CN108751344A - A kind of batch type processing system and treatment process of industrial wastewater middle and high concentration COD - Google Patents
A kind of batch type processing system and treatment process of industrial wastewater middle and high concentration COD Download PDFInfo
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- CN108751344A CN108751344A CN201810900873.6A CN201810900873A CN108751344A CN 108751344 A CN108751344 A CN 108751344A CN 201810900873 A CN201810900873 A CN 201810900873A CN 108751344 A CN108751344 A CN 108751344A
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- 238000000034 method Methods 0.000 title claims abstract description 49
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- 239000002351 wastewater Substances 0.000 claims abstract description 117
- 230000003647 oxidation Effects 0.000 claims abstract description 77
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 77
- 239000003814 drug Substances 0.000 claims abstract description 20
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- 239000001301 oxygen Substances 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 6
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- 238000012544 monitoring process Methods 0.000 claims description 6
- 238000007781 pre-processing Methods 0.000 claims description 5
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 4
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 4
- 238000007789 sealing Methods 0.000 claims description 4
- 239000013589 supplement Substances 0.000 claims description 4
- 239000006185 dispersion Substances 0.000 claims description 3
- 239000010865 sewage Substances 0.000 abstract description 18
- 238000004065 wastewater treatment Methods 0.000 abstract description 8
- 238000004043 dyeing Methods 0.000 abstract description 4
- 241000276457 Gadidae Species 0.000 abstract description 3
- 239000010893 paper waste Substances 0.000 abstract description 2
- 239000004912 1,5-cyclooctadiene Substances 0.000 abstract 1
- 238000005516 engineering process Methods 0.000 description 12
- -1 hydroxyl radical free radical Chemical class 0.000 description 10
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 8
- 238000010586 diagram Methods 0.000 description 8
- 230000008859 change Effects 0.000 description 6
- 239000005416 organic matter Substances 0.000 description 6
- 230000015556 catabolic process Effects 0.000 description 4
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- 238000006731 degradation reaction Methods 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 239000003344 environmental pollutant Substances 0.000 description 3
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229910000619 316 stainless steel Inorganic materials 0.000 description 2
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
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- 238000001311 chemical methods and process Methods 0.000 description 2
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- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000013461 design Methods 0.000 description 2
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- 235000003891 ferrous sulphate Nutrition 0.000 description 2
- 239000011790 ferrous sulphate Substances 0.000 description 2
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- PUKLDDOGISCFCP-JSQCKWNTSA-N 21-Deoxycortisone Chemical compound C1CC2=CC(=O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@@](C(=O)C)(O)[C@@]1(C)CC2=O PUKLDDOGISCFCP-JSQCKWNTSA-N 0.000 description 1
- QJZYHAIUNVAGQP-UHFFFAOYSA-N 3-nitrobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2(C(O)=O)[N+]([O-])=O QJZYHAIUNVAGQP-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- FCYKAQOGGFGCMD-UHFFFAOYSA-N Fulvic acid Natural products O1C2=CC(O)=C(O)C(C(O)=O)=C2C(=O)C2=C1CC(C)(O)OC2 FCYKAQOGGFGCMD-UHFFFAOYSA-N 0.000 description 1
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- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000001112 coagulating effect Effects 0.000 description 1
- 239000003034 coal gas Substances 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
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- 238000003912 environmental pollution Methods 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 239000002509 fulvic acid Substances 0.000 description 1
- 229940095100 fulvic acid Drugs 0.000 description 1
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 1
- 239000004021 humic acid Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
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- 238000007726 management method Methods 0.000 description 1
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- 239000012528 membrane Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- QMQXDJATSGGYDR-UHFFFAOYSA-N methylidyneiron Chemical compound [C].[Fe] QMQXDJATSGGYDR-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000010815 organic waste Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
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- 238000007747 plating Methods 0.000 description 1
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- 238000002834 transmittance Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
- C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
- C02F1/325—Irradiation devices or lamp constructions
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2201/00—Apparatus for treatment of water, waste water or sewage
- C02F2201/32—Details relating to UV-irradiation devices
- C02F2201/322—Lamp arrangement
- C02F2201/3227—Units with two or more lamps
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/001—Upstream control, i.e. monitoring for predictive control
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/003—Downstream control, i.e. outlet monitoring, e.g. to check the treating agents, such as halogens or ozone, leaving the process
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/005—Processes using a programmable logic controller [PLC]
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/02—Temperature
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/06—Controlling or monitoring parameters in water treatment pH
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/08—Chemical Oxygen Demand [COD]; Biological Oxygen Demand [BOD]
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/42—Liquid level
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2301/00—General aspects of water treatment
- C02F2301/04—Flow arrangements
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/026—Fenton's reagent
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Physical Water Treatments (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
The present invention provides a kind of batch type processing system and treatment process of industrial wastewater middle and high concentration COD, which is characterized in that including buffer storage, UV-Cu-Fenton advanced oxidation devices, chemicals dosing plant, wastewater conveyor, reflux line;The wastewater conveyor includes the first waste water delivery pump and the second waste water delivery pump, UV-Cu-Fenton advanced oxidation devices inlet is connected by the first waste water delivery pump and buffer storage outlet, and exit is connect through reflux line with inlet by the second waste water delivery pump;The chemicals dosing plant includes front end dosing pump and midway dosing pump, front end dosing pump is connect by drug feeding pipeline with the entrance of UV-Cu-Fenton advanced oxidation devices, midway dosing pump is connect by drug feeding pipeline with the stage casing of UV-Cu-Fenton advanced oxidation devices, especially suitable for small sewage treatment plant due to the wastewater treatment rich in a large amount of high concentration CODs, hardly degraded organic substance of the generations such as pharmacy waste water, sanitary sewage, dyeing waste water, paper waste, COD contents can reach level-one emission standard A after processing.
Description
Technical field
The present invention relates to Industrial Wastewater Treatment and automatically control the technical field being combined, and in particular to a kind of processing industry
The processing system and treatment process of Coal Gas Washing Cycling Water COD, especially suitable for small sewage treatment plant due to pharmacy waste water, life
A large amount of high concentration CODs of the generations such as sewage, dyeing waste water, paper waste, the wastewater treatment of hardly degraded organic substance and laboratory
Processing high concentration COD, hardly degraded organic substance waste water small testing device.
Background technology
Under the fast development of industry, China achieves economic rapid growth, while environmental pollution also becomes history something lost
The problem of staying.By effort in recent years, China achieves larger achievement, achievement in terms of urban sewage treatment technology
It is plentiful and substantial.As a piece of " the blue sea " for waiting to open up, water process market prospects are very optimistic.According to prediction industrial research institute《It is Chinese dirty
Water treatment field market is looked forward to the prospect reports with investment analysis》It has been shown that, the existing waterworks in China family more than 4000, sewage treatment plant 3500
More, with the gradual perfection of sewage treatment facility, wastewater treatment in China rate has risen to a high position at present.By year ends 2016, city
City's wastewater treatment rate has reached 93.4%, and county town wastewater treatment rate has also reached 87.4%.As industry environmental protection cry day edges up
Height, industrial wastewater treatment demand is ubiquitous, in factory of enterprise, is mainly distributed on electronics, plastic cement, plating, hardware, printing, food
The industries such as product, printing and dyeing.However these factories generate most of sewage needs can be just discharged into after certain processing river,
In the Cultivated waters such as sea, rivers, lakes pool, reservoir, pond.But in the prior art, using in the sewage after conventional process still
So there are many impurity to be difficult to handle, especially the organic matter etc. of the waste water of high concentration COD and difficult for biological degradation, treated water
In there are still colorations higher, humic acid, the problems such as fulvic acid content is higher.In being formed due to the water inlet of sewage treatment plant, big portion
It is divided into industrial tail water, also least a portion of sanitary sewage.It is remaining organic in water body after A/O processing by conventional processes
Object is largely hardly degraded organic substance, and treated water body COD is far above level-one emission standard A between 100~380mg/L.
Keep its organic matter degradation, stable water outlet up to standard, advanced treatment process need to be used.
The further treatment technique of waste water includes mainly physico-chemical process, bioanalysis, high-level oxidation technology etc..Physico-chemical process includes mainly
Absorption method, membrane separation process, Coagulation Method etc.;Bioanalysis includes oxidation pond further treatment technique, biological aerated filter process etc.;It is advanced
Oxidation technology includes the methods of Fenton methods and class Fenton technology, photocatalytic oxidation.Wherein, high-level oxidation technology is stablized the most
Reliably.
High-level oxidation technology is by generating OH (hydroxyl radical free radical) come to cannot be by universal oxidizing in sewage
Pollutant carry out oxidative degradation process.It is numerous studies have shown that the pollutant of bio-refractory usually has corresponding chemistry
Stability, it is difficult to which, by common oxidants permineralization, this requires used chemical agents to have enough oxidabilities thorough
Organic matter is destroyed at bottom, this trend has promoted the rapid hair to generate hydroxyl radical free radical as the high-level oxidation technology of main feature
Exhibition.Simultaneously because the hydroxyl radical free radical that tradition Fenton processes generate is influenced by the form of catalyst, the hydroxyl free of generation
Radix amount and oxidation efficiency cannot effectively play a role, and the irradiation of UV light can strengthen the yield and time effect of hydroxyl radical free radical
Can, therefore UV collaboration high-level oxidation technologies are developed at present.The technology is mainly characterized by:1) strengthen the generation of hydroxyl radical free radical
Amount;2) efficiency of the hydroxyl radical free radical to mineralization of organic material is improved.This trend has promoted to generate hydroxyl radical free radical to be main special
The high-level oxidation technology of point rapidly develops.
Chinese patent literature CN102849893B discloses a kind of high concentration hard-degraded organic waste water processing method, this method
Through coagulation air-float preprocessing process, the COD of suspended matter and part reduction waste water in water removal is removed;Through iron-carbon micro-electrolysis process, pass through
Electrochemical action, redox etc. make the organic matter in waste water obtain part removal, and B/C is worth to raising, to COD
Disposable removal rate up to 50% or more;Through ultraviolet Fenton oxidation process, under the irradiation of the ultraviolet lamp of corresponding power, it is added
H2O2, after ultraviolet Fenton oxidation, adjust pH and carry out coagulating sedimentation;Through A2/O biochemical processes, pollutant is ultimately breaks down into dioxy
Change carbon and water, producing water water quality is stablized.The invention has the advantages that ultraviolet Fenton oxidation reactor is arranged after light electrolysis, drop
Low H2O2Consumption and further improve the biodegradability of waste water.But the waste water COD after this method final process still compared with
Height is 200mg/L, and which provides only preliminary treatment methods, do not provide specific processing system and processing step.
Invention content
Based on existing Treatment of Industrial Water there are the shortcomings that, it is an object of the present invention to provide one kind can realize manually with from
Dynamic control is combined, and implements dynamic supervision, STOCHASTIC CONTROL added amount of chemical, is discharged COD after reducing Treatment of Industrial Water, it is ensured that water
The processing system of matter safety, the system operability is strong, and effect is good, and provides a kind of scientific and reasonable, highly practical reduction water body
The treatment process of COD.
Realize one of the object of the invention the technical solution adopted is that, a kind of intermittent place of industrial wastewater middle and high concentration COD
Reason system, which is characterized in that including buffer storage, UV-Cu-Fenton advanced oxidation devices, chemicals dosing plant, waste water conveying dress
It sets, reflux line;
The wastewater conveyor includes the first waste water delivery pump and the second waste water delivery pump, the UV-Cu-Fenton high
Grade oxidation unit inlet is connected by the first waste water delivery pump and buffer storage outlet, and exit passes through the second waste water delivery pump
It is connect with inlet through reflux line;
The chemicals dosing plant includes front end dosing pump and midway dosing pump, and front end dosing pump passes through drug feeding pipeline and UV-Cu-
The entrance of Fenton advanced oxidation devices connects, and midway dosing pump passes through drug feeding pipeline and UV-Cu-Fenton advanced oxidation devices
Stage casing connection.
Preferably, the UV-Cu-Fenton advanced oxidation devices are S types structure or continuous S types structure, including straight line portion
Divide and racetrack portion, straight line portion are internally provided with the UV modules of multiple laid out in parallel, the UV modules include holder, bottom plate, purple
Outer lamp, the holder are multilayer, are equipped with bottom plate on every layer of holder, are provided with multiple eyelets on the bottom plate, in every ultraviolet lamp
It is placed in a quartz socket tube, one end of the quartz socket tube is closed end, and the other end is equipped with sealing structure, every quartz socket tube
It is fixed on eyelet vertically across the eyelet, and by O-shaped rubber ring.
Preferably, the UV modules further include the attachment strap that rear and front end is stretched out, for riding upon the UV-Cu-Fenton
On advanced oxidation device, the racetrack portion of the UV-Cu-Fenton advanced oxidation devices is additionally provided with sector cover plate, sector cover plate
It is laid on above racetrack portion, the odor dispersion for obstructing waste water;
The UV modules further include warning device, and ultraviolet lamp is connect by electric wire with warning device, when the ultraviolet lamp
When spoilage is more than 20%, the warning device sends out alarm signal;
Each UV modules include multiple UV units being set up in parallel, and each UV units include the multiple ultraviolet lamps of a row and are located at
Coupled rectangle upper cover above ultraviolet lamp, upper lid is equipped with handle, for lifting the UV units.
Preferably, the first water quality on-line detector is equipped in the buffer storage, for detecting COD contents in water;It is described
Processing system further includes telemetering type pH meter, ultrasonic liquid level meter and the temperature being set in the UV-Cu-Fenton advanced oxidation devices
Meter, and the second water quality on-line detector, bottom bypass pipe set on exit, the bottom bypass pipe and UV-Cu-Fenton
Advanced oxidation device junction is equipped with electrically operated valve.
Preferably, the processing system further includes pretreatment unit, pretreatment unit outlet and the buffer storage entrance
Connection;
Preferably, the processing system further includes display device, for showing the state of ultraviolet lamp, Industry Waste in UV modules
The content, waste water liquid level, the pH value of reaction and reaction temperature of COD in water.
Preferably, the processing system further includes PLC automatic control system, the PLC automatic control system with first, the
Two waste water delivery pumps, front end dosing pump, midway dosing pump, electrically operated valve, ultraviolet lamp, warning device, display device, thermometer,
Telemetering type pH meter, ultrasonic liquid level meter and the connection of the first, second water quality on-line detector.
In addition, the present invention also provides a kind of intermittent treatment process of industrial wastewater middle and high concentration COD, which is characterized in that
Include the following steps:
Step 1:Industrial wastewater is delivered in buffer storage, COD in waste water is detected by the first water quality on-line detector
Content;
Step 2:The waste water in buffer storage is delivered to UV-Cu-Fenton advanced oxidations by the first waste water delivery pump
Device portal, while starting front end dosing pump, front end dosing is passed through according to the content of COD in the buffer storage measured in step 2
A certain amount of medicament is delivered to UV-Cu-Fenton advanced oxidation device entrances by pump, and the medicament is FeSO4With H2O2Mixing
Object or CuO and H2O2Mixture;
More preferable CuO and H2O2Mixture;UV-Cu-Fenton advanced oxidation devices are to traditional Fenton advanced oxidations
Depth improvement, one is by the effect of ultraviolet irradiation, improve the yield of hydroxyl radical free radical;The second is passing through copper catalyst
Instead of ferrous catalyst, while avoiding solid residue " iron cement " generated, the oxygen of organic matter is improved by the catalytic action of copper
Change efficiency.The hardly degraded organic substance that can not be removed in this method energy the efficient oxidation removal conventional waste water, its essence is H2O2In Cu2+
Catalytic action under the hydroxyl radical free radical (OH) that generates, OH can be acted on most of organic matters make its degradation, due to Cu2+With
Ultraviolet light is to H2O2Catalysis there are synergistic effects, reduce catalyst Cu2+Dosage improves H2O2Utilization rate, to difficult to degrade
Organic matter has higher decomposition efficiency.
Step 3:The waste water for being mixed with medicament is delivered to exit from UV-Cu-Fenton advanced oxidation device entrances, this
When close the first waste water delivery pump;
Step 4:By the second waste water delivery pump by the waste water in UV-Cu-Fenton advanced oxidation devices exit by returning
Flow tube road is sent UV-Cu-Fenton advanced oxidation devices inlet back to and is recycled;
Step 5:Second water quality on-line detector monitors COD in water body content in real time, when detecting exit water
When COD contents are not up to standard in body, electrically operated valve is opened, water body is discharged from bottom bypass pipe;When detecting COD in water body content
When undesirable, continuous repeatedly step 4, until up to standard.
Preferably, further include preprocessing process, it is defeated for tentatively reduction waste water COD and waste water SS, pretreated waste water
It send to buffer storage;Pretreated waste water COD content is less than 800mg/L, and waste water SS is less than 500mg/L.
Preferably, the water in UV-Cu-Fenton advanced oxidation devices is detected in entire processing procedure at any time by liquid level gauge
Position, water level should ensure that slightly below ultraviolet lamp tube top, when water level is significantly lower than requiring, starts the first waste water delivery pump and carry out water
Amount supply;PH monitorings are carried out by telemetering type pH meter, pH requires to be 3-4, it is found that when pH is undesirable, starts midway dosing pump
Supplement medicament.
Preferably, at 10-30 DEG C, the amount for handling hydrogen peroxide needed for the waste water of 1t is for water temperature control in entire processing procedure
0.5%-2%, H2O2With Fe2+/Cu2+Molar ratio be 35:1-20:1.
Compared with prior art, technical solution advantage provided by the invention is embodied in:
1. reach the degradation treatment of high COD in processing industrial wastewater by changing traditional process system or method,
Both it can slightly change pipeline in original treatment process system and carry out upgrading, the subsequent processing as existing treatment process
Device;It again can independent independent operating.
2. UV-Cu-Fenton advanced oxidation devices are passed in and out to monitor waste water in real time by PLC automatic control system, and
Water quality, water level conditions and UV lamp work operation conditions etc..
3. water quality testing meter carries out intermittent sampling Detection water quality, the hysteresis quality continuously examined is avoided, if detection water quality
Corresponding measure is taken when larger with normal water quality difference, if water quality can not be up to standard, pH is undesirable to need adjusting double
The dosage of oxygen water medicament is to ensure effluent quality.
4. the present invention both can be adapted for small sewage treatment plant due to pharmacy waste water, sanitary sewage, dyeing waste water, papermaking
A large amount of high concentration CODs of the generations such as waste water, the wastewater treatment of hardly degraded organic substance, but the processing that can be adapted for laboratory is highly concentrated
The small testing device for spending COD, hardly degraded organic substance waste water, can flexibly be arranged UV modules and the advanced oxygen of UV-Cu-Fenton as needed
Disguise the size set.
5. all data-signals are connected with display device by PLC control system by the present invention can dynamic ultraviolet lamp in real time
Observation can be switched to manual mode control whole system work, in order to prevent because having a power failure if automatically controlling and going wrong
And failure problems can not start when automatically controlling, and MANUAL CONTROL mode is provided at the switches such as electrically operated valve.
6. processing system provided by the invention uses intermittent sewage treatmentmethod, it is suitable for the timely place of small lot waste water
Reason, processing procedure are more convenient flexibly.
7. the processing system that the present invention handles high COD in industrial wastewater by the continous way of offer can handle high concentration
The industrial wastewater of COD, hardly degraded organic substance so that treated COD, BOD5, TN, N-NH3, TP, pH, SS reach level-one A mark
Standard, and its operational management is convenient, process stabilizing, investment operating cost is low.
Description of the drawings
Fig. 1 is the batch type processing system structural schematic diagram of industrial wastewater middle and high concentration COD provided by the invention a kind of;
Fig. 2 is UV modular structure schematic diagrams provided by the invention;
Fig. 3 is the holder and floor structure schematic diagram of UV modules provided by the invention;
Fig. 4 is UV cellular construction schematic diagrams provided by the invention;
Fig. 5 is ultraviolet lamp structural schematic diagram provided by the invention;
Fig. 6 is sector cover plate structural schematic diagram provided by the invention.
Reference numeral:1:Buffer storage;2:UV-Cu-Fenton advanced oxidation devices;3:Reflux line;4:First waste water
Delivery pump;5:Second waste water delivery pump;6:Front end dosing pump;7:Midway dosing pump;8:Telemetering type pH meter;9:Ultrasonic liquid level meter;
10:Thermometer;11:Second water quality on-line detector;12:Bottom bypass pipe;13:Holder;14:Bottom plate;15:Ultraviolet lamp;16:Hole
Eye;17:Quartz socket tube;18:O-shaped rubber ring;19:Upper cover;20:Handle;21:Electric wire;22:Attachment strap;23:Sector cover plate.
Specific implementation mode
The specific embodiment of the invention is described with reference to the accompanying drawings and embodiments:
As shown in Figure 1, the batch type processing system of industrial wastewater middle and high concentration COD provided by the invention a kind of, including it is pre-
Processing unit, buffer storage 1, UV-Cu-Fenton advanced oxidation devices 2, chemicals dosing plant, wastewater conveyor, reflux line 3;
Wherein pretreatment unit is connect with 1 entrance of buffer storage, and wastewater conveyor includes that the first waste water delivery pump 4 and the second waste water are defeated
Pump 5,2 inlet of UV-Cu-Fenton advanced oxidation devices is sent to be connected by the first waste water delivery pump 4 and the outlet of buffer storage 1,
Exit is connect through reflux line 3 with inlet by the second waste water delivery pump 5;Chemicals dosing plant includes front end dosing pump 6 in
Way dosing pump 7, front end dosing pump 6 are connect by drug feeding pipeline with the entrance of UV-Cu-Fenton advanced oxidation devices 2, and midway adds
Teat pipette 7 is connect by drug feeding pipeline with the stage casing of UV-Cu-Fenton advanced oxidation devices 2.UV-Cu-Fenton advanced oxidations fill
2 are set as S types structure or continuous S types structure, including straight line portion and racetrack portion, straight line portion are internally provided with multiple laid out in parallel
UV modules.The first water quality on-line detector is equipped in buffer storage 1, for detecting COD contents in water;Processing system further includes
Telemetering type pH meter 8, ultrasonic liquid level meter 9 in UV-Cu-Fenton advanced oxidation devices 2 and thermometer 10, and be set to out
The second water quality on-line detector 11, bottom bypass pipe 12 at mouthful, bottom bypass pipe 12 are filled with UV-Cu-Fenton advanced oxidations
It sets 2 junctions and is equipped with electrically operated valve.Processing system further includes display device, for show the state of ultraviolet lamp 15 in UV modules,
The content, waste water liquid level of COD in industrial wastewater, reaction pH value and reaction temperature.
Also, processing system provided by the invention further includes PLC automatic control system, PLC automatic control system with first,
Second waste water delivery pump 5, front end dosing pump 6, midway dosing pump 7, electrically operated valve, ultraviolet lamp 15, warning device, display device,
Thermometer 10, telemetering type pH meter 8, ultrasonic liquid level meter 9 are connected with the first, second water quality on-line detector.The system by PLC from
Autocontrol system realizes, the opening/stop of all devices in whole system, interlock protection realized by PLC automatic control system,
Central Control Room is enable to monitor following signals:15 run signal of ultraviolet lamp, fault-signal, each UV modules usage time, electric current letter
Number, water level signal, water quality signal, fluorescent tube failure, low ultraviolet it is strong etc..
The control of UV modules has also needed to ultraviolet intensity monitoring system, and the monitoring system is mainly by UV intensity sensor
It is constituted with circuit, UV intensity sensor model number is SUV-G6DA24IS-SW9 (4-20mA), directly can really react ultraviolet
The real-time change of luminous intensity.Liquid level gauge is additionally provided in the system, liquid level gauge uses low water level sensor, using floating ball continous way liquid
Position meter, using two-wire system, operating current 4-20mA, voltage 24V can be with measure water positions using 316 stainless steels.
System provided by the invention further includes power control cabinet, and rectifier, fan, protective relaying device, electricity are equipped in power control cabinet
The cities Xiang Yu are electrically connected, and ultraviolet lamp 15 is connect with electric wire 21 and warning device.Power control cabinet uses bottom incoming mode, power control cabinet also band
There is maintenance power outlet, indicator light is provided in power control cabinet, shows that the operation of every equipment, malfunction, power control cabinet can be with
Realize the self-shield of all UV control systems electrical equipments, when any type fault condition occurs in every equipment, it can be automatic
It shuts down.The degree of protection and the class of insulation of all electric components of power control cabinet all need to meet the requirement used steadily in the long term.
It is as shown in Figure 2-5 the structural schematic diagram of UV modules and UV units in the present invention, UV module packets provided by the invention
Holder 13, bottom plate 14, ultraviolet lamp 15 are included, holder 13 is multilayer, and bottom plate 14 is equipped on every layer of holder 13, and holder 13 is square steel,
Bottom plate 14 is 316 stainless-steel sheets.Multiple eyelets 16 are provided on bottom plate 14, every ultraviolet lamp 15 is built in a quartz socket tube 17
Interior, one end of quartz socket tube 17 is closed end, and the other end is equipped with sealing structure, and every quartz socket tube 17 passes through eyelet 16, and leads to
It crosses O-shaped rubber ring 18 to be fixed on vertically on eyelet 16, so that quartz socket tube 17 is not in contact with any steel body on holder 13.
And each 15 modular assembly above water of ultraviolet lamp and underwater portion have the sealing grade of identical equivalent.Before UV modules further include
The attachment strap 22 that both ends are stretched out afterwards, for riding upon UV-Cu-Fenton advanced oxidation devices 2, UV modules further include alarm dress
It sets, ultraviolet lamp 15 is connect by electric wire 21 with warning device, and when the spoilage of ultraviolet lamp 15 is more than 20%, warning device is sent out
Alarm signal;Each UV modules include multiple UV units being set up in parallel, and each UV units include multiple 15 Hes of ultraviolet lamp of row
The coupled rectangle upper cover 19 above ultraviolet lamp 15, upper cover 19 is equipped with handle 20, for lifting the UV units.It is purple
Outer lamp 15 belongs to easily worn part, therefore warning device when circuit connection cannot go bad a lamp alarm once, in this way alarm frequency
Rate is too high not to meet control condition yet, therefore when being designed as spoilage and reaching 20%, and alarm is replaced again.Also, by aobvious
Showing device can be which part ultraviolet lamp 15 breaks down with real-time display, be convenient for changing UV units.Ultraviolet lamp 15 also passes through electric wire
21 are electrically connected with city, and the electric wire 21 of connecting tube has waterproof jacket protection.
Each UV modules are separately provided in the present invention, and the UV units in each UV modules are separately provided, and each UV is mono-
Member and module can be lifted by crane individually, and not influence other units and module work.Replacing fluorescent tube, quartz socket tube 17 and cleaning
When quartz socket tube 17, system still can work on.The design of holder 13 of entire UV modules can prevent ultraviolet lamp 15 and incline
, and when toppling over protection ultraviolet lamp 15 is remained to work on.
It is illustrated in figure 6 23 schematic diagram of sector cover plate provided by the invention, sector cover plate 23 is layed in UV-Cu-Fenton
Above the racetrack portion of advanced oxidation device 2, the odor dispersion for obstructing waste water.
In addition, being equipped with electromagnetic flowmeter, motor-driven valve in wastewater conveyor and chemicals dosing plant pipeline in the present invention
The necessary valve accessories such as door and corresponding check-valves, and PLC can be achieved at the same time and automatically control and manually control.
The intermittent treatment process of industrial wastewater middle and high concentration COD provided by the invention includes the following steps:
Step 1:It pre-processes (being arranged as required to)
COD contents in usual industrial wastewater or sanitary sewage can reach thousand mg/litre ranks, and it is right first to need at this time
It is pre-processed, and pretreatment mode is removed by the way of reducing COD contents in traditional wastewater processing by pre-processing
The impurity in waste water is removed, it is preliminary to reduce COD concentration, and waste water SS is reduced, it is convenient for subsequent processing.Pretreated waste water COD contains
Amount is less than 800mg/L, and waste water SS is less than 500mg/L, and pretreated waste water is delivered to buffer storage 1.After reduction SS is conducive to
Ultraviolet lamp 15 plays a role in continuous processing step.
It, can not be preprocessed when COD contents are less than 800mg/L in pending waste water, and waste water SS is less than 500mg/L
Step is directly entered system provided by the invention and is handled, i.e., system provided by the invention can be with isolated operation.
Step 2:Pretreated industrial wastewater is delivered in buffer storage 1, is examined by the first water quality on-line detector
COD contents in waste water are surveyed, the ferrous sulfate (FeSO for needing to add is calculated according to the COD initial contents measured4) or copper oxide
(CuO) amount and hydrogen peroxide (H2O2) amount, wherein ferrous sulfate and copper oxide select a use, handles double needed for the waste water of 1t
The amount of oxygen water is 0.5%-2%, H2O2With Fe2+/Cu2+Molar ratio be 35:1-20:1.
Step 3:The waste water in buffer storage 1 is delivered to the advanced oxygen of UV-Cu-Fenton by the first waste water delivery pump 4
2 entrances are set in makeup, while starting front end dosing pump 6, before being passed through according to the content of COD in the buffer storage 1 measured in step 2
A certain amount of medicament is delivered to 2 entrance of UV-Cu-Fenton advanced oxidation devices, medicament FeSO by end dosing pump 64With H2O2's
Mixture or CuO and H2O2Mixture.
Step 4:The waste water for being mixed with medicament enters UV-Cu-Fenton advanced oxidation devices 2, ultraviolet lamp 15 and water inlet water
It is vertical to flow direction, 15 outside of ultraviolet lamp is cased with quartz socket tube 17 as protection, and ultraviolet lamp 15 is put into the hole of ready-made holder 13
In eye 16 (13 structure of holder is similar to rack for test tube structure), 15 top of ultraviolet lamp has rectifier and electric wire 21 to be embedded in top band
Have in the structure of handle 20 (structure is similar to power saving fluorescent lamps connection structure), passes through ultrasonic liquid level meter 9 in entire processing procedure
Water level in detection UV-Cu-Fenton advanced oxidation devices 2 at any time, 15 bottom of ultraviolet lamp needs advanced with UV-Cu-Fenton
Oxidation unit 2 reserves certain space, and 15 top of ultraviolet lamp then needs all to flood in water, therefore whole device circuit needs
Water-proofing treatment is carried out, but UV modules top should retain a part above the water surface, ensures the external components such as handle 20 not by water logging
Not yet.When water level is significantly lower than requiring, starts the first waste water delivery pump 4 and carry out water supply;PH is carried out by telemetering type pH meter 8
Monitoring, pH requires to be 3-4, it is found that when pH is undesirable, starts midway dosing pump 7 and supplement H2O2.Wait for that waste water is delivered to UV-Cu-
When at 2 inlet port of Fenton advanced oxidation devices, the first waste water delivery pump 4 is closed.
Step 5:The waste water in 2 exit of UV-Cu-Fenton advanced oxidation devices is passed through by the second waste water delivery pump 5
Reflux line 3 is sent 2 inlet of UV-Cu-Fenton advanced oxidation devices back to and is recycled.Water temperature control exists in entire processing procedure
10-30℃。
Step 6:COD in water body content is detected by the second water quality on-line detector 11, COD in water body contains when exit
When amount reaches first level A, electrically operated valve is opened, water body is discharged from bottom bypass pipe 12;When to COD in water body content up to not
When to first level A, waste water constantly recycles in UV-Cu-Fenton advanced oxidation devices 2 until up to standard.
According to actual measurement, under normal conditions mean residence time control of the waste water in UV-Cu-Fenton advanced oxidation devices 2
System is in 30mim or so.
Embodiment 1
The sewage collected in the present embodiment all is from Yongning county industrial park, wherein 60% or more industrial wastewater accounting,
Remaining is sanitary sewage.Waste water is in UV-Cu-Fenton advanced oxidation devices 2 after processing, and reaching level-one A, (COD contents are less than
50mg/L) discharge standard.
Specific treatment process is as follows:
Step 1:Pretreated industrial wastewater is delivered in buffer storage 1, is examined by the first water quality on-line detector
COD contents in waste water are surveyed, the copper oxide (CuO) for needing to add and hydrogen peroxide (H are calculated according to the COD initial contents measured2O2)
Amount, the amount for calculating hydrogen peroxide needed for the waste water of gained processing 1t are 1%, H2O2With Cu2+Molar ratio be 30:1.
Step 2:The waste water in buffer storage 1 is delivered to the advanced oxygen of UV-Cu-Fenton by the first waste water delivery pump 4
2 entrances are set in makeup, while starting front end dosing pump 6, before being passed through according to the content of COD in the buffer storage 1 measured in step 2
Hold dosing pump 6 by a certain amount of copper oxide (CuO) and hydrogen peroxide (H2O2) be delivered to UV-Cu-Fenton advanced oxidation devices 2 and enter
Mouthful.
Step 3:It is mixed with copper oxide (CuO) and hydrogen peroxide (H2O2) waste water enter UV-Cu-Fenton advanced oxidations dress
2 are set, water inlet water (flow) direction is vertical with ultraviolet lamp 15, and 15 top of ultraviolet lamp needs all to flood in water.When water level is significantly lower than
It is required that when, start the first waste water delivery pump 4 and carries out water supply;PH monitorings are carried out by telemetering type pH meter 8, pH requires to be 3-4,
It was found that when pH is undesirable, starts midway dosing pump 7 and supplement medicament.Wait for that waste water is delivered to UV-Cu-Fenton advanced oxidations dress
When setting at 2 inlet ports, the first waste water delivery pump 4 is closed.
Step 4:The waste water in 2 exit of UV-Cu-Fenton advanced oxidation devices is passed through by the second waste water delivery pump 5
Reflux line 3 is sent 2 inlet of UV-Cu-Fenton advanced oxidation devices back to and is recycled.Water temperature control exists in entire processing procedure
10-30℃。
Step 5:COD in water body content is detected by the second water quality on-line detector 11, waste water is in UV-Cu-Fenton high
In grade oxidation unit 2 when cycle about 28min, water quality reaches level-one A standards, and water body is discharged from bottom bypass pipe 12.
Effluent quality is good after processing for waste water.
The waste water quality parameter of the present embodiment before and after the processing is as shown in table 1, wherein design influent quality is pretreated
Waste water quality:
The waste water quality (pH dimensionless) of table 1 before and after the processing
Component and detection device used are commercial product in the present embodiment.Wherein, 15 model of ultraviolet lamp
ZW150D19W-Z1554, manufacturer are Shelley spy CNLIGHT, and 15 power of ultraviolet lamp is 150W, and lamp type is low-pressure mercury
Lamp, all instrument of uv transmittance 253.7nm, UV module are controlled by PLC automatic control system.Institute of the present invention
It is commercial sensor with 316L stainless steels, water pump, ultrasonic liquid level meter 9 and pipeline valve attachment etc.;PLC, which is automatically controlled, is
System uses SIEMENS PLC S7-300 programmable controllers, model 6ES7314-1AG14-0AB0, by Guangzhou ant as automatic
Change System Co., Ltd to sell;Software used in the present invention is technology known to this field, using KingView software, WINCC groups
State software, STEP7 softwares these softwares can be conventional and be easy to download and obtain.
The specific implementation mode of the present invention has made detailed explanation to present disclosure, but does not limit to this implementation
Example, those skilled in the art are according to the present invention to enlighten any obvious change done, and belongs to right of the present invention and protects
The range of shield.
Claims (10)
1. a kind of batch type processing system of industrial wastewater middle and high concentration COD, which is characterized in that including buffer storage, UV-Cu-
Fenton advanced oxidation devices, chemicals dosing plant, wastewater conveyor, reflux line;
The wastewater conveyor includes the first waste water delivery pump and the second waste water delivery pump, the advanced oxygen of UV-Cu-Fenton
Disguise and is connected by the first waste water delivery pump and buffer storage outlet at posting port, the UV-Cu-Fenton advanced oxidation devices
Exit is connect through reflux line with inlet by the second waste water delivery pump;
The chemicals dosing plant includes front end dosing pump and midway dosing pump, and front end dosing pump passes through drug feeding pipeline and UV-Cu-
The entrance of Fenton advanced oxidation devices connects, and midway dosing pump passes through drug feeding pipeline and UV-Cu-Fenton advanced oxidation devices
Stage casing connection.
2. a kind of processing system as described in claim 1, which is characterized in that the UV-Cu-Fenton advanced oxidation devices are
S types structure or continuous S types structure, including straight line portion and racetrack portion, straight line portion are internally provided with the UV of multiple laid out in parallel
Module, the UV modules include holder, bottom plate, ultraviolet lamp, and the holder is multilayer, and bottom plate is equipped on every layer of holder, described
Multiple eyelets are provided on bottom plate, every ultraviolet lamp is built in a quartz socket tube, and one end of the quartz socket tube is closed end,
The other end is equipped with sealing structure, and every quartz socket tube passes through the eyelet, and is fixed on eyelet vertically by O-shaped rubber ring.
3. a kind of processing system as claimed in claim 2, which is characterized in that the UV modules further include what rear and front end was stretched out
Attachment strap, for riding upon the UV-Cu-Fenton advanced oxidation devices, the UV-Cu-Fenton advanced oxidation devices
Racetrack portion is additionally provided with sector cover plate, and sector cover plate is laid on above racetrack portion, the odor dispersion for obstructing waste water;
The UV modules further include warning device, and ultraviolet lamp is connect by electric wire with warning device, when the damage of the ultraviolet lamp
When rate is more than 20%, the warning device sends out alarm signal;
Each UV modules include multiple UV units being set up in parallel, and each UV units include the multiple ultraviolet lamps of a row and are located at ultraviolet
Coupled rectangle upper cover above lamp, upper lid is equipped with handle, for lifting the UV units.
4. a kind of processing system as claimed in claim 3, which is characterized in that it is online to be equipped with the first water quality in the buffer storage
Detector, for detecting COD contents in water;The processing system further includes being set to the UV-Cu-Fenton advanced oxidation devices
Interior telemetering type pH meter, ultrasonic liquid level meter and thermometer, and the second water quality on-line detector, bottom bypass set on exit
Pipe, the bottom bypass pipe are equipped with electrically operated valve with UV-Cu-Fenton advanced oxidation devices junction.
5. a kind of processing system as claimed in claim 4, which is characterized in that the processing system further includes that PLC is automatically controlled
System, the PLC automatic control system and the first, second waste water delivery pump, front end dosing pump, midway dosing pump, electrically operated valve,
Ultraviolet lamp, warning device, display device, thermometer, telemetering type pH meter, ultrasonic liquid level meter and the first, second water quality on-line checking
Instrument connects.
6. a kind of processing system as claimed in claim 2, which is characterized in that the processing system further includes pretreatment unit,
Pretreatment unit outlet is connect with the buffer storage entrance;
The processing system further includes display device, for showing in UV modules containing for COD in the state of ultraviolet lamp, industrial wastewater
Amount, waste water liquid level, the pH value of reaction and reaction temperature.
7. a kind of intermittent treatment process of industrial wastewater middle and high concentration COD, which is characterized in that include the following steps:
Step 1:Industrial wastewater is delivered in buffer storage, detecting COD in waste water by the first water quality on-line detector contains
Amount;
Step 2:The waste water in buffer storage is delivered to UV-Cu-Fenton advanced oxidation devices by the first waste water delivery pump
Entrance, while starting front end dosing pump, it will by front end dosing pump according to the content of COD in the buffer storage measured in step 2
A certain amount of medicament is delivered to UV-Cu-Fenton advanced oxidation device entrances, and the medicament is FeSO4With H2O2Mixture,
Or CuO and H2O2Mixture;
Step 3:The waste water for being mixed with medicament is delivered to exit from UV-Cu-Fenton advanced oxidation device entrances, closes at this time
Close the first waste water delivery pump;
Step 4:The waste water in UV-Cu-Fenton advanced oxidation devices exit is passed through into return duct by the second waste water delivery pump
Road is sent UV-Cu-Fenton advanced oxidation devices inlet back to and is recycled;
Step 5:Second water quality on-line detector monitors COD in water body content in real time, when detecting in the water body of exit
When COD contents are not up to standard, electrically operated valve is opened, water body is discharged from bottom bypass pipe;When detecting that COD in water body content is not inconsistent
When conjunction requires, continuous repeatedly step 4, until up to standard.
8. treatment process as claimed in claim 7, which is characterized in that further include preprocessing process, for tentatively reducing waste water
COD and waste water SS, pretreated waste water are delivered to buffer storage;Pretreated waste water COD content is less than 800mg/L, gives up
Water SS is less than 500mg/L.
9. treatment process as claimed in claim 7, which is characterized in that examined at any time by ultrasonic liquid level meter in entire processing procedure
The water level in UV-Cu-Fenton advanced oxidation devices is surveyed, water level should ensure that slightly below UV modules top, when water level is significantly lower than
It is required that when, start the first waste water delivery pump and carries out water supply;PH monitorings are carried out by telemetering type pH meter, pH requires to be 3-4, hair
When now pH is undesirable, starts midway dosing pump and supplement H2O2。
10. treatment process as claimed in claim 7, which is characterized in that water temperature is controlled at 10-30 DEG C in entire processing procedure,
The amount for handling hydrogen peroxide needed for the waste water of 1t is 0.5%-2%, H2O2With Fe2+/Cu2+Molar ratio be 35:1-20:1.
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