is that ultrasound is anti-
Device is answered, under acoustic cavitation effect, so that organic pollutant occurs advanced oxidation, pyrolysis and/or supercritical oxidation and then obtains
Initial breakdown；
Step (2) electrocatalytic oxidation: enters electrocatalytic oxidation unit through the processed concentrated water of the supersonic reaction device, in sun
Pole occurs oxidation reaction and generates the intermediate product with strong oxidizing property, and the intermediate product of generation destroys the organic pollutant
Molecular structure, finally make organic pollutant mineralising；
Step (3), hyperfiltration treatment: the concentrated water crossed through electrocatalytic oxidation cell processing enters ultra filtration unit, removes through ultra filtration unit
The wadding body that generates in reaction process and the organic pollutant is further removed, processes concentrated water later and be discharged through ultra filtration unit.
2. according to claim 1 a kind of using ultrasound-electrocatalytic oxidation-ultrafiltration group technology processing reverse osmosis concentrated water
The method of middle organic matter, it is characterised in that: further include step (4), ultrafiltration cleaning unit: the sewage after cleaning ultra filtration unit is discharged into
In tank equipped with reverse osmosis concentrated water.
3. according to claim 1 a kind of using ultrasound-electrocatalytic oxidation-ultrafiltration group technology processing reverse osmosis concentrated water
The method of middle organic matter, it is characterised in that: in step (1), the hydraulic detention time of the supersonic reaction device is 5-20min,
The supersonic reaction device is equipped with supersonic generator, and the supersonic frequency that the supersonic generator generates is 1-10MHz.
4. according to claim 1 a kind of using ultrasound-electrocatalytic oxidation-ultrafiltration group technology processing reverse osmosis concentrated water
The method of middle organic matter, it is characterised in that: in rapid (2), the electrocatalytic oxidation unit includes electrochemical reactor, the electrification
Reactor hydraulic detention time 30-120min is learned, the water inlet end of the electrochemical reactor is connected with the supersonic reaction device,
The water outlet of the electrochemical reactor is connected with ultra filtration unit.
5. according to claim 4 a kind of using ultrasound-electrocatalytic oxidation-ultrafiltration group technology processing reverse osmosis concentrated water
The method of middle organic matter, it is characterised in that: the electrochemical reactor includes electrolytic cell, constant voltage dc source, cathode plate and sun
Pole plate；The anode plate is parallel to each other with cathode plate to intersect, and is vertically arranged in electrolytic cell, and the anode plate and described steady
The anode of DC power supply is pressed to be connected, the cathode plate is connected with the cathode of the constant voltage dc source.
6. according to claim 5 a kind of using ultrasound-electrocatalytic oxidation-ultrafiltration group technology processing reverse osmosis concentrated water
The method of middle organic matter, it is characterised in that: the anode plate uses metal oxide electrode, and pole plate coating selects oxygen evolution potential high
Metal oxide or ion doping type metal oxide；The cathode plate uses graphite plate, titanium plate or stainless steel plate.
7. according to claim 5 a kind of using ultrasound-electrocatalytic oxidation-ultrafiltration group technology processing reverse osmosis concentrated water
The method of middle organic matter, it is characterised in that: the logarithm of cathode-anode plate is 10-50 pairs in the electrochemical reactor, and the sun
The spacing of pole plate and the cathode plate is 2-10cm.
8. according to claim 1 a kind of using ultrasound-electrocatalytic oxidation-ultrafiltration group technology processing reverse osmosis concentrated water
The method of middle organic matter, it is characterised in that: the constant voltage dc source output electric current is 2000-6000A.
9. according to claim 1 a kind of using ultrasound-electrocatalytic oxidation-ultrafiltration group technology processing reverse osmosis concentrated water
The method of middle organic matter, it is characterised in that: the ultra filtration unit is ultrafiltration apparatus, uses external-compression type hollow in the ultrafiltration apparatus
Fiber film component, membrane aperture are 0.01-0.1 μm, and membrane material is Kynoar, and membrane flux is 15-25L/ (m2·h)。
10. according to claim 9 a kind of reverse osmosis concentrated using ultrasound-electrocatalytic oxidation-ultrafiltration group technology processing
The method of organic matter in water, it is characterised in that: the ultrafiltration apparatus use single hop intermittent duty mode, runing time 5-10min,
Dwell time 1-3min, transmembrane pressure 0-50kpa.
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| CN112679008A (en) * | 2020-12-14 | 2021-04-20 | 江苏卓博环保科技有限公司 | Reverse osmosis concentrated water multi-stage combined technology treatment device and treatment method |
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