CN105601039A - Method for treating nitrobenzene wastewater - Google Patents

Method for treating nitrobenzene wastewater Download PDF

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Publication number
CN105601039A
CN105601039A CN201511024989.0A CN201511024989A CN105601039A CN 105601039 A CN105601039 A CN 105601039A CN 201511024989 A CN201511024989 A CN 201511024989A CN 105601039 A CN105601039 A CN 105601039A
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fenton
groove
treatment
adds
electrocatalysis
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CN105601039B (en
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谭芳
郑琦
刘继延
李光
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Wuhan Weimeng Environmental Protection Technology Co ltd
Jianghan University
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Wuhan Weimeng Environmental Protection Technology Co ltd
Jianghan University
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    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F9/00Multistage treatment of water, waste water, or sewage
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/46Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/467Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
    • C02F1/4672Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/52Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/5236Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/52Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/54Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
    • C02F1/56Macromolecular compounds
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/66Treatment of water, waste water, or sewage by neutralisation; pH adjustment
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/72Treatment of water, waste water, or sewage by oxidation
    • C02F1/722Oxidation by peroxides
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/72Treatment of water, waste water, or sewage by oxidation
    • C02F1/74Treatment of water, waste water, or sewage by oxidation with air
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/30Organic compounds
    • C02F2101/38Organic compounds containing nitrogen
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2301/00General aspects of water treatment
    • C02F2301/08Multistage treatments, e.g. repetition of the same process step under different conditions
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2305/00Use of specific compounds during water treatment
    • C02F2305/02Specific form of oxidant
    • C02F2305/026Fenton's reagent

Abstract

The invention discloses a method for treating nitrobenzene wastewater. The method is characterized by including the steps that the wastewater with the COD content of 5,000-30,000 mg/L is added to inorganic acid for acidification; an electrolyte is added to supernatant of the acidified wastewater, and the mixture enters an electro-catalysis advanced oxidation tank to be electrolyzed; the mixture continues to enter an electro-Fenton tank to be electrolyzed to generate Fe2+, the mixture enters a Fenton oxidation tank, hydrogen peroxide is added, and a Fenton reaction is generated; a flocculating agent is added for settling, and the supernatant enters a biochemical system to be treated. The electro-catalysis advanced oxidation technology and an electro-Fenton oxidation method are adopted and combined, the wastewater is treated and modified through an electro-catalysis oxidation method, the iron dissolution amount can be greatly reduced through the electro-Fenton oxidation method, the adding quantity of H2O2 can be reduced, energy consumption and cost are reduced, and the method is environmentally friendly and economical.

Description

A kind of method for the treatment of of Nitrobenzene class waste water
Technical field
The present invention relates to Industrial Wastewater Treatment field, refer to particularly a kind for the treatment of of Nitrobenzene classThe method of waste water.
Background technology
Nitrobenzene compounds is one of important source material of organic chemistry industry. This class chemical combinationThing is extensively present in the chemistry such as petrochemical industry, soap, spices, dyestuff, explosive, pharmacyAmong the waste water of industry industry, this compounds has larger toxicity to people. Make at presentThe cost of processing industrial wastewater by biotechnology is lower, and microorganism has again stronger adaptationProperty and can variability, can not cause secondary pollution. Therefore use biological treatment to becomeThe ideal method of processing at present organic pollution is stronger but nitrobenzene compounds hasToxicity, intake very large to the burden of microorganism, directly biodegradation is processed more difficult. ElectricityCatalytic oxidation and Fenton (electric Fenton) oxidizing process is locating of applying in recent years morelyReason method, but still there are separately some defects.
By Electrocatalytic Oxidation energy consumption is high: in prior art, current efficiency optimum state is about40%, generally all at 20% left and right, 1000Ah/m3Electric weight in theory in current efficiency 100%Situation under, can only remove COD (1Ah=3600C, the M of 298mg/LO2=32g/molWhen 1mol electronics shifts, required electric weight is 96500C, and therefore every cubic metre of waste water can be processedCOD:1000*3600C/ (96500C/mol*4) * 32g/mol=298g), remove 10000The COD of mg/L, by 20% current efficiency, needs 167785Ah/m3Electric weight,Groove is pressed and only have 3V, need 503 degree electricity, cause energy expenditure higher.
The molten iron amount of electricity Fenton oxidation method is large: 1000Ah/m3Electric weight can produce in theory1.04 ‰ Fe2+, after follow-up Fenton's reaction, can produce the body refuse that approximately 2% moisture content is 90%,If supply with 3000Ah/m3Electric weight, can produce the body refuse that approximately 6% moisture content is 90%,This has significantly improved solid waste output, causes processing cost to rise suddenly and sharply.
Application number is that 201010181115.7 Chinese patent discloses a kind of polyphase electrocatalytic oxidationMethod and the reactor thereof of change-Fenton coupled method degrading nitrobenzene class waste water, have between electrodeApart from large (4-8cm), groove is pressed the shortcoming of high (20-40V), and granule electrode and solid are urgedAgent can continuous collision friction in the time of aeration, and chip runs off with waste water, therefore in electrolytic cell, needsTo constantly add new granule electrode and solid catalyst, increase the operation easier of actual motionAnd operating cost.
Summary of the invention
Object of the present invention is exactly the deficiency that will solve above-mentioned background technology, and a kind of energy consumption is providedThe method of the treatment of Nitrobenzene class waste water low, degradation efficiency is high, molten iron amount is few.
Technical scheme of the present invention is: a kind of method for the treatment of of Nitrobenzene class waste water, its featureBe, step is:
Be that 5000-30000mg/L waste water adds inorganic acid to carry out acid out by COD content; AcidWastewater supernatant fluid after analysing adds electrolyte to enter electrocatalysis high-grade oxidized groove electrolysis; Continue intoEnter electrolysis in Fenton groove and produce Fe2+, then enter in Fenton oxidation trough and add dioxygenWater generation Fenton's reaction; Add flocculant sedimentation, supernatant enters biochemical system processing.
Preferably, step is:
A. acid out
Add inorganic acid to regulate pH value of waste water to 1.5-2.5, leave standstill and get wastewater supernatant fluid for placeReason liquid;
B. electrocatalysis high-grade oxidized
In treatment fluid, add electrolyte, then enter anode be ti-supported lead dioxide electric, negative electrode be copper,Electrolysis 0.5-3h in the electrocatalysis high-grade oxidized groove of iron or stainless steel electrode;
C. Fenton electrolysis
Add inorganic acid to regulate the water outlet pH value of electrocatalysis high-grade oxidized groove to 2-3, at anodeBe electrolysis 0.5-3h in the Fenton groove of the ferroelectric utmost point with negative electrode and produce Fe2+
D.Fenton oxidation
The water outlet of Fenton groove enters Fenton oxidation trough, add hydrogen peroxide after air expose to the sunThere is Fenton's reaction in gas 30-90min;
E. flocculating setting
Water outlet pH value after use CaO adjusting aeration, to 6-9, adds flocculant, mixesQuiet heavy evenly, lower floor's mud enters sludge treating system processing, and supernatant enters department of biochemistrySystem is processed.
Further, in step a and step c, inorganic acid is in sulfuric acid, nitric acid, hydrochloric acidOne or more combination. The inorganic acid using in step a and step c can be identical or different.
Further, in step b, electrolyte is NaCl solid or the aqueous solution, adds electrolysisIn matter, containing NaCl quality is the 0.5-10 ‰ for the treatment of fluid quality.
Further, Fenton groove in electrocatalysis high-grade oxidized groove and step c in step bAll adopt the pulse power.
Further, in steps d hydrogen peroxide to add quality be the 1-10 ‰ for the treatment of fluid quality.
Further, in step e, flocculant is aluminium polychloride and polyacrylamide, polymerizationAluminium chloride add quality be treatment fluid quality for 0.1-1 ‰, polyacrylamide adds quality to beThe 0.01-0.1 ‰ for the treatment of fluid quality.
Further, in described electrocatalysis high-grade oxidized groove, electrode spacing is 2-3.5cm, instituteStating electrode spacing in Fenton groove is 2-3.5cm.
Further, the electricity that in described electrocatalysis high-grade oxidized groove, unit volume treatment fluid addsAmount is 3000-12000Ah/m3
Further, the electric weight that in described Fenton groove, unit volume treatment fluid adds is1000-3000Ah/m3
In the present invention, through acid out, (acid out is under acid condition waste water, in waste water, hasA little materials are converted into suspended state by solubilised state or colloidal attitude, and recycling precipitates it from solutionSeparate), can tentatively remove part COD. In electrocatalysis high-grade oxidized groove, titanium baseAnode of lead dioxide is because high oxygen separated position produces active OH (hydroxyl radical free radical), by portionDivide nitrobenzene to degrade, final mineralising is CO2And H2O. In Fenton groove, negative and positiveTwo-stage is Fe, the oxidized generation of anode Fe2+, general-NO on negative electrode2Be reduced into-NH2。In Fenton oxidation trough, owing to being contained in the Fe of Fenton groove generation in treatment fluid2+, and addThe hydrogen peroxide generation Fenton's reaction entering, produces and has the OH of strong oxidizing property, by nitrobenzene orIntermediate product aniline deoxidization, degradation.
Electrode spacing is 2-3.5cm, and electrode spacing is larger to energy consumption, and electrode spacing moreNarrow, between negative and positive two-plate, resistance is less, and power consumption is less; But the little meeting during to certain value of spacingMake the diffusion of negative and positive two-stage reaction product, affect follow-up electrolysis.
The pulse power can periodically be exported the direct current of short time, in the time that electric current turn-offs, and polar regionNear ion returns to again initial concentration, and concentration polarization is eliminated, and is conducive to next pulse weekPhase is continued electrolysis, also can prevent the passivation of electrode.
Beneficial effect of the present invention is:
1. adopt electrocatalysis high-grade oxidized technology, Fenton oxidizing process to combine, electricity is urgedChange oxidizing process by wastewater treatment modification, Fenton oxidizing process can be by molten iron amount greatly more afterwardsReduce H2O2Addition also can reduce, saved energy consumption and cost, green economy.
2. in Fenton groove, electrolysis is heavy to closing to Fenton's reaction in follow-up Fenton oxidation troughWant, Fenton reagent Fe is not only provided2+, also by nitrobenzene-NO2Be reduced into-NH2,·OHIntermediate product aniline is degraded more much easier than direct-reduction nitrobenzene, greatly improvedOrganic degradation rate.
3. each stage process division of labor is clear and definite, and electrochemical processing apparatus easily is automated, rightThe poisonous and harmful substance removal effects such as nitrobenzene are remarkable. The present invention is not only applicable to nitrobenzeneClass wastewater treatment, also can be applicable to the processing containing pollutant waste water such as nitrotoleune, aniline.
Brief description of the drawings
Fig. 1 is process chart of the present invention
Detailed description of the invention
Below in conjunction with the drawings and specific embodiments, the present invention is described in further detail.
Embodiment 1
The method of the present embodiment treatment of Nitrobenzene class waste water, step is:
A. acid out
Getting COD initial concentration is the waste water that 30000mg/L, nitrobenzene are 7mg/L,Add inorganic acid (sulfuric acid) to regulate pH value of waste water to 1.5-2.5 (preferably pH=1.5), quietPutting and getting wastewater supernatant fluid is treatment fluid, and the present embodiment treatment fluid is 500ml;
B. electrocatalysis high-grade oxidized
In treatment fluid, add electrolyte NaCl solid, add in NaCl solid and contain NaClQuality is 2 ‰ for the treatment of fluid quality; Enter electrocatalysis high-grade oxidized electrolytic cell, anode is titaniumBase lead dioxide electrode, negative electrode is copper electrode, electrode spacing is 2cm, electric current I=3A,Voltage U=4V, electrolysis time t=2h, the electric weight that unit volume waste water adds is12000Ah/m3, wherein electrocatalysis high-grade oxidized electrolytic cell proportion is that 5~5000Hz is straightThe stream pulse power;
C. Fenton electrolysis
Add inorganic acid (sulfuric acid) to regulate the water outlet pH value of electrocatalysis high-grade oxidized groove to 2-3(preferably pH=2), the water outlet of electrocatalysis high-grade oxidized groove enters the electrolysis of Fenton groove, electricityFenton groove anode and negative electrode are the ferroelectric utmost point, and electrode spacing is 3cm, electric current I=1A,Groove is pressed U=1V, electrolysis time t=1.5h, and the electric weight that unit volume waste water adds is3000Ah/m3,, wherein Fenton groove proportion is 5~5000Hz direct current pulse power source;
D.Fenton oxidation
The water outlet of Fenton groove, adds the hydrogen peroxide for the treatment of fluid quality 10 ‰, air aeration90min;
E. flocculating setting
PH is adjusted to 6-9 (preferably pH=6) with CaO, adds successively treatment fluid quality 0.1 ‰The polyacrylamide of aluminium polychloride, treatment fluid quality 0.01 ‰, it is rear quiet heavy to mix,Lower floor's mud enters sludge treating system processing, and supernatant can enter biochemical system, carries outBiochemical treatment.
After testing, the supernatant C OD concentration of the above-mentioned e of step is after treatment reduced to2900mg/L, clearance is 90%; Nitrobenzene fails to detect, and clearance approaches 100%.
Embodiment 2
The method of the present embodiment treatment of Nitrobenzene class waste water, step is:
A. acid out
Getting COD initial concentration is the waste water that 5000mg/L, nitrobenzene are 3mg/L,Add inorganic acid (hydrochloric acid) to regulate pH value of waste water to 1.5-2.5 (preferably pH=2.5), quietPutting and getting wastewater supernatant fluid is treatment fluid, and the present embodiment treatment fluid is 500ml;
B. electrocatalysis high-grade oxidized
In treatment fluid, add the electrolyte NaCl aqueous solution, in the NaCl aqueous solution adding, containNaCl quality is 1 ‰ for the treatment of fluid quality; Enter electrocatalysis high-grade oxidized electrolytic cell, anodeFor ti-supported lead dioxide electric pole, negative electrode is stainless steel electrode, and electrode spacing is 3.5cm, electricityStream I=3A, voltage U=5V, electrolysis time t=0.5h, unit volume waste water addsElectric weight is 3000Ah/m3, wherein electrocatalysis high-grade oxidized electrolytic cell proportion be 5~5000Hz direct current pulse power source;
C. Fenton electrolysis
Add inorganic acid (hydrochloric acid) to regulate the water outlet pH value of electrocatalysis high-grade oxidized groove to 2-3(preferably pH=3), the water outlet of electrocatalysis high-grade oxidized groove enters the electrolysis of Fenton groove, sunThe utmost point and negative electrode are the ferroelectric utmost point, and electrode spacing is 2cm, electric current I=1A, and groove is pressed U=0.7V,Electrolysis time t=0.5h, the electric weight that unit volume waste water adds is 1000Ah/m3,, whereinFenton groove proportion is 5~5000Hz direct current pulse power source;
D.Fenton oxidation
The water outlet of Fenton groove, adds the hydrogen peroxide for the treatment of fluid quality 1 ‰, air aeration 90min;
E. flocculating setting
PH is adjusted to 6-9 (preferably pH=9) with CaO, adds successively treatment fluid quality 1 ‰The polyacrylamide of aluminium polychloride, treatment fluid quality 0.1 ‰, it is rear quiet heavy to mix,Lower floor's mud enters sludge treating system processing, and supernatant can enter biochemical system, carries outBiochemical treatment.
After testing, the supernatant C OD concentration of the above-mentioned e of step is after treatment reduced to2100mg/L, clearance is 58%; Nitrobenzene fails to detect, and clearance approaches 100%.
Embodiment 3
The method of the present embodiment treatment of Nitrobenzene class waste water, step is:
A. acid out
Getting COD initial concentration is the waste water that 10000mg/L, nitrobenzene are 5mg/L,Add inorganic acid (nitric acid) to regulate pH value of waste water to 1.5-2.5 (preferably pH=2), leave standstillGetting wastewater supernatant fluid is treatment fluid, and the present embodiment treatment fluid is 500ml;
B. electrocatalysis high-grade oxidized
In treatment fluid, add electrolyte NaCl solid, add in NaCl solid and contain NaClQuality is 1 ‰ for the treatment of fluid quality; Enter electrocatalysis high-grade oxidized electrolytic cell, anode is titaniumBase lead dioxide electrode, negative electrode is the ferroelectric utmost point, electrode spacing is 3cm, electric current I=3A,Voltage U=4.5V, electrolysis time t=1h, the electric weight that unit volume waste water adds is6000Ah/m3, wherein electrocatalysis high-grade oxidized electrolytic cell proportion is that 5~5000Hz is straightThe stream pulse power;
C. Fenton electrolysis
Add inorganic acid (nitric acid) to regulate the water outlet pH value of electrocatalysis high-grade oxidized groove to 2-3(preferably pH=2.5), the water outlet of electrocatalysis high-grade oxidized groove enters the electrolysis of Fenton groove,Fenton groove anode and negative electrode are the ferroelectric utmost point, and electrode spacing is 3cm, electric current I=1A,Groove is pressed U=0.9V, electrolysis time t=1h, and the electric weight that unit volume waste water adds is2000Ah/m3,, wherein Fenton groove proportion is 5~5000Hz direct current pulse power source;
D.Fenton oxidation
The water outlet of Fenton groove, adds the hydrogen peroxide for the treatment of fluid quality 5 ‰, air aeration 30min;
E. flocculating setting
PH is adjusted to 6-9 (preferably pH=8.5) with CaO, adds successively treatment fluid qualityThe polyacrylamide of 0.5 ‰ aluminium polychlorides, treatment fluid quality 0.05 ‰, mixes rear quietHeavy, lower floor's mud enters sludge treating system processing, and supernatant can enter biochemical system,Carry out biochemical treatment.
After testing, the supernatant C OD concentration of the above-mentioned e of step is after treatment reduced to2700mg/L, clearance is 73%; Nitrobenzene fails to detect, and clearance approaches 100%.
Embodiment 4
The method of the present embodiment treatment of Nitrobenzene class waste water, step is:
A. acid out
Getting COD initial concentration is the waste water that 15000mg/L, nitrobenzene are 10mg/L,Add inorganic acid (sulfuric acid and mixed in hydrochloric acid that mol ratio is 1:1 form) to regulate wastewater pHBe worth to 1.5-2.5 (preferably 1.5), leaving standstill and getting wastewater supernatant fluid is treatment fluid, the present embodiment placeReason liquid is 500ml;
B. electrocatalysis high-grade oxidized
In treatment fluid, add the electrolyte NaCl aqueous solution, in the NaCl aqueous solution adding, containNaCl quality is 0.5 ‰ for the treatment of fluid quality; Enter electrocatalysis high-grade oxidized electrolytic cell, sunVery ti-supported lead dioxide electric pole, negative electrode is copper electrode, electrode spacing is 2cm, electric currentI=12A, voltage U=16V, electrolysis time t=0.5h, the electricity that unit volume waste water addsAmount is 12000Ah/m3, wherein electrocatalysis high-grade oxidized electrolytic cell proportion be 5~5000Hz direct current pulse power source;
C. Fenton electrolysis
Add inorganic acid (sulfuric acid and mixed in hydrochloric acid that mol ratio is 1:1 form) to regulate electricity to urgeChange the water outlet pH value of advanced oxidation groove to 2-3 (preferably pH=2), electrocatalysis high-grade oxidized grooveWater outlet enter the electrolysis of Fenton groove, Fenton groove anode and negative electrode are the ferroelectric utmost point,Electrode spacing is 3.5cm, electric current I=3A, and groove is pressed U=3.6V, electrolysis time t=0.5h,Be that the electric weight that unit volume waste water adds is 3000Ah/m3,, wherein Fenton groove adopts frequentlyRate is 5~5000Hz direct current pulse power source;
D.Fenton oxidation
The water outlet of Fenton groove, adds the hydrogen peroxide for the treatment of fluid quality 10 ‰, air aeration60min;
E. flocculating setting
PH is adjusted to 6-9 (preferably pH=7) with CaO, adds successively treatment fluid quality 0.1 ‰The polyacrylamide of aluminium polychloride, treatment fluid quality 0.01 ‰, it is rear quiet heavy to mix,Lower floor's mud enters sludge treating system processing, and supernatant can enter biochemical system, carries outBiochemical treatment.
After testing, the supernatant C OD concentration of the above-mentioned e of step is after treatment reduced to2500mg/L, clearance is 83%; Nitrobenzene fails to detect, and clearance approaches 100%.
Embodiment 5
The method of the present embodiment treatment of Nitrobenzene class waste water, step is:
A. acid out
Getting COD initial concentration is the waste water that 20000mg/L, nitrobenzene are 12mg/L,Add inorganic acid (sulfuric acid and nitric acid that mol ratio is 1:1 mix) to regulate wastewater pHBe worth to 1.5-2.5 (preferably pH=2.5), leaving standstill and getting wastewater supernatant fluid is treatment fluid, this enforcementExample treatment fluid is 500ml;
B. electrocatalysis high-grade oxidized
In treatment fluid, add electrolyte NaCl solid, add in NaCl solid and contain NaClQuality is 5 ‰ for the treatment of fluid quality; Enter electrocatalysis high-grade oxidized electrolytic cell, anode is titaniumBase lead dioxide electrode, negative electrode is stainless steel electrode, electrode spacing is 3.5cm, electric currentI=3A, voltage U=5V, electrolysis time t=1.5h, the electric weight that unit volume waste water addsFor 9000Ah/m3, wherein electrocatalysis high-grade oxidized electrolytic cell proportion is 5~5000HzDirect current pulse power source;
C. Fenton electrolysis
Add inorganic acid (nitric acid) to regulate the water outlet pH value of electrocatalysis high-grade oxidized groove to 2-3(preferably pH=3), the water outlet of electrocatalysis high-grade oxidized groove enters the electrolysis of Fenton groove, electricityFenton groove anode and negative electrode are the ferroelectric utmost point, and electrode spacing is 2.5cm, electric current I=0.25A,Groove is pressed U=0.2V, electrolysis time t=2h, and the electric weight that unit volume waste water adds is1000Ah/m3,, wherein Fenton groove proportion is 5~5000Hz direct current pulse power source;
D.Fenton oxidation
The water outlet of Fenton groove, adds the hydrogen peroxide for the treatment of fluid quality 1 ‰, air aeration 90min;
E. flocculating setting
PH is adjusted to 6-9 (preferably pH=8) with CaO, adds successively treatment fluid quality 1 ‰The polyacrylamide of aluminium polychloride, treatment fluid quality 0.1 ‰, it is rear quiet heavy to mix,Lower floor's mud enters sludge treating system processing, and supernatant can enter biochemical system, carries outBiochemical treatment.
After testing, the supernatant C OD concentration of the above-mentioned e of step after treatment reduces to 3000Mg/L, clearance is 85%; Nitrobenzene fails to detect, and clearance approaches 100%.
Embodiment 6
The method of the present embodiment treatment of Nitrobenzene class waste water, step is:
A. acid out
Getting COD initial concentration is the waste water that 25000mg/L, nitrobenzene are 8mg/L,Add inorganic acid (nitric acid and mixed in hydrochloric acid that mol ratio is 1:1 form) to regulate wastewater pHBe worth to 1.5-2.5 (preferably pH=2), leaving standstill and getting wastewater supernatant fluid is treatment fluid, the present embodimentTreatment fluid is 500ml;
B. electrocatalysis high-grade oxidized
In treatment fluid, add the electrolyte NaCl aqueous solution, in the NaCl aqueous solution adding, containNaCl quality is 8 ‰ for the treatment of fluid quality; Enter electrocatalysis high-grade oxidized electrolytic cell, anodeFor ti-supported lead dioxide electric pole, negative electrode is the ferroelectric utmost point, and electrode spacing is 3cm, electric current I=2A,Voltage U=3V, electrolysis time t=2.5h, the electric weight that unit volume waste water adds is10000Ah/m3, wherein electrocatalysis high-grade oxidized electrolytic cell proportion is that 5~5000Hz is straightThe stream pulse power;
C. Fenton electrolysis
Add inorganic acid (hydrochloric acid) to regulate the water outlet pH value of electrocatalysis high-grade oxidized groove to 2-3(preferably pH=2.5), the water outlet of electrocatalysis high-grade oxidized groove enters the electrolysis of Fenton groove,Fenton groove anode and negative electrode are the ferroelectric utmost point, and electrode spacing is 2cm, electric current I=0.4A,Groove is pressed U=0.3V, electrolysis time t=2.5h, and the electric weight that unit volume waste water adds is2000Ah/m3,, wherein Fenton groove proportion is 5~5000Hz direct current pulse power source;
D.Fenton oxidation
The water outlet of Fenton groove, adds the hydrogen peroxide for the treatment of fluid quality 5 ‰, air aeration 30min;
E. flocculating setting
PH is adjusted to 6-9 (preferably pH=9) with CaO, adds successively treatment fluid quality 0.8 ‰The polyacrylamide of aluminium polychloride, treatment fluid quality 0.06 ‰, it is rear quiet heavy to mix,Lower floor's mud enters sludge treating system processing, and supernatant can enter biochemical system, carries outBiochemical treatment.
After testing, the supernatant C OD concentration of the above-mentioned e of step is after treatment reduced to2000mg/L, clearance is 92%; Nitrobenzene fails to detect, and clearance approaches 100%.
Embodiment 7
The method of the present embodiment treatment of Nitrobenzene class waste water, step is:
A. acid out
Getting COD initial concentration is the waste water that 30000mg/L, nitrobenzene are 6mg/L,Add inorganic acid (sulfuric acid, hydrochloric acid and nitric acid that mol ratio is 1:1:1 mix) to regulatePH value of waste water is to 1.5-2.5 (preferably pH=1.8), and leaving standstill and getting wastewater supernatant fluid is treatment fluid,The present embodiment treatment fluid is 500ml;
B. electrocatalysis high-grade oxidized
In treatment fluid, add electrolyte NaCl solid, add in NaCl solid and contain NaClQuality is 10 ‰ for the treatment of fluid quality; Enter electrocatalysis high-grade oxidized electrolytic cell, anode is titaniumBase lead dioxide electrode, negative electrode is copper electrode, electrode spacing is 2.5cm, electric current I=1.5A,Voltage U=2V, electrolysis time t=1h, the electric weight that unit volume waste water adds is3000Ah/m3, wherein electrocatalysis high-grade oxidized electrolytic cell proportion is that 5~5000Hz is straightThe stream pulse power;
C. Fenton electrolysis
Add inorganic acid (sulfuric acid) to regulate the water outlet pH value of electrocatalysis high-grade oxidized groove to 2-3(preferably pH=2.4), the water outlet of electrocatalysis high-grade oxidized groove enters the electrolysis of Fenton groove,Fenton groove anode and negative electrode are the ferroelectric utmost point, and electrode spacing is 2.4cm, electric currentI=0.25A, groove is pressed U=0.25V, electrolysis time t=3h, unit volume waste water addsElectric weight is 1500Ah/m3,, wherein Fenton groove proportion is 5~5000Hz direct currentThe pulse power;
D.Fenton oxidation
The water outlet of Fenton groove, adds the hydrogen peroxide for the treatment of fluid quality 4 ‰, air aeration 50min;
E. flocculating setting
PH is adjusted to 6-9 (preferably pH=6) with CaO, adds successively treatment fluid quality 0.4 ‰The polyacrylamide of aluminium polychloride, treatment fluid quality 0.08 ‰, it is rear quiet heavy to mix,Lower floor's mud enters sludge treating system processing, and supernatant can enter biochemical system, carries outBiochemical treatment.
After testing, the supernatant C OD concentration of the above-mentioned e of step is after treatment reduced to1800mg/L, clearance is 94%; Nitrobenzene fails to detect, and clearance approaches 100%.
Embodiment 8
The method of the present embodiment treatment of Nitrobenzene class waste water, step is:
A. acid out
Getting COD initial concentration is the waste water that 5000mg/L, nitrobenzene are 5mg/L,Add inorganic acid (sulfuric acid) to regulate pH value of waste water to 1.5-2.5 (preferably 2.4), leave standstill and getWastewater supernatant fluid is treatment fluid, and the present embodiment treatment fluid is 500ml;
B. electrocatalysis high-grade oxidized
In treatment fluid, add the electrolyte NaCl aqueous solution, in the NaCl aqueous solution adding, containNaCl quality is 10 ‰ for the treatment of fluid quality; Enter electrocatalysis high-grade oxidized electrolytic cell, sunVery ti-supported lead dioxide electric pole, negative electrode is copper electrode, electrode spacing is 3.2cm, electric currentI=1A, voltage U=1.5V, electrolysis time t=3h, the electric weight that unit volume waste water addsFor 6000Ah/m3, wherein electrocatalysis high-grade oxidized electrolytic cell proportion is 5~5000HzDirect current pulse power source;
C. Fenton electrolysis
Add inorganic acid (sulfuric acid) to regulate the water outlet pH value of electrocatalysis high-grade oxidized groove to 2-3(preferably pH=2.8), the water outlet of electrocatalysis high-grade oxidized groove enters the electrolysis of Fenton groove,Fenton groove anode and negative electrode are the ferroelectric utmost point, and electrode spacing is 3.2cm, electric currentI=0.5A, groove is pressed U=0.6V, electrolysis time t=2.5h, unit volume waste water addsElectric weight is 2500Ah/m3, wherein Fenton groove proportion is 5~5000Hz direct current arteries and veinsRush power supply;
D.Fenton oxidation
The water outlet of Fenton groove, adds the hydrogen peroxide for the treatment of fluid quality 8 ‰, air aeration 80min;
E. flocculating setting
PH is adjusted to 6-9 (preferably pH=8) with CaO, adds successively treatment fluid quality 0.5 ‰The polyacrylamide of aluminium polychloride, treatment fluid quality 0.04 ‰, it is rear quiet heavy to mix,Lower floor's mud enters sludge treating system processing, and supernatant can enter biochemical system, carries outBiochemical treatment.
After testing, the supernatant C OD concentration of the above-mentioned e of step is after treatment reduced to 500mg/L,Clearance is 90%; Nitrobenzene fails to detect, and clearance approaches 100%.

Claims (10)

1. a method for treatment of Nitrobenzene class waste water, is characterized in that, step is:
Be that 5000-30000mg/L waste water adds inorganic acid to carry out acid out by COD content; AcidWastewater supernatant fluid after analysing adds electrolyte to enter electrocatalysis high-grade oxidized groove electrolysis; Continue intoEnter electrolysis in Fenton groove and produce Fe2+, then enter in Fenton oxidation trough and add dioxygenWater generation Fenton's reaction; Add flocculant sedimentation, supernatant enters biochemical system processing.
2. the method for the treatment of of Nitrobenzene class waste water as claimed in claim 1, is characterized in that,Step is:
A. acid out
Add inorganic acid to regulate pH value of waste water to 1.5-2.5, leave standstill and get wastewater supernatant fluid for placeReason liquid;
B. electrocatalysis high-grade oxidized
Treatment fluid adds electrolyte, then to enter anode be that ti-supported lead dioxide electric pole, negative electrode areElectrolysis 0.5-3h in the electrocatalysis high-grade oxidized groove of copper, iron or stainless steel electrode;
C. Fenton electrolysis
Add inorganic acid to regulate the water outlet pH value of electrocatalysis high-grade oxidized groove to 2-3, at anodeBe electrolysis 0.5-3h in the Fenton groove of the ferroelectric utmost point with negative electrode and produce Fe2+
D.Fenton oxidation
The water outlet of Fenton groove enters Fenton oxidation trough, add hydrogen peroxide after air expose to the sunThere is Fenton's reaction in gas 30-90min;
E. flocculating setting
Water outlet pH value after use CaO adjusting aeration, to 6-9, adds flocculant, mixesQuiet heavy evenly, lower floor's mud enters sludge treating system processing, and supernatant enters department of biochemistrySystem is processed.
3. method as claimed in claim 2, is characterized in that, in step a and step cInorganic acid is the one or more combination in sulfuric acid, nitric acid, hydrochloric acid.
4. method as claimed in claim 2, is characterized in that, in step b, electrolyte isNaCl solid or the NaCl aqueous solution, adding and containing NaCl quality in electrolyte is treatment fluidThe 0.5-10 ‰ of quality.
5. method as claimed in claim 2, is characterized in that, in step b, electro-catalysis is highIn level oxidation trough and step c, Fenton groove all adopts the pulse power.
6. method as claimed in claim 2, is characterized in that, in steps d, hydrogen peroxide addsEntering quality is the 1-10 ‰ for the treatment of fluid quality.
7. method as claimed in claim 2, is characterized in that, in step e, flocculant isAluminium polychloride and polyacrylamide, it is treatment fluid quality that aluminium polychloride adds quality0.1-1 ‰, it is the 0.01-0.1 ‰ for the treatment of fluid quality that polyacrylamide adds quality.
8. method as claimed in claim 2, is characterized in that, the senior oxygen of described electro-catalysisChanging electrode spacing in groove is 2-3.5cm, and in described Fenton groove, electrode spacing is 2-3.5cm.
9. method as claimed in claim 2, is characterized in that, the senior oxygen of described electro-catalysisChanging the electric weight that in groove, unit volume treatment fluid adds is 3000-12000Ah/m3
10. method as claimed in claim 2, is characterized in that, described Fenton grooveThe electric weight that interior unit volume treatment fluid adds is 1000-3000Ah/m3
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CN108862753A (en) * 2018-07-11 2018-11-23 湖北东方化工有限公司 The method of nitrobenzene wastewater electrochemistry advanced treating
CN109020070A (en) * 2018-08-23 2018-12-18 广东海瑞环保科技有限公司 The processing method of anti-oxidant agent production waste water
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CN109626726A (en) * 2018-12-20 2019-04-16 浙江迪邦化工有限公司 A kind of processing method of benzene-containing wastewater
CN109856301A (en) * 2019-01-09 2019-06-07 中北大学 A kind of method of gas chromatography-mass spectrography measurement nitrobenzene degradation process intermediate product
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