CN109467265A - A kind of method of electricity Fenton-biological treatment collaboration Phenol-Containing Wastewater Treatment - Google Patents

A kind of method of electricity Fenton-biological treatment collaboration Phenol-Containing Wastewater Treatment Download PDF

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CN109467265A
CN109467265A CN201811416474.9A CN201811416474A CN109467265A CN 109467265 A CN109467265 A CN 109467265A CN 201811416474 A CN201811416474 A CN 201811416474A CN 109467265 A CN109467265 A CN 109467265A
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waste water
beaker
phenol
biological treatment
fenton
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陈世良
谢文杰
廖芳群
周杰
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Qianjiang College of Hangzhou Normal University
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Qianjiang College of Hangzhou Normal University
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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
    • C02F9/00—Multistage treatment of water, waste water or sewage
    • 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
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/46104—Devices therefor; Their operating or servicing
    • C02F1/46109—Electrodes
    • 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
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
    • 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
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/46104—Devices therefor; Their operating or servicing
    • C02F1/46109—Electrodes
    • C02F2001/46133—Electrodes characterised by the material
    • 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
    • C02F3/00—Biological treatment of water, waste water, or sewage
    • C02F3/30—Aerobic and anaerobic processes

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Water Treatment By Electricity Or Magnetism (AREA)

Abstract

The invention discloses a kind of electric Fenton-biodegrade collaboration Phenol-Containing Wastewater Treatment methods.Traditional Phenol-Containing Wastewater Treatment technique is extremely difficult to ideal effect, although some effects are obvious, there may be some other problems such as secondary pollution and energy consumption height.The present invention is as follows: one, phenol wastewater being delivered to waste water reaction container by noncorrosive pump, and adjust pH value and electrolyte concentration.Two, electro-Fenton reaction device is built in waste water reaction container and is reacted.Three, the pH value for adjusting waste water in waste water reaction container to neutrality and filters.Four, filtrate obtained by step 3 is passed through anaerobic reactor.Five, the resulting biological treatment waste water of step 4 is passed through aerobic reactor.Six, the second biological treatment waste water obtained by step 5 is flowed into sedimentation basin, after being precipitated, being filtered, resulting filtrate is outer draining.The present invention organically combines electric Fenton and biological treatment processing method, substantially increases the biodegradability and subsequent biological treatment treatment effeciency of waste water.

Description

A kind of method of electricity Fenton-biological treatment collaboration Phenol-Containing Wastewater Treatment
Technical field
The invention belongs to technical field of sewage, and in particular to a kind of electricity Fenton-biological treatment collaboration processing is useless containing phenol The method of water.
Background technique
Phenol wastewater is as industries raw material and the intermediates such as papermaking, coking, oil refining, plastics, pesticide, medicine synthesis, pollution Range is wide, harmfulness is big, can accumulate and shift in water body, constitute great threat to environment.Not with modern industry Disconnected development, phenol wastewater becomes one of the important pollution sources of human production life, therefore must be located before phenol wastewater discharge Reason, otherwise can cause serious harm to ecological environment and human body.Traditional Phenol-Containing Wastewater Treatment technique is (such as: absorption method, solvent Extraction, membrane separation process etc.) it is extremely difficult to ideal effect, although some effects are obvious, there may be secondary dirts Some other problems such as dye and energy consumption height.Therefore find low energy consumption, efficiently, the method Phenol-Containing Wastewater Treatment that does not generate secondary pollution it is outstanding It is important.
Summary of the invention
The purpose of the present invention is to provide a kind of electric Fenton-biological treatment collaboration Phenol-Containing Wastewater Treatment methods.
The present invention is specific as follows:
Step 1: phenol wastewater is delivered to waste water reaction container by noncorrosive pump, and acid and electrolyte is added, adjusts pH Being worth range is 1~5, adjusts electrolyte concentration range in 0.05~0.5mol/L.
Step 2: building electro-Fenton reaction device in waste water reaction container.The cathode material of electro-Fenton reaction device is adopted With carbon nanotube/activated carbon fiber felt composite material or carbon nanotube/graphite felt composite material.In the yin of electro-Fenton reaction device Aerator is installed at pole.Later, electro-Fenton reaction device is passed through the direct current that voltage is 0.5~3V；Aerator is to waste water Reaction vessel is passed through air；The flow velocity of the be passed through air of aerator is 1~20m3/ h, the energization period of electro-Fenton reaction device For 0.5~4h.
Step 3: electro-Fenton reaction device powers off, aerator stops being passed through air to waste water reaction container；Later, to Alkali is added in waste water obtained by step 2, adjusts the pH value of waste water in waste water reaction container to neutrality；To in waste water reaction container Waste water is precipitated, is filtered, and filtrate is obtained.
Step 4: filtrate obtained by step 3 is passed through anaerobic reactor, and 6h~36h is stopped, obtains the first biological treatment Waste water.Adjusting pH value range in anaerobic reactor is 6~9, and dissolved oxygen range is 0~2mg/L.
Step 5: the resulting first biological treatment waste water of step 4 is passed through aerobic reactor, and 4h~36h is stopped, obtained To the second biological treatment waste water.Adjusting pH value range in aerobic reactor is 6~9, and dissolved oxygen range is 2~20mg/L.
Step 6: the second biological treatment waste water obtained by step 5 is flowed into sedimentation basin, it is resulting after being precipitated, being filtered Filtrate is outer draining.
Further, cathode material described in step 2 uses carbon nanotube/activated carbon fiber felt composite material.Carbon is received Mass percent of the mitron in cathode material is 1%~35%.Carbon nanotube/activated carbon fiber felt composite material passes through as follows Method is prepared:
(1) taking areal extent is that 2cm × 2cm~50cm × 50cm active carbon fiber felt is placed in the first dry beaker In.
(2) into the first beaker be added mass concentration range be 0.01%~1% carbon nano tube dispersion liquid 100mL~ Active carbon fiber felt is totally submerged by 2000mL.Adjust carbon nano tube dispersion liquid in the first beaker temperature range be 25 DEG C~ 60 DEG C, infiltrate 2h after, in the first beaker carbon nano tube dispersion liquid and active carbon fiber felt carry out ultrasonic disperse 30min~ 90min。
(3) active carbon fiber felt is taken out from the first beaker, be placed in the second dry beaker.Add into the second beaker Enter carbon nano tube dispersion liquid 100mL~2000mL that mass concentration range is 0.01%~1%, active carbon fiber felt is soaked completely Not yet.The temperature range for adjusting carbon nano tube dispersion liquid in the second beaker is 25 DEG C~60 DEG C, after infiltrating 2h, in the second beaker Carbon nano tube dispersion liquid and active carbon fiber felt carry out ultrasonic disperse 30min.
(4) active carbon fiber felt is taken out from the second beaker, is placed in 60 DEG C of vacuum environment and is dried, obtains carbon Nanotube/activated carbon fiber felt composite material.
Further, cathode material described in step 2 uses carbon nanotube/graphite felt composite material.Carbon nanotube exists Mass percent in cathode material is 1%~30%.Carbon nanotube/graphite felt composite material is prepared via a method which It arrives:
(1) taking areal extent is that 2cm × 2cm~50cm × 50cm graphite felt is placed in the first dry beaker.
(2) into the first beaker be added mass concentration range be 0.01%~1% carbon nano tube dispersion liquid 100mL~ Graphite felt is totally submerged by 2000mL.The temperature range for adjusting carbon nano tube dispersion liquid in the first beaker is 25 DEG C~60 DEG C, leaching After moistening 2h, to the carbon nano tube dispersion liquid and graphite felt progress ultrasonic disperse 30min~90min in the first beaker.
(3) graphite felt taken out from the first beaker is placed in pre-dry second beaker.Add into the second beaker Enter carbon nano tube dispersion liquid 100mL~2000mL that mass concentration range is 0.01%~1%, graphite felt is totally submerged.It adjusts The temperature range for saving carbon nano tube dispersion liquid in the second beaker is 25 DEG C~60 DEG C, after heat preservation infiltration 2h, in the second beaker Carbon nano tube dispersion liquid and graphite felt carry out ultrasonic disperse 30min.
(4) graphite felt is taken out from the second beaker, is placed in 60 DEG C of vacuum environment and is dried, obtain carbon nanometer Pipe/graphite felt composite material.
Further, carbon nanotube described in step 2 is single-walled carbon nanotube or multi-walled carbon nanotube.Outside carbon nanotube Diameter range is 5~20nm, and length range is 10~100 μm.The active carbon fiber felt or graphite felt with a thickness of 3~ 15mm。
Further, the anaerobic reactor uses the high-efficient contact composite anaerobic equipped with electron temperature-control system to react Device.Temperature range in anaerobic reactor is adjusted to 15 DEG C~60 DEG C.The aerobic reactor is used equipped with electron temperature-control The interior circulating biological of system contacts aerobic reactor；Temperature range in aerobic reactor is 15 DEG C~60 DEG C.
Further, the anode material of electro-Fenton reaction device described in step 2 uses stainless steel plate.The area of anode with The area equation of cathode.In electro-Fenton reaction device, cathode face parallel with anode is placed, and spacing is 1~20cm.
Further, the phenol contained in phenol wastewater described in step 1 be phenol, o-cresol, m-cresol, to first One of phenol is a variety of.
Further, acid described in step 1 uses sulfuric acid, and nitric acid or sulfuric acid, nitric acid are arbitrarily than mixing resulting mixing Acid.Electrolyte is sodium sulphate, sodium nitrate, potassium sulfate or potassium nitrate.
Further, alkali described in step 3 uses the oxide or hydroxide of potassium, calcium, sodium.
Further, aerator is installed in aerobic reactor described in step 5.
The invention has the advantages that:
1, the present invention organically combines electric Fenton and biological treatment processing method, is carried out by electric Fenton technology to phenols wastewater Pretreatment, effectively reduces the COD value of waste water, greatly increases the biodegradability and subsequent biological treatment processing effect of waste water Rate.
2, the cathode and anode material that electric Fenton-like system of the invention uses can generate H respectively2O2、Fe2+, the two combine formed The OH (hydroxyl radical free radical) of high reaction activity.And OH can capture the organic matter in waste water and decompose its efficient oxidation.
3, the cathode material that electric Fenton-like system of the invention uses is carbon nanotube/activated carbon fiber felt composite material or carbon Nanotube/graphite felt composite material, non-toxic, chemical stability, electric conductivity and corrosion resistance are good, while can promote O2It is quick Absorption, reduction and H2O2Generation.Compared to conventional cathode material or undoped with the active carbon fiber felt or graphite of carbon nanotube Felt, carbon nanotube/activated carbon fiber felt composite material used in the present invention or carbon nanotube/graphite felt composite material can be more Quickly and efficiently form H2O2.Therefore, the present invention has more preferably phenol wastewater removal efficiency.
4, the present invention carries out biochemical reaction in such a way that anaerobism, aerobic two kinds of reactors are used in combination, and in reactor It is equipped with electron temperature-control system, substantially increases bacterial activity and waste water treatment efficiency.
5, processing technique of the present invention is reliable, and required occupied area is small, and operation is simple, and the operating cost of system is low.
Specific embodiment
The invention will be further described below.
Specific step is as follows for a kind of method of electricity Fenton-biological treatment collaboration Phenol-Containing Wastewater Treatment:
Step 1: phenol wastewater is delivered to waste water reaction container by noncorrosive pump, and acid and electrolyte is added, adjusts pH Being worth range is 1~5, adjusts electrolyte concentration range in 0.05~0.5mol/L.Acid uses sulfuric acid, and nitric acid or sulfuric acid, nitric acid are appointed Meaning is than mixing resulting mixed acid.Electrolyte is sodium sulphate, sodium nitrate, potassium sulfate or potassium nitrate.
Step 2: building electro-Fenton reaction device in waste water reaction container.In electro-Fenton reaction device, the area of anode With the area equation of cathode, parallel face is placed, and spacing is 1~20cm.The anode material of electro-Fenton reaction device is not using Become rusty steel plate, and cathode material uses carbon nanotube/activated carbon fiber felt composite material or carbon nanotube/graphite felt composite material.Yin Carbon nanotube used in the material of pole is single-walled carbon nanotube or multi-walled carbon nanotube.Carbon nanotube external diametrical extent is 5~20nm, Length range is 10~100 μm.The active carbon fiber felt or graphite felt with a thickness of 3~15mm.
Aerator is installed at the cathode of electro-Fenton reaction device.Later, it is 0.5 that electro-Fenton reaction device, which is passed through voltage, The direct current of~3V；Aerator is passed through air to waste water reaction container；The flow velocity of the be passed through air of aerator be 1~ 20m3/h.0.5~4h is reacted at room temperature.
Step 3: electro-Fenton reaction device powers off, aerator stops being passed through air to waste water reaction container；Later, to Alkali is added in waste water obtained by step 2, adjusts the pH value of waste water in waste water reaction container to neutrality；It is anti-to waste water at room temperature It answers waste water in container to be precipitated, filtered, obtains filtrate.Alkali uses the oxide or hydroxide of potassium, calcium, sodium.
Step 4: filtrate obtained by step 3 is passed through anaerobic reactor, and 6h~36h is stopped, obtains the first biological treatment Waste water.Adjusting temperature range in anaerobic reactor is 15 DEG C~60 DEG C, and pH value range is 6~9, and dissolved oxygen range is 0~2mg/ L.Anaerobic reactor uses the high-efficient contact hybrid anaerobic reactor equipped with electron temperature-control system.
Step 5: the resulting first biological treatment waste water of step 4 is passed through aerobic reactor, and 4h~36h is stopped, obtained To the second biological treatment waste water.Adjusting temperature range in aerobic reactor is 15 DEG C~60 DEG C, and dissolved oxygen range is 2~20mg/ L, pH value range are 6~9.Aerobic reactor uses the interior circulating biological equipped with electron temperature-control system to contact aerobic reactor
Step 6: the second biological treatment waste water obtained by step 5 is flowed into sedimentation basin, it is resulting after being precipitated, being filtered Filtrate is the outer draining for meeting emission request.
Case study on implementation
Embodiment 1
The phenol wastewater being added in step 1 into waste water reaction container contains only a kind of pollutant of phenol, volume 500mL, Initial COD value is 20000mg/L.The acid being added in step 1 is sulfuric acid, and adjusting phenol wastewater pH value is 3.It is added in step 1 Electrolyte be sodium sulphate, additional amount 15g.
The electro-Fenton reaction device built in step 2 uses carbon nanotube/activated carbon fiber felt composite material as yin Pole material, uses stainless steel plate as anode material；The area of cathode is 5cm × 5cm, with a thickness of 10mm；The area of anode is 5cm × 5cm, with a thickness of 10mm.The DC voltage that electro-Fenton reaction device is passed through is 1.5V.Aerator is passed through the stream of air Speed is 5m3/h.A length of 2h when reaction at room temperature.
Mass percent of the carbon nanotube in cathode material is 1%~35%.Carbon nanotube/active carbon fiber felt is compound Material by active carbon fiber felt doped carbon nanometer pipe be prepared, specific preparation process are as follows:
(1) taking and being cut into areal extent in advance is that 2cm × 2cm~50cm × 50cm active carbon fiber felt is placed in and is pre-dried The first beaker in.
(2) into the first beaker be added mass concentration range be 0.01%~1% carbon nano tube dispersion liquid 100mL~ Active carbon fiber felt is totally submerged by 2000mL.Adjust carbon nano tube dispersion liquid in the first beaker temperature range be 25 DEG C~ 60 DEG C, infiltrate 2h after, in the first beaker carbon nano tube dispersion liquid and active carbon fiber felt carry out ultrasonic disperse 30min~ 90min。
(3) treated active carbon fiber felt is taken out from the first beaker, is placed in pre-dry second beaker.To Carbon nano tube dispersion liquid 100mL~2000mL that mass concentration range is 0.01%~1% is added in second beaker, by activated carbon Fibrofelt is totally submerged.The temperature range for adjusting carbon nano tube dispersion liquid in the second beaker is 25 DEG C~60 DEG C, right after infiltrating 2h Carbon nano tube dispersion liquid and active carbon fiber felt in second beaker carry out ultrasonic disperse 30min.
(4) active carbon fiber felt is taken out from the second beaker, is placed in 60 DEG C of vacuum environment and is dried, obtains carbon Nanotube/activated carbon fiber felt composite material.
It is sodium hydroxide that alkali is added in step 3, adjusts pH to 7.
The range of reaction temperature of anaerobic reactor is 35 DEG C in step 4, pH value 7, and the residence time is for 24 hours that dissolved oxygen is 0.5mg/L。
The range of reaction temperature of aerobic reactor is 35 DEG C in step 5, pH value 7, and the residence time is for 24 hours that dissolved oxygen is 4mg/L。
After step 1 to six processing, the COD value drained outside gained is down to 16mg/L, meets the discharge mark of national regulation It is quasi-.
In the case where keeping other reaction conditions constant, using the active carbon fiber felt undoped with carbon nanotube as yin Pole material, the outer COD value drained of step 6 gained drop to 127mg/L.It can be seen that using carbon nanotube/activated carbon fiber Felt composite material has more preferably treatment effect to phenol wastewater as the cathode material of electric Fenton processing.
Embodiment 2
The phenol wastewater being added in step 1 into waste water reaction container contains only a kind of pollutant of o-cresol, and volume is 500mL, initial COD value are 12000mg/L.The acid being added in step 1 is sulfuric acid, and adjusting phenol wastewater pH value is 2.5.Step The electrolyte being added in one is sodium sulphate, additional amount 15g.
The electro-Fenton reaction device built in step 2 uses carbon nanotube/activated carbon fiber felt composite material as yin Pole material uses stainless steel plate as anode material, and the area of cathode is 5cm × 5cm, and with a thickness of 5mm, the area of anode is 5cm × 5cm, with a thickness of 5mm.The DC voltage that electro-Fenton reaction device is passed through is 1.5V.Aerator is passed through the stream of air Speed is 5m3/h.A length of 2h when reaction at room temperature.Mass percent of the carbon nanotube in cathode material is 1%~35%. Carbon nanotube/activated carbon fiber felt composite material preparation method is in the same manner as in Example 1.
It is sodium hydroxide that alkali is added in step 3, adjusts pH to 7.
The range of reaction temperature of anaerobic reactor is 35 DEG C in step 4, pH value 6.5, residence time 12h, dissolved oxygen For 0.5mg/L.
The range of reaction temperature of aerobic reactor is 35 DEG C in step 5, pH value 6.5, residence time 12h, dissolved oxygen For 6mg/L.
After step 1 to six processing, the COD value drained outside gained is down to 15mg/L, meets the discharge mark of national regulation It is quasi-.
Keep other reaction conditions constant, the reaction temperature for adjusting anaerobic reactor and aerobic reactor is 15 DEG C, step The outer COD value drained of six gained drops to 82mg/L.As it can be seen that the selection of temperature has larger shadow to the treatment effect of phenol wastewater It rings.
Embodiment 3
The phenol wastewater being added in step 1 into waste water reaction container contains only a kind of pollutant of phenol, and volume is 3000mL, initial COD value are 30000mg/L.The acid being added in step 1 is sulfuric acid, and adjusting phenol wastewater pH value is 2.8.Step The electrolyte being added in one is sodium sulphate, additional amount 100g.
The electro-Fenton reaction device built in step 2 uses carbon nanotube/graphite felt composite material as cathode material, Use stainless steel plate as anode material, the area of cathode is 10cm × 10cm, with a thickness of 10mm, the area of anode be 10cm × 10cm, with a thickness of 10mm.The DC voltage that electro-Fenton reaction device is passed through is 1.5V.The flow velocity that aerator is passed through air is 8m3/h.A length of 3h when reaction at room temperature.
Mass percent of the carbon nanotube in cathode material is 1%~30%.Carbon nanotube/graphite felt composite material is logical It crosses the doped carbon nanometer pipe in graphite felt to be prepared, specific preparation process are as follows:
(1) taking and being cut into areal extent in advance is that 2cm × 2cm~50cm × 50cm graphite felt is placed in pre-dry first In beaker.
(2) into the first beaker be added mass concentration range be 0.01%~1% carbon nano tube dispersion liquid 100mL~ Graphite felt is totally submerged by 2000mL.The temperature range for adjusting carbon nano tube dispersion liquid in the first beaker is 25 DEG C~60 DEG C, leaching After moistening 2h, to the carbon nano tube dispersion liquid and graphite felt progress ultrasonic disperse 30min~90min in the first beaker.
(3) treated graphite felt is taken out from the first beaker, is placed in pre-dry second beaker.It is burnt to second Carbon nano tube dispersion liquid 100mL~2000mL that mass concentration range is 0.01%~1% is added in cup, graphite felt is soaked completely Not yet.The temperature range for adjusting carbon nano tube dispersion liquid in the second beaker is 25 DEG C~60 DEG C, after heat preservation infiltration 2h, to the second beaker Interior carbon nano tube dispersion liquid and graphite felt carry out ultrasonic disperse 30min.
(4) graphite felt is taken out from the second beaker, is placed in 60 DEG C of vacuum environment and is dried, obtain carbon nanometer Pipe/graphite felt composite material.
It is sodium hydroxide that alkali is added in step 3, adjusts pH to 7.
The range of reaction temperature of anaerobic reactor is 30 DEG C in step 4, pH value 7, and the residence time is for 24 hours that dissolved oxygen is 0.6mg/L。
The range of reaction temperature of aerobic reactor is 30 DEG C in step 5, pH value 7, and the residence time is for 24 hours that dissolved oxygen is 8mg/L。
After step 1 to six processing, the COD value drained outside gained is down to 16mg/L, meets the discharge mark of national regulation It is quasi-.
In the case where keeping other reaction conditions constant, using the graphite felt undoped with carbon nanotube as cathode material Material, the outer COD value drained of step 6 gained drop to 127mg/L.It can be seen that using carbon nanotube/graphite felt composite material Cathode material as the processing of electric Fenton has more preferably treatment effect to phenol wastewater.
Embodiment 4
The phenol wastewater being added in step 1 into waste water reaction container contains three kinds of phenol, m-cresol and p-cresol dirts Object, volume 2000mL are contaminated, initial COD value is 25000mg/L.The acid being added in step 1 is sulfuric acid, adjusts phenol wastewater pH Value is 2.5.The electrolyte being added in step 1 is sodium sulphate, additional amount 120g.
The electro-Fenton reaction device built in step 2 uses carbon nanotube/activated carbon fiber felt composite material as yin Pole material uses stainless steel plate as anode material, and the area of cathode is 10cm × 10cm, with a thickness of 10mm, the area of anode For 10cm × 10cm, with a thickness of 10mm.The DC voltage that electro-Fenton reaction device is passed through is 1.5V.Aerator is passed through air Flow velocity be 8m3/ h, when reaction at room temperature a length of 2.5h.Mass percent of the carbon nanotube in cathode material is 1% ~35%.Carbon nanotube/activated carbon fiber felt composite material preparation method is in the same manner as in Example 1.
It is sodium hydroxide that alkali is added in step 3, adjusts pH to 7.
The range of reaction temperature of anaerobic reactor is 30 DEG C in step 4, pH value 6.5, and the residence time is dissolved oxygen for 24 hours For 0.2mg/L.
The range of reaction temperature of aerobic reactor is 30 DEG C in step 5, pH value 6.5, and the residence time is dissolved oxygen for 24 hours For 10mg/L.
After step 1 to six processing, the COD value drained outside gained is down to 12mg/L, meets the discharge mark of national regulation It is quasi-.
Embodiment 5
The phenol wastewater being added in step 1 into waste water reaction container two kinds of pollutants containing phenol and p-cresol, volume For 1000mL, initial COD value is 20000mg/L.The acid being added in step 1 is sulfuric acid, and adjusting phenol wastewater pH value is 3.Step The electrolyte being added in one is sodium sulphate, additional amount 50g.
The electro-Fenton reaction device built in step 2 uses carbon nanotube/activated carbon fiber felt composite material as yin Pole material uses stainless steel plate as anode material, and the area of cathode is 5cm × 5cm, and with a thickness of 5mm, the area of anode is 5cm × 5cm, with a thickness of 5mm.The DC voltage that electro-Fenton reaction device is passed through is 1.5V.Aerator is passed through the stream of air Speed is 8m3/ h, micro- aeration time are 2h.A length of 2h when reaction at room temperature.
It is sodium hydroxide that alkali is added in step 3, adjusts pH to 7.
The range of reaction temperature of anaerobic reactor is 30 DEG C in step 4, pH value 6.5, residence time 12h, dissolved oxygen For 0.2mg/L.
The range of reaction temperature of aerobic reactor is 30 DEG C in step 5, pH value 6.5, and the residence time is dissolved oxygen for 24 hours For 8mg/L.
After step 1 to six processing, the COD value drained outside gained is down to 20mg/L, meets the discharge mark of national regulation It is quasi-.

Claims (10)

1. a kind of electricity Fenton-biological treatment collaboration Phenol-Containing Wastewater Treatment method, it is characterised in that: Step 1: by phenol wastewater Waste water reaction container is delivered to by noncorrosive pump, and acid and electrolyte is added, adjusting pH value range is 1~5, and it is dense to adjust electrolyte Range is spent in 0.05~0.5mol/L；
Step 2: building electro-Fenton reaction device in waste water reaction container；The cathode material of electro-Fenton reaction device uses carbon Nanotube/activated carbon fiber felt composite material or carbon nanotube/graphite felt composite material；At the cathode of electro-Fenton reaction device Aerator is installed；Later, electro-Fenton reaction device is passed through the direct current that voltage is 0.5~3V；Aerator is to waste water reaction Container is passed through air；The flow velocity of the be passed through air of aerator is 1~20m3The energization period of/h, electro-Fenton reaction device is 0.5~4h；
Step 3: electro-Fenton reaction device powers off, aerator stops being passed through air to waste water reaction container；Later, to step It is added alkali in two gained waste water, adjusts the pH value of waste water in waste water reaction container to neutrality；To waste water in waste water reaction container It precipitated, filtered, obtain filtrate；
Step 4: filtrate obtained by step 3 is passed through anaerobic reactor, and 6h~36h is stopped, obtains the first biological treatment waste water； Adjusting pH value range in anaerobic reactor is 6~9, and dissolved oxygen range is 0~2mg/L；
Step 5: the resulting first biological treatment waste water of step 4 is passed through aerobic reactor, and 4h~36h is stopped, obtains Two biological treatment waste water；Adjusting pH value range in aerobic reactor is 6~9, and dissolved oxygen range is 2~20mg/L；
Step 6: the second biological treatment waste water obtained by step 5 is flowed into sedimentation basin, after being precipitated, being filtered, resulting filtrate As outer draining.
2. a kind of electric Fenton according to claim 1-biological treatment collaboration Phenol-Containing Wastewater Treatment method, feature exist In: cathode material described in step 2 uses carbon nanotube/activated carbon fiber felt composite material；Carbon nanotube is in cathode material In mass percent be 1%~35%；Carbon nanotube/activated carbon fiber felt composite material is prepared via a method which to obtain:
(1) taking areal extent is that 2cm × 2cm~50cm × 50cm active carbon fiber felt is placed in the first dry beaker；
(2) into the first beaker be added mass concentration range be 0.01%~1% carbon nano tube dispersion liquid 100mL~ Active carbon fiber felt is totally submerged by 2000mL；Adjust carbon nano tube dispersion liquid in the first beaker temperature range be 25 DEG C~ 60 DEG C, infiltrate 2h after, in the first beaker carbon nano tube dispersion liquid and active carbon fiber felt carry out ultrasonic disperse 30min~ 90min；
(3) active carbon fiber felt is taken out from the first beaker, be placed in the second dry beaker；Matter is added into the second beaker Carbon nano tube dispersion liquid 100mL~2000mL that concentration range is 0.01%~1% is measured, active carbon fiber felt is totally submerged； The temperature range for adjusting carbon nano tube dispersion liquid in the second beaker is 25 DEG C~60 DEG C, after infiltrating 2h, to the carbon in the second beaker Nanotube dispersion liquid and active carbon fiber felt carry out ultrasonic disperse 30min；
(4) active carbon fiber felt is taken out from the second beaker, is placed in 60 DEG C of vacuum environment and is dried, obtain carbon nanometer Pipe/activated carbon fiber felt composite material.
3. a kind of electric Fenton according to claim 1-biological treatment collaboration Phenol-Containing Wastewater Treatment method, feature exist In: cathode material described in step 2 uses carbon nanotube/graphite felt composite material；Matter of the carbon nanotube in cathode material Measuring percentage is 1%~30%；Carbon nanotube/graphite felt composite material is prepared via a method which to obtain:
(1) taking areal extent is that 2cm × 2cm~50cm × 50cm graphite felt is placed in the first dry beaker；
(2) into the first beaker be added mass concentration range be 0.01%~1% carbon nano tube dispersion liquid 100mL~ Graphite felt is totally submerged by 2000mL；The temperature range for adjusting carbon nano tube dispersion liquid in the first beaker is 25 DEG C~60 DEG C, leaching After moistening 2h, to the carbon nano tube dispersion liquid and graphite felt progress ultrasonic disperse 30min~90min in the first beaker；
(3) graphite felt taken out from the first beaker is placed in pre-dry second beaker；Matter is added into the second beaker Carbon nano tube dispersion liquid 100mL~2000mL that concentration range is 0.01%~1% is measured, graphite felt is totally submerged；Adjust the The temperature range of carbon nano tube dispersion liquid is 25 DEG C~60 DEG C in two beakers, after heat preservation infiltration 2h, is received to the carbon in the second beaker Mitron dispersion liquid and graphite felt carry out ultrasonic disperse 30min；
(4) graphite felt is taken out from the second beaker, is placed in 60 DEG C of vacuum environment and is dried, obtain carbon nanotube/stone Black felt composite material.
4. a kind of electric Fenton according to claim 2 or 3-biological treatment collaboration Phenol-Containing Wastewater Treatment method, feature Be: carbon nanotube described in step 2 is single-walled carbon nanotube or multi-walled carbon nanotube；Carbon nanotube external diametrical extent be 5~ 20nm, length range are 10~100 μm；The active carbon fiber felt or graphite felt with a thickness of 3~15mm.
5. a kind of electric Fenton according to claim 1-biological treatment collaboration Phenol-Containing Wastewater Treatment method, feature exist In: the anaerobic reactor uses the high-efficient contact hybrid anaerobic reactor equipped with electron temperature-control system；Anaerobic reactor Interior temperature range is adjusted to 15 DEG C~60 DEG C；The aerobic reactor uses the interior circulation equipped with electron temperature-control system raw Object contacts aerobic reactor；Temperature range in aerobic reactor is 15 DEG C~60 DEG C.
6. a kind of electric Fenton according to claim 1-biological treatment collaboration Phenol-Containing Wastewater Treatment method, feature exist In: the anode material of electro-Fenton reaction device described in step 2 uses stainless steel plate；The area of anode and the area equation of cathode； In electro-Fenton reaction device, cathode face parallel with anode is placed, and spacing is 1~20cm.
7. a kind of electric Fenton according to claim 1-biological treatment collaboration Phenol-Containing Wastewater Treatment method, feature exist In: the phenol contained in phenol wastewater described in step 1 be one of phenol, o-cresol, m-cresol, p-cresol or It is a variety of.
8. a kind of electric Fenton according to claim 1-biological treatment collaboration Phenol-Containing Wastewater Treatment method, feature exist In: acid described in step 1 uses sulfuric acid, and nitric acid or sulfuric acid, nitric acid are arbitrarily than mixing resulting mixed acid；Electrolyte is sulphur Sour sodium, sodium nitrate, potassium sulfate or potassium nitrate.
9. a kind of electric Fenton according to claim 1-biological treatment collaboration Phenol-Containing Wastewater Treatment method, feature exist In: alkali described in step 3 uses the oxide or hydroxide of potassium, calcium, sodium.
10. a kind of electric Fenton according to claim 1-biological treatment collaboration Phenol-Containing Wastewater Treatment method, feature exist In: aerator is installed in aerobic reactor described in step 5.
CN201811416474.9A 2018-11-26 2018-11-26 A kind of method of electricity Fenton-biological treatment collaboration Phenol-Containing Wastewater Treatment Pending CN109467265A (en)

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