CN108217907A - A kind of parameter control method in phenolic waste water processing procedure - Google Patents

A kind of parameter control method in phenolic waste water processing procedure Download PDF

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Publication number
CN108217907A
CN108217907A CN201810139478.0A CN201810139478A CN108217907A CN 108217907 A CN108217907 A CN 108217907A CN 201810139478 A CN201810139478 A CN 201810139478A CN 108217907 A CN108217907 A CN 108217907A
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Prior art keywords
waste water
fenton
oxidation reactor
batch
fenton oxidation
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Chinese (zh)
Inventor
张小雨
高尚
李娜
张旭
刘海燕
吴相会
王元涛
刘时光
刘文锐
余俊洁
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Jilin Jianzhu University
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Jilin Jianzhu University
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Priority to CN201810139478.0A priority Critical patent/CN108217907A/en
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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
    • C02F1/72—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
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • 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
    • C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
    • 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
    • C02F2001/007—Processes including a sedimentation step
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/34—Organic compounds containing oxygen
    • C02F2101/345—Phenols
    • 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
    • C02F2209/04—Oxidation reduction potential [ORP]
    • 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
    • C02F2305/00—Use of specific compounds during water treatment
    • C02F2305/02—Specific form of oxidant
    • C02F2305/026—Fenton's reagent

Abstract

The present invention discloses the parameter control method in a kind of phenolic waste water processing procedure.This method includes：Phenolic waste water is imported to Fenton oxidation reactor and adds acid solution, makes the pH value of phenolic waste water between 35, so as to provide acidic environment for Fenton oxidation reaction；Fenton reagent is added into phenolic waste water makes Fenton reagent be reacted with phenolic waste water progress Fenton oxidation, and the oxidation reduction potential value that oxidation-reduction potential on-line detector detects is obtained in real time, stop adding Fenton reagent when the oxidation reduction potential value of phenolic waste water meets preset condition；It adds the phenolic waste water after Fenton reagent and carries out oxidative degradation；Lye is added, the pH value of phenolic waste water is regulated and controled between 78, so as to which Pyrogentisinic Acid's waste water carries out flocculation treatment, the waste water after being flocculated；Wastewater sedimentation after flocculation is for a period of time afterwards discharged the supernatant after precipitation and useless mud from Fenton oxidation reactor.Method disclosed by the invention can improve the treatment effect of phenolic waste water.

Description

A kind of parameter control method in phenolic waste water processing procedure
Technical field
The present invention relates to phenolic waste water process field, more particularly to the state modulator in a kind of phenolic waste water processing procedure Method.
Background technology
Recently as the development of petrochemical industry, phenolic waste water pollution problem is outstanding day by day.Phenol has stable phenyl ring Structure, not degradable, direct Applied Physics, biochemical process processing phenolic waste water are difficult to reach ideal treatment effect, it is necessary to carry out Advanced treating.Currently used advanced treatment process includes：Activated carbon adsorption, coagulating sedimentation, ozone oxidation, Fenton oxidation etc.. Fenton oxidation has had one-hundred-year history, as a kind of effective height so far since 1894 are found by French scientist Fenton Grade oxidation technology, since its equipment is simple, oxidability is strong, treatment effeciency is high, is widely used in handling various works difficult to degrade Industry waste water.The essence of Fenton oxidation method is ferrous ion (Fe in acid condition2+) and hydrogen peroxide generation chain reaction, catalysis Generate hydroxyl radical free radical.Hydroxyl radical free radical has stronger oxidability, and oxidation-reduction potential is only second to fluorine, up to 2.80V； In addition, hydroxyl radical free radical electron affinity energy power reaches 569.3kJ, there is very strong addition reaction characteristic, thus Fenton reagent can nothing Selectively most of organic matters in oxidized waste water, hard to work especially suitable for bio-refractory or general chemical oxidation is organic Wastewater oxidation processing.Fe2+With H2O2Between reaction speed quickly, generation hydroxyl radical free radical generate Fe simultaneously3+.In alkaline condition Lower Fe3+Fe (OH) of the generation with absorption, flocculation3, further remove Organic substance in water matter.
The key that Fenton oxidation reacts it can be seen from Fenton's reaction mechanism is hydroxyl radical free radical, therefore Fe2+With H2O2Dosage is very big to the influential effect of advanced treating phenolic waste water.Work as Fe2+And H2O2When throwing amount is relatively low, hydroxyl radical free radical ( OH production quantity) is relatively fewer, and then treatment effeciency is relatively low.But H2O2Simultaneously be hydroxyl radical free radical capturing agent, H2O2Throwing was measured Gao Shi, the hydroxyl radical free radical that the system of capture is generated.When the throwing amount of iron is excessively high, H2O2It is generated by promptly catalytic decomposition a large amount of Reactive hydroxyl radical, however hydroxyl radical free radical is with the reaction of matrix that in contrast speed is slower, so unconsumed free Reaction generation water is quenched in hydroxyl radical free radical each other.The coloration of the excessively high water for not only increasing processing of iron throwing amount, but also generate more More sludge.In addition, Fe2+And H2O2Reagent cost is higher.Along with phenolic waste water have in water concentration, water etc. it is larger Variation, and Fenton's reaction and oxidation process are considerably complicated dynamic processes, if Fenton reagent is not added process monitored, Control, it will be difficult to reach expected treatment effect.
Invention content
The object of the present invention is to provide a kind of batch-type Fenton oxidation reactions for the treatment of effect that can improve phenolic waste water Course control method for use.
To achieve the above object, the present invention provides following schemes：
A kind of parameter control method in phenolic waste water processing procedure, obtains as follows：
Selected water is 20-50m3/ d, the phenolic waste water that phenol concentration is 30-50mg/L, as pending phenolic waste water；
Batch-type Fenton oxidation reactor is run, the batch-type Fenton oxidation reactor group number is 1-3 groups, and by every group The hydraulic detention time of the batch-type Fenton oxidation reactor is set as 6-10 hours；Batch-type Fenton oxidation is anti-described in every group Device is answered by periodic duty, per the 2-4 period of day operation；The batch-type Fenton oxidation reactor each cycle includes：Water inlet process, Regulation and control pH value process, Fenton reagent add process, Fenton oxidation reactor process, flocculation operation, precipitation process, draining and spoil disposal 7 processes of process；
The batch-type Fenton oxidation reactor is equipped with pH value on-line detector and oxidation-reduction potential on-line detector； The installation site of the pH value on-line detector and oxidation-reduction potential on-line detector is apart from Fenton oxidation reactor bottom At 20cm, at the intermediate depth of the phenolic waste water and below the water surface of the phenolic waste water at 20cm；
In batch-type Fenton oxidation reactor water inlet process, import the phenol to the Fenton oxidation reactor and give up Water, the batch-type Fenton oxidation reactor water inlet activity time is 10-30 minutes；
Regulate and control pH value process in the batch-type Fenton oxidation reactor, add acid solution, make the pH value of the phenolic waste water It is maintained between 3-5, so as to provide acidic environment for Fenton oxidation reaction；The batch-type Fenton oxidation reactor regulates and controls pH value When 5-15 minutes before the water inlet process that the Fenton oxidation reactor is imported apart from the phenolic waste water terminates；The batch-type For Fenton oxidation reactor pH value regulation and control process using mechanical agitation mode, mixing speed gradient is 720~900s-1；
Process is added in the batch-type Fenton oxidation reactor Fenton reagent, Fenton examination is added into the phenolic waste water Agent；Process is added in the batch-type Fenton oxidation reactor Fenton reagent, obtained oxidation-reduction potential every 30 seconds examines online The oxidation reduction potential value that instrument detects is surveyed, and calculates the average value of oxidation reduction potential value, and whether judge the average value Between 450-500mV, judging result is calculated using pid algorithm, and according to judging judging result control Fenton reagent The reagent of dosing system adds process；The Fenton reagent adds process using mechanical agitation mode, mixing speed for 720~ 900s-1, to be stirred to the phenolic waste water for adding Fenton reagent；Hydrogen peroxide stock solution in the Fenton reagent A concentration of 330g/L is added, every group of Fenton oxidation reactor each cycle adds flow as 0.2~3.0L/min, ferrous sulfate reserve Liquid adds a concentration of 22.67g/L, and every group of Fenton oxidation reactor each cycle adds flow as 40~160L/min；
In the batch-type Fenton oxidation reactor Fenton reagent reaction process, using mechanical agitation mode, mixing speed Gradient is 240~300s-1, to be stirred to the phenolic waste water for adding the Fenton reagent；The batch-type Fenton The oxidation reactor Fenton oxidation reaction process time is 5-7 hours；
In the batch-type Fenton oxidation reactor flocculation operation, lye is added into the phenolic waste water, is thrown in lye Add in the stage with 720~900s-1Mixing speed gradient the waste water for adding lye is stirred, and is examined online using pH value The pH that instrument detection in real time adds the waste water of lye is surveyed, adding for lye is adjusted according to the pH value for the waste water for adding lye in real time Flow makes the pH for adding the waste water of lye maintain between 7-8；After the lye adds, with 20~60s-1Stir It mixes velocity gradient to be stirred the waste water for adding lye, so as to which Pyrogentisinic Acid's waste water carries out flocculation treatment, after being flocculated Waste water；The batch-type Fenton oxidation reactor flocculation operation time is 20-40 minutes；
Process, the wastewater sedimentation after the flocculation are precipitated in the batch-type Fenton oxidation reactor；The batch-type is fragrant The oxidation reactor precipitation activity time that pauses is 0.5 hour；
The batch-type Fenton oxidation reactor draining and spoil disposal activity time are 1-1.5 hours.
Optionally, a length of 20 minutes during the batch-type Fenton oxidation reactor water inlet process.
Optionally, regulation and control pH processes when a length of 10 minutes.
Optionally, every group of Fenton oxidation reactor flow that adds of ferrous sulfate stock solution within each period is 100L/ min；Every group of Fenton oxidation reactor adds flow as 2.25L/min each period hydrogen peroxide stock solution.
Optionally, a length of 6 hours during the batch-type Fenton oxidation reactor Fenton oxidation reaction process.
Optionally, flocculation operation when a length of 30 minutes.
Optionally, draining and spoil disposal process when a length of 1.2 hours.
Optionally, oxidation-reduction potential setting value is 475mV.
Optionally, the hydraulic detention time in the batch-type Fenton oxidation reactor is 8 hours.
According to specific embodiment provided by the invention, the invention discloses following technique effects：Parameter disclosed by the invention Control method, during Fenton reagent is added using oxidation-reduction potential on-line detector to oxidation reduction potential value into reality When be detected, so as to according to oxidation reduction potential value control Fenton reagent dosage, can realize well to Fenton try The control of agent dosage, Fenton reagent is avoided, which to add, very few makes that phenolic waste water processing is not thorough and Fenton reagent adds excessive make Into the wasting of resources and waste water recontamination, the effect of wastewater treatment is improved.
Description of the drawings
It in order to illustrate more clearly about the embodiment of the present invention or technical scheme of the prior art, 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 present invention Example, for those of ordinary skill in the art, without having to pay creative labor, can also be according to these attached drawings Obtain other attached drawings.
Fig. 1 is the method flow diagram of the parameter control method embodiment one in phenolic waste water processing procedure of the present invention.
Specific embodiment
Below in conjunction with the attached drawing in the embodiment of the present invention, the technical solution in the embodiment of the present invention is carried out clear, complete Site preparation describes, it is clear that described embodiment is only part of the embodiment of the present invention, instead of all the embodiments.It is based on Embodiment in the present invention, those of ordinary skill in the art are obtained every other without making creative work Embodiment shall fall within the protection scope of the present invention.
The reaction process of batch-type Fenton oxidation method removal phenol is complicated, and Fenton reagent dosage is to reaction effect, operation Cost, specific resistance to filtration are affected, and dosage should use automatic control system to regulate and control, but lack reliable control parameter. Phenol industrial wastewater of the present invention is provided one and Fenton reagent dosage can be carried out based on batch-type Fenton oxidation reactor Control system phenolic waste water processing method.Control parameter of the present invention is oxidation-reduction potential (Oxidation- ReductionPotential, ORP) value is PLC controller to the controller that parameter is controlled, oxidation-reduction potential is set Value is arranged in PLC controller.
Oxidation-reduction potential is an important factor for determining redox reaction direction and degree.Oxidation-reduction potential is reacted The synthesis redox ability of one system.On microcosmic apparently, in some system, each substance has unique oxidation also Proper energy power, and different material can react to each other, and influence each other, and finally macroscopically show corresponding ORP.In water body solution In, ORP is a complicated system being made of multiple oxidation-reduction pairs.Therefore, although ORP cannot show certain completely Oxide either the concentration of reduzate but can reflect the oxidisability of some system or the opposite journey of reproducibility power Degree.Fenton oxidation technology is a kind of high-level oxidation technology, has unique advantage, this method in terms of organic wastewater with difficult degradation thereby processing Reacting quintessence is redox reaction.In batch-type Fenton oxidation reactor, Fe2+And H2O2The hydroxyl generated in acid condition Base free radical is main oxidizing substance, and main reducing substances are refractory organic compounds and Fe in waste water2+, it is above-mentioned The concentration variation of several substances affects ORP value.Batch-type Fenton oxidation reaction system adds Fe2+And H2O2Afterwards, because the two is given birth to Into oxidizing species hydroxyl radical free radical, the reaction rate is larger, so hydroxy free radical concentration quickly increases, according to energy, this is special Equation, ORP value reaches maximum value, and ORP maximum values and initial H in reactor also by rapid increase in reactor2O2Dosage It is proportionate.In addition, experimental study and engineering practice result show Fenton oxidation system, there are best hydrogen peroxide initially to throw Dosage.To sum up, the number of hydrogen peroxide dosage can be reflected using batch-type Fenton oxidation reaction system ORP value changing rule, Therefore, it can be used as control parameter regulation and control Fenton reagent and add process.
The present invention is provided a batch-type Fenton oxidation reactor Fenton reagent and is thrown by theory analysis and verification experimental verification Dosage control parameter is controlled, management with reaching higher phenolic waste water removal efficiency with the process operation being easier to.By testing Arrived processing phenolic waste water hydrogen peroxide dosage ORP optimum value, provide technical support for practical application, using its as Control parameter has the characteristics that detection is accurate, simple and practicable, controllability is high.
In order to make the foregoing objectives, features and advantages of the present invention clearer and more comprehensible, it is below in conjunction with the accompanying drawings and specific real Applying mode, the present invention is described in further detail.
Embodiment one：
The selected water of the present invention is 20-50m3/ d, the benzene that main feature pollutant phenol concentration is 30-50mg/L Phenol waste water, as pending phenolic waste water；
Using batch-type Fenton oxidation reactor, the hydraulic detention time of the Fenton oxidation reactor is 6-10 hours, fragrant The group number of oxidation reactor is 1-3 groups, by periodic duty, can run 2-4 period daily according to hydraulic detention time. Each cycle is including water inlet, regulation and control pH, Fenton reagent adds, Fenton oxidation reacts, flocculates, precipitates, 7 works of draining and spoil disposal Sequence.The present invention increases the process of pH detections and the process of oxidation reduction potential value detection on the basis of 7 processes.PH's Detection is using pH value on-line detector, and using oxidation-reduction potential on-line detector, pH value exists for the detection of oxidation reduction potential value The installation site of line detector and oxidation-reduction potential on-line detector be at Fenton oxidation reactor bottom 20cm, At the intermediate depth of phenolic waste water and below the water surface of phenolic waste water at 20cm.The agitating mode that the present invention uses is mechanical agitation Mode.The specific introduction of process is carried out below.
Fig. 1 is the method flow diagram of the parameter control method embodiment one in phenolic waste water processing procedure of the present invention.
Referring to Fig. 1, this method includes：
Step 1：Water inlet and regulation and control pH processes：Phenolic waste water is imported to Fenton oxidation reactor and is importing phenolic waste water Acid solution is added in the process, makes the pH value of phenolic waste water between 3-5, so as to provide acidic environment for Fenton oxidation reaction.The step In rapid, acid solution can be added after water inlet process carries out a period of time.Finally also terminate to add acid solution at the end of process of intaking. Intake process when a length of 10~30 minutes.Regulate and control pH processes when it is 5-15 minutes a length of.
It specifically includes：
Phenolic waste water is imported in Fenton oxidation reactor；
It is anti-to the Fenton oxidation when being imported before the Fenton oxidation reactor terminates 5-15 minutes apart from phenolic waste water It answers and starts to add acid solution in device, and detect the pH of the phenolic waste water in real time using pH value on-line detector；Acid solution adds process Middle Pyrogentisinic Acid's waste water is stirred, and mixing speed gradient is 720~900s-1。
According to the pH of the phenolic waste water adjust in real time the acid solution flow make the pH of phenolic waste water maintain 3-5 it Between.
PH of the step due to being detected the phenolic waste water in real time using pH value on-line detector is realized in water inlet process Regulate and control pH in the process, saved the process occupied time of regulation and control pH, effectively saved hydraulic detention time, waste water can be improved The speed of processing.
Step 2：Fenton reagent adds process：Adding Fenton reagent into the phenolic waste water makes Fenton reagent give up with phenol Water carries out Fenton oxidation reaction, and obtains the oxidation reduction potential value that oxidation-reduction potential on-line detector detects in real time, when Stop adding Fenton reagent when the oxidation reduction potential value of the phenolic waste water meets preset condition；The oxidation-reduction potential exists Line detector is mounted in the Fenton oxidation reactor；Fenton reagent dosing system include ferrous sulfate stock solution tuner, Hydrogen peroxide stock solution tuner, ferrous sulfate metering pump and hydrogen peroxide metering pump.Ferrous sulfate stock solution tuner is used for The concentration of ferrous sulfate stock solution is allocated, hydrogen peroxide stock solution tuner is used to allocate the concentration of hydrogen peroxide stock solution, sulphur Sour ferrous iron metering pump is for regulating and controlling the flow that adds of ferrous sulfate stock solution, and hydrogen peroxide metering pump is in regulation and control hydrogen peroxide reserve Liquid adds flow.
The Fenton reagent that added into the phenolic waste water in step 2 makes Fenton reagent carry out Fenton with phenolic waste water Oxidation reaction specifically includes：
The hydrogen peroxide stock solution of a concentration of 330g/L and the sulphur of a concentration of 22.67g/L are added into the phenolic waste water Sour ferrous iron stock solution, it is 0.2 that every group of Fenton oxidation reactor of the hydrogen peroxide stock solution adds flow within each period ~3.0L/min, every group of Fenton oxidation reactor of the ferrous sulfate stock solution added within each period flow for 40~ 160L/min；
With 720~900s during Fenton reagent adds-1Mixing speed gradient to adding the phenol of Fenton reagent Waste water is stirred.
The real-time oxidation reduction potential value for obtaining oxidation-reduction potential on-line detector and detecting in step 2, when Stop adding Fenton reagent when the oxidation reduction potential value of the phenolic waste water meets preset condition, specifically include：
Once oxidation reduction potential on-line detector is obtained every preset time period to detect in the preset time period Multiple oxidation reduction potential values.
Calculate the average value of the multiple oxidation reduction potential value.
Judge whether the average value meets preset condition, obtain the first judging result.The preset condition is described flat Mean value meets oxidation-reduction potential setting value；The oxidation-reduction potential setting value is between 450-500mV.It is sharp in the present invention It is calculated by the use of pid algorithm and converts result of calculation as output valve.
When first judging result expression meets, then stop adding the Fenton reagent.
When first judging result expression is not met, then continue to add the Fenton reagent.
Stop adding in the present invention Fenton reagent and continuing add the Fenton reagent rate-determining steps be pass through by What the input value that output valve is directly inputted to terminal execution installation electromagnetical valve control was realized.
Step 3：Fenton oxidation reaction process：With 240~300s-1Mixing speed gradient to adding the benzene of Fenton reagent Phenol waste water is stirred.The Fenton oxidation reaction process when it is 5-7 hours a length of.
Step 4：Flocculation operation：Lye is added into the phenolic waste water, by the pH value of the waste water after the oxidative degradation Regulate and control between 7-8, so as to which Pyrogentisinic Acid's waste water carries out flocculation treatment, the waste water after being flocculated.It is a length of during the flocculation operation 20-40 minutes.
The step 4 specifically includes：
Lye is added into the phenolic waste water, is added in initial stage with 720~900s in lye-1Mixing speed ladder Degree is stirred the waste water for adding lye, is added in stage middle and later periods with 20~60s in lye-1Mixing speed gradient pair The waste water for adding lye is stirred；And the pH of the waste water of lye is added using the detection in real time of pH value on-line detector；
Flow is added according to what the pH for the waste water for adding lye adjusted lye in real time, makes to add the pH of the waste water of lye It maintains between 7-8.
Step 5：Precipitation and draining and spoil disposal process：It will will be precipitated respectively after wastewater sedimentation one end time after the flocculation Supernatant and useless mud afterwards is discharged from the Fenton oxidation reactor.
A length of 0.5 hour during the precipitation of the waste water after the flocculation, the discharge duration of waste water and useless mud after the precipitation It is 1-1.5 hours.
Embodiment two：
The present embodiment is unlike embodiment one：In step 1 intake process when a length of 20 minutes.
Embodiment three：
The present embodiment is unlike embodiment one or embodiment two：In step 2 regulate and control pH processes when a length of 10 minutes, It is anti-to the Fenton oxidation when being imported before the Fenton oxidation reactor terminates 10 minutes apart from phenolic waste water i.e. in step 2 It answers and starts to add acid solution in device.
Example IV：
The present embodiment is unlike any one embodiment in embodiment one to embodiment three：Every group of Fenton in step 2 Oxidation reactor flow that adds of ferrous sulfate stock solution within each period is 100L/min；Every group of Fenton oxidation reactor exists Each period hydrogen peroxide stock solution adds flow as 2.25L/min.
Embodiment five：
The present embodiment is unlike any one embodiment in embodiment one to example IV：Fenton oxidation in step 3 Reaction process when a length of 6 hours.
Embodiment six：
The present embodiment is unlike any one embodiment in embodiment one to embodiment five：Flocculation operation in step 4 When a length of 30 minutes.
Embodiment seven：
The present embodiment is unlike any one embodiment in embodiment one to embodiment six：Draining and row in step 5 Bricklayer's's sequence when a length of 1.2 hours.
Embodiment eight：
The present embodiment is unlike any one embodiment in embodiment one to embodiment seven：Redox in step 2 Potential setting value is 475mV.
Embodiment nine：
The present embodiment is unlike any one embodiment in embodiment one to embodiment eight：In Fenton oxidation reactor Hydraulic detention time be 8 hours.
According to specific embodiment provided by the invention, the invention discloses following technique effects：Phenol disclosed by the invention Parameter control method in wastewater treatment process utilizes oxidation-reduction potential on-line detector during Fenton reagent is added To oxidation reduction potential value into being detected in real time, so as to control the dosage of Fenton reagent, energy according to oxidation reduction potential value The enough control realized well to Fenton reagent dosage, avoid Fenton reagent add it is very few be not thorough phenolic waste water processing with And Fenton reagent adds and excessively causes the wasting of resources and waste water recontamination, improves the effect of wastewater treatment.
Each embodiment is described by the way of progressive in this specification, the highlights of each of the examples are with other The difference of embodiment, just to refer each other for identical similar portion between each embodiment.
Specific case used herein is expounded the principle of the present invention and embodiment, and above example is said The bright method and its core concept for being merely used to help understand the present invention；Meanwhile for those of ordinary skill in the art, foundation The thought of the present invention, in specific embodiments and applications there will be changes.In conclusion the content of the present specification is not It is interpreted as limitation of the present invention.

Claims (9)

1. the parameter control method in a kind of phenolic waste water processing procedure, it is characterised in that the parameter control method is by following step It is rapid to obtain：
Selected water is 20-50m3/ d, the phenolic waste water that phenol concentration is 30-50mg/L, as pending phenolic waste water；
Batch-type Fenton oxidation reactor is run, the batch-type Fenton oxidation reactor group number is 1-3 groups, and will be described in every group The hydraulic detention time of batch-type Fenton oxidation reactor is set as 6-10 hours；Batch-type Fenton oxidation reactor described in every group By periodic duty, per the 2-4 period of day operation；The batch-type Fenton oxidation reactor each cycle includes：Water inlet process, regulation and control PH value process, Fenton reagent add process, Fenton oxidation reactor process, flocculation operation, precipitation process, draining and spoil disposal process 7 processes；
The batch-type Fenton oxidation reactor is equipped with pH value on-line detector and oxidation-reduction potential on-line detector；It is described The installation site of pH value on-line detector and oxidation-reduction potential on-line detector is apart from Fenton oxidation reactor bottom 20cm Place, the phenolic waste water intermediate depth at and the water surface of the phenolic waste water below at 20cm；
In batch-type Fenton oxidation reactor water inlet process, the phenolic waste water is imported to the Fenton oxidation reactor, The batch-type Fenton oxidation reactor water inlet activity time is 10-30 minutes；
Regulate and control pH value process in the batch-type Fenton oxidation reactor, add acid solution, keep the pH value of the phenolic waste water Between 3-5, so as to provide acidic environment for Fenton oxidation reaction；Batch-type Fenton oxidation reactor regulation and control pH value away from When water inlet process from the phenolic waste water importing Fenton oxidation reactor terminates 5-15 minutes first；The batch-type Fenton For oxidation reactor pH value regulation and control process using mechanical agitation mode, mixing speed gradient is 720~900s-1；
Process is added in the batch-type Fenton oxidation reactor Fenton reagent, Fenton reagent is added into the phenolic waste water； Process is added in the batch-type Fenton oxidation reactor Fenton reagent, oxidation-reduction potential on-line detector was obtained every 30 seconds The oxidation reduction potential value detected, and the average value of oxidation reduction potential value is calculated, and judge whether the average value is in Between 450-500mV, judging result is calculated using pid algorithm, and according to judging that the judging result controls Fenton reagent to add The reagent of system adds process；The Fenton reagent adds process using mechanical agitation mode, and mixing speed is 720~900s-1, To be stirred to the phenolic waste water for adding Fenton reagent；In the Fenton reagent hydrogen peroxide stock solution add it is dense It spends for 330g/L, every group of Fenton oxidation reactor adds flow as 0.2~3.0L/min each cycle, ferrous sulfate stock solution Add a concentration of 22.67g/L, every group of Fenton oxidation reactor each cycle adds flow as 40~160L/min；
In the batch-type Fenton oxidation reactor Fenton reagent reaction process, using mechanical agitation mode, mixing speed gradient For 240~300s-1, to be stirred to the phenolic waste water for adding the Fenton reagent；The batch-type Fenton oxidation The reactor Fenton oxidation reaction process time is 5-7 hours；
In the batch-type Fenton oxidation reactor flocculation operation, lye is added into phenolic waste water, is added in the stage in lye With 720~900s-1Mixing speed gradient the waste water for adding lye is stirred, and using pH value on-line detector it is real-time Detection adds the pH of the waste water of lye, adds flow according to what the pH value for the waste water for adding lye adjusted lye in real time, makes The pH for adding the waste water of lye is maintained between 7-8；After the lye adds, with 20~60s-1Mixing speed ladder Degree is stirred the waste water for adding lye, so as to which Pyrogentisinic Acid's waste water carries out flocculation treatment, the waste water after being flocculated；It is described The batch-type Fenton oxidation reactor flocculation operation time is 20-40 minutes；
Process, the wastewater sedimentation after the flocculation are precipitated in the batch-type Fenton oxidation reactor；The batch-type Fenton oxygen It is 0.5 hour to change reactor precipitation activity time；
The batch-type Fenton oxidation reactor draining and spoil disposal activity time are 1-1.5 hours.
2. the parameter control method in a kind of phenolic waste water processing procedure according to claim 1, it is characterised in that described A length of 20 minutes during batch-type Fenton oxidation reactor water inlet process.
3. the parameter control method in a kind of phenolic waste water processing procedure according to claim 1, it is characterised in that regulation and control PH processes when a length of 10 minutes.
4. the parameter control method in a kind of phenolic waste water processing procedure according to claim 1, it is characterised in that every group Fenton oxidation reactor flow that adds of ferrous sulfate stock solution within each period is 100L/min；Every group of Fenton oxidation reaction Device adds flow as 2.25L/min each period hydrogen peroxide stock solution.
5. the parameter control method in a kind of phenolic waste water processing procedure according to claim 1, it is characterised in that described A length of 6 hours during batch-type Fenton oxidation reactor Fenton oxidation reaction process.
6. the parameter control method in a kind of phenolic waste water processing procedure according to claim 1, it is characterised in that flocculation Process when a length of 30 minutes.
7. the parameter control method in a kind of phenolic waste water processing procedure according to claim 1, it is characterised in that draining With spoil disposal process when a length of 1.2 hours.
8. the parameter control method in a kind of phenolic waste water processing procedure according to claim 1, it is characterised in that oxidation Reduction potential setting value is 475mV.
9. the parameter control method in a kind of phenolic waste water processing procedure according to claim 1, it is characterised in that described Hydraulic detention time in batch-type Fenton oxidation reactor is 8 hours.
CN201810139478.0A 2018-02-11 2018-02-11 A kind of parameter control method in phenolic waste water processing procedure Pending CN108217907A (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002079276A (en) * 2000-09-11 2002-03-19 Nec Corp Wastewater treatment method and apparatus
CN103601317A (en) * 2013-11-20 2014-02-26 山东省环境保护科学研究设计院 Interlock-control modular Fenton reagent wastewater treatment method and device
CN103979647A (en) * 2014-06-11 2014-08-13 中国科学院生态环境研究中心 Method for regulating, controlling and optimizing inductive electro-Fenton based on pH indication
CN104370363A (en) * 2014-11-09 2015-02-25 吉林建筑大学 Microaerobic SBR (sequencing batch reactor) control parameters for treating nondegradable industrial wastewater

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002079276A (en) * 2000-09-11 2002-03-19 Nec Corp Wastewater treatment method and apparatus
CN103601317A (en) * 2013-11-20 2014-02-26 山东省环境保护科学研究设计院 Interlock-control modular Fenton reagent wastewater treatment method and device
CN103979647A (en) * 2014-06-11 2014-08-13 中国科学院生态环境研究中心 Method for regulating, controlling and optimizing inductive electro-Fenton based on pH indication
CN104370363A (en) * 2014-11-09 2015-02-25 吉林建筑大学 Microaerobic SBR (sequencing batch reactor) control parameters for treating nondegradable industrial wastewater

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Application publication date: 20180629