CN109879399A - A kind of composite catalytic oxidation processing used water difficult to degradate system - Google Patents

A kind of composite catalytic oxidation processing used water difficult to degradate system Download PDF

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Publication number
CN109879399A
CN109879399A CN201910113081.9A CN201910113081A CN109879399A CN 109879399 A CN109879399 A CN 109879399A CN 201910113081 A CN201910113081 A CN 201910113081A CN 109879399 A CN109879399 A CN 109879399A
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China
Prior art keywords
ozone
bucket
pipeline
degradate
reactor
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CN201910113081.9A
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Chinese (zh)
Inventor
卞兆娥
刘恒池
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Lianyungang Radiation Environmental Monitoring And Management Station
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Lianyungang Radiation Environmental Monitoring And Management Station
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Priority to CN201910113081.9A priority Critical patent/CN109879399A/en
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Abstract

The present invention discloses a kind of composite catalytic oxidation processing used water difficult to degradate system, including inlet bucket, inlet bucket is connected with device for catalyzing and oxidating ozone by pipeline, device for catalyzing and oxidating ozone is connected with intermediate bucket by pipeline, intermediate bucket is connected with electrocatalysis oxidation apparatus by pipeline, electrocatalysis oxidation apparatus is connected with out of the bucket by pipeline, the present invention is by connecting ozone reaction with electrocatalytic reaction, utilize the synergistic effect of catalytic ozonation and electrocatalytic oxidation, ozone is by micro easily biodegradable organics direct oxidation, macromolecular hardly degraded organic substance is resolved into small organic molecule simultaneously, so that being easier to by electrocatalytic oxidation, hardly degraded organic substance can be removed with high efficiency.Compared with other modes, the two series connection avoids influence of the air-flow to electro-catalysis mass-transfer efficiency, achievees the purpose that save energy consumption.

Description

A kind of composite catalytic oxidation processing used water difficult to degradate system
Technical field
The present invention relates to technical field of waste water processing, and in particular to a kind of composite catalytic oxidation processing used water difficult to degradate system System.
Background technique
At present in water treatment field difficult to degrade, the processing mode of advanced oxidation is usually utilized.Catalytic ozonation is using directly Oxidation and indirect oxidation hardly degraded organic substance are connect, wherein direct oxidation mode is that have selective direct oxidation by ozone molecule Hardly degraded organic substance, indirect oxidation mode are to generate hydroxyl radical free radical exhaustive oxidation hardly degraded organic substance by catalysis ozone;Electricity Catalysis oxidation utilizes direct oxidation and indirect oxidation hardly degraded organic substance, and wherein direct oxidation mode is electronics direct oxidation effect In hardly degraded organic substance, indirect oxidation mode is to generate hydroxyl radical free radical exhaustive oxidation hardly degraded organic substance by anode surface. However whether catalytic ozonation or electrocatalytic oxidation have that energy consumption is higher to be caused to give up when handling used water difficult to degradate The larger problem of cost of water treatment.
Summary of the invention
The object of the present invention is to provide a kind of composite catalytic oxidations to handle used water difficult to degradate system, to solve above-mentioned existing skill Art there are the problem of, high efficiency remove hardly degraded organic substance.Exempt from influence of the air-flow to electro-catalysis mass-transfer efficiency, reaches saving energy The purpose of consumption.
To achieve the above object, the present invention provides following schemes:
The present invention provides a kind of composite catalytic oxidation processing used water difficult to degradate system, including inlet bucket, inlet bucket pass through pipe Road is connected with device for catalyzing and oxidating ozone, and device for catalyzing and oxidating ozone is connected with intermediate bucket by pipeline, and intermediate bucket passes through Pipeline is connected with electrocatalysis oxidation apparatus, and electrocatalysis oxidation apparatus is connected with out of the bucket by pipeline, in which: the ozone is urged Changing oxidation unit includes ozone reactor, and ozone reactor gas outlet is connected with vent ozone destructor, ozone reactor by pipeline Water inlet be connected with inlet bucket by pipeline, the air inlet of ozone reactor is connected with aeration mechanism, and aeration mechanism passes through Pipeline is connected with ozone generation mechanism, and electrocatalysis oxidation apparatus includes electric catalysis reactor, is fixed with electricity on electric catalysis reactor Pole, electric catalysis reactor connect DC power supply, and electric catalysis reactor is connected with out of the bucket by pipeline.
Preferably, the sample tap of ozone reactor is sequentially connected with the second valve and the first sample bucket by pipeline.
Preferably, ozone generation mechanism includes passing through the sequentially connected source of oxygen of pipeline, corrosion-resistant gas flowmeter, ozone Generator, third valve and ozone concentration on-line determination instrument.
Preferably, the first valve, the first water pump and have been sequentially arranged in inlet bucket and the connecting pipe of ozone reactor Two fluid flowmeters.
Preferably, the 5th valve is provided on the pipeline that aeration mechanism is connect with ozone generation mechanism.
Preferably, the 4th valve, the second water are disposed on the pipeline that intermediate bucket is connect with electrocatalysis oxidation apparatus Pump and the first fluid flowmeter.
Preferably, it has been sequentially connected with the 6th valve and probe tube in electric catalysis reactor and out of the bucket connecting pipe, it is described The 7th valve is provided on probe tube, probe tube connects the second sample bucket.
Preferably, the electrode includes that electro-catalysis anode described in electro-catalysis anode and electro-catalysis cathode is board-like using DSA Anode, electro-catalysis cathode use titanium plate formula cathode.
Preferably, the electric catalysis reactor bottom is equipped with separators.
Preferably, the aeration mechanism is titanium alloy aeration head or aeration plate.
The invention discloses following technical effects:
The present invention utilizes the association of catalytic ozonation and electrocatalytic oxidation by the way that ozone reaction is connected with electrocatalytic reaction Macromolecular hardly degraded organic substance is resolved into small molecule and had by micro easily biodegradable organics direct oxidation by same-action, ozone Machine object can remove hardly degraded organic substance so that being easier to by electrocatalytic oxidation with high efficiency.Compared with other modes, the two string Connection avoids influence of the air-flow to electro-catalysis mass-transfer efficiency, achievees the purpose that save energy consumption.
Detailed description of the invention
It in order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, below will be to institute in embodiment Attached drawing to be used is needed to be briefly described, it should be apparent that, the accompanying drawings in the following description is only some implementations of the invention Example, for those of ordinary skill in the art, without any creative labor, can also be according to these attached drawings Obtain other attached drawings.
Fig. 1 is schematic structural view of the invention;
Fig. 2 is ozone reactor structural schematic diagram of the present invention;
Fig. 3 is electric catalysis reactor structural schematic diagram of the present invention;
Fig. 4 is electric catalysis reactor overlooking structure diagram of the present invention;
Wherein, 1- inlet bucket;The first valve of 2-;The first water pump of 3-;4- ozone reactor;5- vent ozone destructor;6- second Valve;The first sample bucket of 7-;8- source of oxygen;9- ozone generator;10- corrosion-resistant gas flowmeter;11- ozone concentration is surveyed online Determine instrument;12- third valve;Bucket among 13-;The 4th valve of 14-;The second water pump of 15-;The 5th valve of 16-;The first liquid of 17- Flowmeter;18- DC power supply;19- electric catalysis reactor;The 6th valve of 20-;The 7th valve of 21-;The second sample bucket of 22-;23- Out of the bucket;24- water inlet;25- air inlet;26- sample tap;The gas outlet 27-;28- evacuation port;29- water outlet;30- electrode; 31- lid;32- pedestal;33- is aerated mechanism;34- second liquid flowmeter;35- separators;36- probe tube.
Specific embodiment
Following will be combined with the drawings in the embodiments of the present invention, and technical solution in the embodiment of the present invention carries out clear, complete Site preparation description, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.It is based on Embodiment in the present invention, it is obtained by those of ordinary skill in the art without making creative efforts every other Embodiment shall fall within the protection scope of the present invention.
In order to make the foregoing objectives, features and advantages of the present invention clearer and more comprehensible, with reference to the accompanying drawing and specific real Applying mode, the present invention is described in further detail.
With reference to Fig. 1-4, the present invention provides a kind of composite catalytic oxidation processing used water difficult to degradate system, including inlet bucket 1, into Bucket 1 is connected with device for catalyzing and oxidating ozone by pipeline, and device for catalyzing and oxidating ozone is connected with intermediate bucket 13 by pipeline, Intermediate bucket 13 is connected with electrocatalysis oxidation apparatus by pipeline, and electrocatalysis oxidation apparatus is connected with out of the bucket 23 by pipeline, Wherein: the device for catalyzing and oxidating ozone includes ozone reactor 4, and ozone reactor 4 uses the cylinder of oxidation and corrosion Shell, 4 gas outlet of ozone reactor are connected with vent ozone destructor 5, and 4 bottom of ozone reactor is equipped with evacuation port 28, ozone reaction The water inlet 24 of device 4 is connected with inlet bucket 23 by pipeline, and the air inlet 25 of ozone reactor 4 is connected with aeration mechanism 33, It is aerated mechanism 33 and ozone generation mechanism is connected with by pipeline, electrocatalysis oxidation apparatus includes electric catalysis reactor 19, electro-catalysis Reactor 19 uses oxidation and corrosion shell, and 19 top of electric catalysis reactor is connected with lid 31, leads in electric catalysis reactor 19 It crosses the 35 control electrode spacing of separators being provided with and is fixed with electrode 30,19 bottom of electric catalysis reactor is equipped with separators 35, electric catalysis reactor 19 connects DC power supply 18, and DC power supply is preferably alternating current-direct current constant voltage constant current power, electric catalysis reactor 19 are connected with out of the bucket 23 by pipeline.
Scheme is advanced optimized, the sample tap 26 of ozone reactor 4 is sequentially connected with the second valve 6 and first by pipeline and takes Sample bucket 7.
Scheme is advanced optimized, ozone generation mechanism includes by the sequentially connected source of oxygen 8 of pipeline, preferably high pure oxygen Source, corrosion-resistant gas flowmeter 10, ozone generator 9, third valve 12 and ozone concentration on-line determination instrument 11.
It advanced optimizes scheme, the first valve 2, the has been sequentially arranged in the connecting pipe of inlet bucket 1 and ozone reactor 4 One water pump 3 and second liquid flowmeter 34.
Scheme is advanced optimized, is provided with the 5th valve 16 on the pipeline that aeration mechanism 33 is connect with ozone generation mechanism.
Scheme is advanced optimized, is disposed with the 4th valve on the pipeline that intermediate bucket 13 is connect with electrocatalysis oxidation apparatus The 14, second water pump 15 of door and the first fluid flowmeter 17.
Scheme is advanced optimized, the 6th valve has been sequentially connected on the pipeline that electric catalysis reactor 19 is connect with out of the bucket 23 20 and probe tube 36, the 7th valve 21 is provided on probe tube 36, and probe tube 36 connects the second sample bucket 22.
Scheme is advanced optimized, electrode 30 includes electro-catalysis anode and electro-catalysis cathode, and the electro-catalysis anode uses DSA Slab anode, electro-catalysis cathode use titanium plate formula cathode.
Scheme is advanced optimized, aeration mechanism 33 is titanium alloy aeration head or aeration plate.
Embodiment 1
Main technologic parameters are as follows:
It is 800mg/L, CON (conductivity) by COD is that the used water difficult to degradate that 28.0mS/cm, pH are 7.5 is added to inlet bucket 1, the first valve 2, third valve 12 and the 4th valve 14 are opened, the second valve 6, the 5th valve 16,20 and of the 6th valve are kept 7th valve 21 is closed, and is opened the first water pump 3, while being adjusted second liquid flowmeter 34, makes in inlet bucket 1 waste water with flow 10mL/min enters ozone reactor 4, until 4 waste water liquid level of ozone reactor and water inlet 24 maintain an equal level, closes the first water pump 3, The air valve of source of oxygen 8 is opened, intake pressure 0.05MPa is controlled, opens ozone generator 9, while adjusting corrosion-resistant gas flow Meter 10 makes gas enter ozone generator 9 with flow 1L/min, and it is online that the ozonisation gas of generation by pipeline enters ozone concentration Analyzer 11, the ozone generation concentration for adjusting ozone generator 9 is 32.0mg/l, and ozone concentration is too low to cause treatment effect low, Ozone concentration is excessively high to lead to energy consumption height.After 11 registration of ozone concentration on-line determination instrument is stablized, the 5th valve 16 is opened, closes the Three valves 12 start timing 10min, after ozone reactor 4 reacts 10min, open the first water pump 3, open simultaneously the second valve Door 6, closes the second valve 6 after the sampling of the first sample bucket 7, carries out the water quality indicators such as COD, CON and pH to institute's water sampling Detection, wherein the water outlet of ozone reactor 4 enters intermediate bucket 13, after 4 successive reaction 30min of ozone reactor, opens the Two water pumps 15, while the first fluid flowmeter 17 is adjusted, make the waste water handled through ozone reactor 4 in intermediate bucket 13 to flow Amount 8.3mL/min enters electric catalysis reactor 19, until 19 waste water liquid level of electric catalysis reactor and electric catalysis reactor 19 into The mouth of a river maintains an equal level, and closes the second water pump 15, connects DC power supply 18, while adjusting output electric current and output voltage, guarantees constant current Condition, the current density for adjusting electric catalysis reactor 19 is 10mA/cm2, wherein electro-catalysis anode uses DSA anode, electro-catalysis Cathode uses Ti cathode, and 30 spacing of electrode is 1cm, and anodic-cathodic replaces in parallel and direction of an electric field is vertically arranged with water (flow) direction, Start timing 30min, after electric catalysis reactor 19 reacts 30min, it is ensured that standard water discharge discharge.Open the second water pump 15, the 6th valve 20 and the 7th valve 21 are opened simultaneously, the 7th valve 21 is closed after the sampling of the second sample bucket 22, to being fetched water Sample carries out the detection of the water quality indicators such as COD, CON and pH, and finally, the water outlet of the processing through electric catalysis reactor 19 enters water outlet Bucket 23.Under above-mentioned process conditions, continuous operation 3h, the COD removal rate for reacting water outlet is 95% or more, and stable effluent quality.
The present invention utilizes the association of catalytic ozonation and electrocatalytic oxidation by the way that ozone reaction is connected with electrocatalytic reaction Macromolecular hardly degraded organic substance is resolved into small molecule and had by micro easily biodegradable organics direct oxidation by same-action, ozone Machine object can remove hardly degraded organic substance so that being easier to by electrocatalytic oxidation with high efficiency.Compared with other modes, the two string Connection avoids influence of the air-flow to electro-catalysis mass-transfer efficiency, achievees the purpose that save energy consumption.
In the description of the present invention, it is to be understood that, term " longitudinal direction ", " transverse direction ", "upper", "lower", "front", "rear", The orientation or positional relationship of the instructions such as "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outside" is based on attached drawing institute The orientation or positional relationship shown is merely for convenience of the description present invention, rather than the device or element of indication or suggestion meaning must There must be specific orientation, be constructed and operated in a specific orientation, therefore be not considered as limiting the invention.
Embodiment described above is only that preferred embodiment of the invention is described, and is not carried out to the scope of the present invention It limits, without departing from the spirit of the design of the present invention, those of ordinary skill in the art make technical solution of the present invention Various changes and improvements, should all fall into claims of the present invention determine protection scope in.

Claims (10)

1. a kind of composite catalytic oxidation handles used water difficult to degradate system, it is characterised in that: including inlet bucket (1), inlet bucket (1) is logical Piping is connected with device for catalyzing and oxidating ozone, and device for catalyzing and oxidating ozone is connected with intermediate bucket (13) by pipeline, intermediate Bucket (13) is connected with electrocatalysis oxidation apparatus by pipeline, and electrocatalysis oxidation apparatus is connected with out of the bucket (23) by pipeline, Wherein: the device for catalyzing and oxidating ozone includes ozone reactor (4), and the gas outlet (27) of ozone reactor (4) passes through pipe Road is connected with vent ozone destructor (5), and the water inlet (24) of ozone reactor (4) is connected with inlet bucket (1) by pipeline, ozone The air inlet (25) of reactor (4) is connected with aeration mechanism (33), is aerated mechanism by pipeline and is connected with ozone generation mechanism, electricity Catalytic oxidizing equipment includes electric catalysis reactor (19), is fixed with electrode (30), electrocatalytic reaction in electric catalysis reactor (19) Device (19) connect DC power supply with conducting wire by bronze medal, and electric catalysis reactor (19) connects out of the bucket (23) by pipeline.
2. composite catalytic oxidation according to claim 1 handles used water difficult to degradate system, it is characterised in that: ozone reactor (4) sample tap (26) is sequentially connected with the second valve (6) and the first sample bucket (7) by pipeline.
3. composite catalytic oxidation according to claim 1 handles used water difficult to degradate system, it is characterised in that: ozone generator Structure includes passing through the sequentially connected source of oxygen of pipeline (8), corrosion-resistant gas flowmeter (10), ozone generator (9), third valve (12) and ozone concentration on-line determination instrument (11).
4. composite catalytic oxidation according to claim 1 handles used water difficult to degradate system, it is characterised in that: inlet bucket (1) With the first valve (2), the first water pump (3) and second liquid flowmeter have been sequentially arranged in the connecting pipe of ozone reactor (4) (34)。
5. composite catalytic oxidation according to claim 1 handles used water difficult to degradate system, it is characterised in that: aeration mechanism (33) the 5th valve (16) is provided on the pipeline connecting with ozone generation mechanism.
6. composite catalytic oxidation according to claim 1 handles used water difficult to degradate system, it is characterised in that: intermediate bucket (13) the 4th valve (14), the second water pump (15) and the first liquid are disposed on the pipeline connecting with electrocatalysis oxidation apparatus Flowmeter (17).
7. composite catalytic oxidation according to claim 1 handles used water difficult to degradate system, it is characterised in that: electrocatalytic reaction The 6th valve (20) and probe tube (36), the probe tube (36) have been sequentially connected in device (19) and out of the bucket (23) connecting pipe On be provided with the 7th valve (21), probe tube (36) connects the second sample bucket (22).
8. composite catalytic oxidation according to claim 1 handles used water difficult to degradate system, it is characterised in that: the electrode It (30) include electro-catalysis anode and electro-catalysis cathode, the electro-catalysis anode uses DSA slab anode, and electro-catalysis cathode uses titanium Board-like cathode.
9. composite catalytic oxidation according to claim 1 handles used water difficult to degradate system, it is characterised in that: the electricity is urged Change reactor (19) bottom and is equipped with separators (35).
10. composite catalytic oxidation according to claim 1 handles used water difficult to degradate system, it is characterised in that: the exposure Mechanism of qi structure (33) is titanium alloy aeration head or aeration plate.
CN201910113081.9A 2019-02-13 2019-02-13 A kind of composite catalytic oxidation processing used water difficult to degradate system Pending CN109879399A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112591948A (en) * 2020-12-23 2021-04-02 轻工业环境保护研究所 Electro-catalytic ozone catalytic device, wastewater treatment system and wastewater treatment method
CN113138159A (en) * 2021-05-21 2021-07-20 中国石油化工股份有限公司 Corrosion evaluation method and corrosion evaluation device in ozone environment
CN116282468A (en) * 2023-02-13 2023-06-23 中建安装集团有限公司 Advanced wastewater treatment system and method

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CN108840404A (en) * 2018-07-04 2018-11-20 北京林业大学 A kind of unipolarity three-diemsnional electrode for reverse osmosis concentrated water with high salt couples ozone integral type reaction unit and application
CN208151130U (en) * 2017-12-15 2018-11-27 西安泰金工业电化学技术有限公司 A kind of processing unit of electrocatalytic oxidation used water difficult to degradate

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Publication number Priority date Publication date Assignee Title
CN201077792Y (en) * 2007-05-22 2008-06-25 华南理工大学 Ozone heterogenous catalysis oxygenize water treating device
CN202046923U (en) * 2011-05-17 2011-11-23 济南市供排水监测中心 Equipment for determining ozone dosage in water treatment
CN103466865A (en) * 2013-08-29 2013-12-25 中国海洋石油总公司 Ozone and photoelectrocatalysis combined treatment method of reverse osmosis membrane concentrated water in refinery waste water
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112591948A (en) * 2020-12-23 2021-04-02 轻工业环境保护研究所 Electro-catalytic ozone catalytic device, wastewater treatment system and wastewater treatment method
CN113138159A (en) * 2021-05-21 2021-07-20 中国石油化工股份有限公司 Corrosion evaluation method and corrosion evaluation device in ozone environment
CN113138159B (en) * 2021-05-21 2024-03-08 中国石油化工股份有限公司 Corrosion evaluation method and corrosion evaluation device in ozone environment
CN116282468A (en) * 2023-02-13 2023-06-23 中建安装集团有限公司 Advanced wastewater treatment system and method

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Application publication date: 20190614