CN109626722A - A kind of aerobic process wastewater treatment method using modified graphene iron carbon material - Google Patents
A kind of aerobic process wastewater treatment method using modified graphene iron carbon material Download PDFInfo
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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
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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
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
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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
- C02F1/46—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
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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
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
- C02F1/56—Macromolecular compounds
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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
- C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
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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
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
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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
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/08—Chemical Oxygen Demand [COD]; Biological Oxygen Demand [BOD]
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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
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/02—Aerobic processes
Abstract
A kind of aerobic process wastewater treatment method using modified graphene iron carbon material disclosed in the method for the present invention, this programme is for the useless Organic substance in water of propylene oxide project, the high feature of salt content, waste water is now passed through into micro- ionization process, achieve the purpose that carry out useless Organic substance in water preliminary electrochemical degradation, reduces the COD value in waste water；The present invention uses a kind of modified graphene iron carbon material, and the potential difference not only generated with itself generates countless primary batteries in equipment, but also enhance the reactivity of material while solves the problems such as filler hardened inactivation；This programme meets national environmental protection requirement, and using a kind of pressure biological reaction apparatus, degradation of organic substances amount is big in waste water, treats the symptoms and effects a permanent cure, settles at one go, energy-saving and emission-reduction and no secondary pollution.
Description
Technical field
The present invention relates to field of industrial waste water treatment, are related to aerobic process processing HPPO propylene oxide industrial wastewater, specifically
For a kind of aerobic process wastewater treatment method using modified graphene iron carbon material.
Background technique
Propylene oxide plays an important role in organic chemical industry produces, and it is more can to produce propylene glycol, propylene glycol, polyethers
The chemical substances such as first alcohol, while being also production farm chemical emulgent, oil field demulsifier, nonionic surfactant, fire retardant, plasticising
The important source material of agent.Industrial wastewater discharge can inevitably be generated during production, waste water treatment process is to this kind of product
It produces extremely important.
201810278212.4 disclose a kind of propylene oxide industrial wastewater treatment system, including heat exchanger, filtration system,
Infiltration evaporation system, condenser, vacuum pump, fluid reservoir, methanol column, king-tower and dealcoholysis tower, by infiltration evaporation workshop section, the third two
Alcohol monomethyl ether concentration can be increased to 25%~30% with a step, and the concentration of methanol is 2% or more, concentration improve after material again into
Enter tri-columns rectification process (methanol column, king-tower and dealcoholysis tower) to carry out separation and recycling, which not only solves methanol and the third two
The problem of alcohol methyl ether cost recovery height, low efficiency, and the purity for recycling obtained methanol and propylene glycol monomethyl ether is all very high.
201810167061.5 provide a kind of epoxy propane waste water pretreatment and isolated method and separator, will contain
There are the waste water of organic matter and entrainer to carry out azeotropic distillation, entrainer and water carry out split-phase processing, water after forming azeotropic light component
Mutually discharge carries out subsequent processing, and entrainer returns in azeotropic distillation system, and remaining heavy constituent enters next azeotropic distillation body
In system, during the azeotropic distillation of afterbody, the azeotropic light component that entrainer and water are formed first is condensed carries out split-phase again,
Water phase after split-phase enters subsequent processing, and entrainer returns in azeotropic distillation system；Contain propylene glycol monomethyl ether, the third two in waste water
The different monomethyl ether of alcohol and propylene glycol；Entrainer is in aromatics, ethers, saturated alkane class, alcohols, esters and halogenated hydrocarbon entrainer
One kind.The invention realizes that epoxy propane waste water component is sufficiently separated, and is that waste water downstream biochemical treatment and corresponding byproduct recycle
Provide realizability.
201510206710.4 disclosing a kind of processing method of production of propylene oxide waste water, belong to field of waste water treatment.
The present invention solves existing epoxy propane waste water processing method there are processing costs that high, treatment process is immature, treatment effect
The problems such as poor, processing method concrete technology is: waste water being carried out homogeneous adjusting first, is then passed through two-stage anaerobic processing system
System makes macromolecular substances in waste water be converted to small molecule, improves wastewater biodegradability；Then passing through two-stage anaerobic, treated
Waste water is further processed by aerobic activated sludge, and the waste water after Aerobic Process for Treatment is finally passed through advanced Fenton oxidation method depth
It manages, the waste water after advanced treating can reach indirect discharge standard through air bearing and neutralization-precipitation reaction.Invention processing method tool
There is the advantages of easy to operate, treatment effeciency is high, processing cost is low, advanced treating ensures discharged wastewater met the national standard.
The process flow of peroxide passivation direct oxidation production of propylene propylene oxide (abbreviation HPPO method) is simpler, reacts item
Part is more mild, and investment most saves；But the saline sewage pollutant component generated in the propylene oxide industry of HPPO legal system is complicated,
Mainly contain methanol, sodium hydroxide, propionic aldehyde hydrazone, sodium formate, hydrazine hydrate, propylene oxide dipropylene glycol monomethyl ether etc..Current life
Changing processing method will receive seriously affecting for these impurity, prevent dirty water pollutant from effectively biodegrade.
Summary of the invention
To solve the above-mentioned problems, the present invention provides a kind of aerobic process waste water using modified graphene iron carbon material
Processing method；A kind of aerobic process wastewater treatment method using modified graphene iron carbon material of the present invention, technology
Scheme is as follows:
Step 1: the hydrochloric acid of 0.5-1.0mol/L is added into HPPO propylene oxide industrial wastewater, by pH in pH value conditioning tank
2-4 is adjusted, then waste liquid is pumped into cell reaction tower and carries out micro-electrolysis reaction, it is characterised in that in the reaction tower
There is a kind of modified graphene iron carbon material；The uniform aeration 30-60min in the cell reaction tower, during aeration constantly plus
Enter hydrochloric acid, waste liquid pH value is made to be maintained at 4 or less；
Step 2: the waste water that step 1 is come out imports biological regulating reservoir, sodium hydroxide is added, adjusting pH value is 6.5-8.5, so
Microcosmic salt is added in waste water according to 0.2-0.7kg/t, urea according to the amount of 0.1-0.5kg/t afterwards, stirring and dissolving is uniform；
Step 3: the waste water regulated is pumped into biochemical system, the biochemical system uses aerobic biochemical reactor, the reaction
Device is pressure biological reaction apparatus, is internally provided with biologic packing material, it is automatic that one is respectively provided at the top of the pressure biological reaction apparatus
Exhaust valve, the automatic exhaust steam valve and an ozone decomposer connection, device oxygen transmission efficiency with higher, high-solubility oxygen and
High-biomass is suitble to the wastewater treatment of high COD content.
Step 4: NaOH solution will be added in the waste water of biochemical treatment, waste liquor PH is adjusted to 8-10, according to 0.01-
Polyaluminum sulfate aluminium flocculating agent is added in 0.05kg/t, is pumped into sedimentation basin after mixing evenly, and supernatant liquor is directly discharged into next processing step
Suddenly, lower layer's turbid passes through filters pressing, removes precipitating, and filtrate is discharged into next processing step；
Step 5: the waste water of step 4 processing is sent into inorganic salts retarding system, one is used in the inorganic salts retarding system
Kind resin blocks filler, removes the purpose of inorganic salts, that is, completes the processing of waste water；Styrene monomer in the resin extender,
Acrylic monomers, methyl methacrylate monomer ratio be 1.5-2.5:0.8-1.5:0.1-0.5, use 0.8%-2.5%'s
Ammonium persulfate is that catalyst reacts 10-15h at 70-90 DEG C, and 0.01-0.05 parts of dimethylamino galliums are added and react 0.2-1.5h,
It is neutrality that the sodium carbonate liquor that 5%-10% is added, which adjusts pH value, then stirs 30-60min, filters, can obtain after washes clean
It arrives.
The modified graphene iron carbon material is prepared according to following scheme:
According to mass fraction, the ethyl alcohol of 50-100 parts of water and 100-150 part, which is added in reaction kettle, to be uniformly mixed, then
By 0.01-0.05 parts of polyoxy isobutylene/methylene urea copolymer and 0.01-0.05 parts of 1- decyl -3- methylimidazole six
Fluorine antimonate is added in reaction kettle, 40-60 DEG C of temperature control, nitrogen protection is added to react, and 0.05-0.2 parts of template is then added
With 5-10 parts of green vitriol, after mixing evenly slowly by the sodium borohydride solution of 10-20 parts of 0.05-0.25g/mL
It is added in reaction kettle, is added in 30-45min；When 30%-50% is added in sodium borohydride solution, by 0.15-0.65 parts of graphite
Alkene is added in reaction kettle, is continued to be stirred to react 20-30min after charging, then be filtered, seals after being washed with dehydrated alcohol
It saves, the modified graphene iron carbon material can be obtained.
The template is Tri-n-Propylamine or F127 or P123 or tetrapropyl amine or quinuclidine hydrochloride.
Microcosmic salt described in step 2 is potassium dihydrogen phosphate or sodium dihydrogen phosphate or sodium phosphate or potassium phosphate.
The COD value of waste water that A/O biochemical system is pumped into the step three can reach 5000ppm.
A kind of aerobic process wastewater treatment method using modified graphene iron carbon material disclosed in the method for the present invention, we
Waste water is now passed through micro- ionization process, reached to useless by case for the useless Organic substance in water of propylene oxide project, the high feature of salt content
Organic substance in water carries out the purpose of preliminary electrochemical degradation, reduces the COD value in waste water；The present invention uses a kind of modified graphene
Iron carbon material, the potential difference not only generated with itself generates countless primary batteries in equipment, but also enhances the anti-of material
Solves the problems such as filler hardened inactivation while answering activity；This programme meets national environmental protection requirement, uses a kind of pressure
Biological reaction apparatus, degradation of organic substances amount is big in waste water, treats the symptoms and effects a permanent cure, settles at one go, energy-saving and emission-reduction and without secondary dirt
Dye.
Specific embodiment
The invention is described further below by specific embodiment:
Embodiment 1
A kind of aerobic process wastewater treatment method using modified graphene iron carbon material of the present invention, technical solution is such as
Under:
Step 1: the hydrochloric acid of 0.8mol/L is added into HPPO propylene oxide industrial wastewater, by pH tune in pH value conditioning tank
It saves to 3, then waste liquid is pumped into cell reaction tower and carries out micro-electrolysis reaction, it is characterised in that have one in the reaction tower
Kind modified graphene iron carbon material；The uniform aeration 45min in the cell reaction tower is continuously added hydrochloric acid during aeration,
Waste liquid pH value is set to be maintained at 4 or less；
Step 2: the waste water that step 1 is come out imports biological regulating reservoir, sodium hydroxide is added, adjusting pH value is 7.5, then will
Microcosmic salt is added in waste water according to 0.5kg/t, urea according to the amount of 0.3kg/t, and stirring and dissolving is uniform；
Step 3: the waste water regulated is pumped into biochemical system, the biochemical system uses aerobic biochemical reactor, the reaction
Device is pressure biological reaction apparatus, is internally provided with biologic packing material, it is automatic that one is respectively provided at the top of the pressure biological reaction apparatus
Exhaust valve, the automatic exhaust steam valve and an ozone decomposer connection, device oxygen transmission efficiency with higher, high-solubility oxygen and
High-biomass is suitble to the wastewater treatment of high COD content.
Step 4: NaOH solution will be added in the waste water of biochemical treatment, waste liquor PH is adjusted to 9, is added according to 0.03kg/t
Polyaluminum sulfate aluminium flocculating agent, is pumped into sedimentation basin after mixing evenly, and supernatant liquor is directly discharged into next processing step, lower layer's turbid warp
Filters pressing is crossed, precipitating is removed, filtrate is discharged into next processing step；
Step 5: the waste water of step 4 processing is sent into inorganic salts retarding system, one is used in the inorganic salts retarding system
Kind resin blocks filler, removes the purpose of inorganic salts, that is, completes the processing of waste water；Styrene monomer in the resin extender,
Acrylic monomers, methyl methacrylate monomer ratio be 2:1.2:0.3, using 1.5% ammonium persulfate be catalyst 80
13h is reacted at DEG C, 0.03 part of dimethylamino gallium reaction 0.8h is added, and the sodium carbonate liquor for being added 8% adjusts pH value for neutrality, so
After stir 45min, filter, can be obtained after washes clean.
The modified graphene iron carbon material is prepared according to following scheme:
According to mass fraction, 80 parts of water and 130 parts of ethyl alcohol are added in reaction kettle and are uniformly mixed, then by 0.03 part
Polyoxy isobutylene/methylene urea copolymer and 0.03 part of 1- decyl -3- methylimidazole hexafluoro antimonate be added to reaction
In kettle, 50 DEG C of temperature control, nitrogen protection is added to react, 0.15 part of template and 8 parts of green vitriol, stirring is then added
Slowly the sodium borohydride solution of 15 parts of 0.15g/mL is added in reaction kettle after uniformly, is added in 40min；In sodium borohydride
When solution is added 40%, 0.35 part of graphene is added in reaction kettle, continues to be stirred to react 25min after charging, then
Filtering, is sealed after being washed with dehydrated alcohol, the modified graphene iron carbon material can be obtained.
The template is Tri-n-Propylamine.
Microcosmic salt described in step 2 is potassium dihydrogen phosphate.
The COD value of waste water that A/O biochemical system is pumped into the step three can reach 5000ppm.
Production of propylene oxide waste water (COD content 12415ppm, inorganic salt content 13681ppm in waste water) is passed through into this work
COD content is 214ppm, inorganic salt content 1151ppm in skill processed waste water.
Embodiment 2
A kind of aerobic process wastewater treatment method using modified graphene iron carbon material of the present invention, technical solution is such as
Under:
Step 1: the hydrochloric acid of 0.5mol/L is added into HPPO propylene oxide industrial wastewater, by pH tune in pH value conditioning tank
It saves to 2, then waste liquid is pumped into cell reaction tower and carries out micro-electrolysis reaction, it is characterised in that have one in the reaction tower
Kind modified graphene iron carbon material；The uniform aeration 30min in the cell reaction tower is continuously added hydrochloric acid during aeration,
Waste liquid pH value is set to be maintained at 4 or less；
Step 2: the waste water that step 1 is come out imports biological regulating reservoir, sodium hydroxide is added, adjusting pH value is 6.5, then will
Microcosmic salt is added in waste water according to 0.2kg/t, urea according to the amount of 0.1kg/t, and stirring and dissolving is uniform；
Step 3: the waste water regulated is pumped into biochemical system, the biochemical system uses aerobic biochemical reactor, the reaction
Device is pressure biological reaction apparatus, is internally provided with biologic packing material, it is automatic that one is respectively provided at the top of the pressure biological reaction apparatus
Exhaust valve, the automatic exhaust steam valve and an ozone decomposer connection, device oxygen transmission efficiency with higher, high-solubility oxygen and
High-biomass is suitble to the wastewater treatment of high COD content.
Step 4: NaOH solution will be added in the waste water of biochemical treatment, waste liquor PH is adjusted to 8, is added according to 0.01kg/t
Polyaluminum sulfate aluminium flocculating agent, is pumped into sedimentation basin after mixing evenly, and supernatant liquor is directly discharged into next processing step, lower layer's turbid warp
Filters pressing is crossed, precipitating is removed, filtrate is discharged into next processing step；
Step 5: the waste water of step 4 processing is sent into inorganic salts retarding system, one is used in the inorganic salts retarding system
Kind resin blocks filler, removes the purpose of inorganic salts, that is, completes the processing of waste water；Styrene monomer in the resin extender,
Acrylic monomers, methyl methacrylate monomer ratio be 1.5:0.8:0.1, using 0.8% ammonium persulfate be catalyst exist
10h to be reacted at 70 DEG C, 0.01 part of dimethylamino gallium reaction 0.2h is added, the sodium carbonate liquor adjusting pH value for being added 5% is neutrality,
Then 30min is stirred, is filtered, can be obtained after washes clean.
The modified graphene iron carbon material is prepared according to following scheme:
According to mass fraction, 50 parts of water and 100 parts of ethyl alcohol are added in reaction kettle and are uniformly mixed, then by 0.01 part
Polyoxy isobutylene/methylene urea copolymer and 0.01 part of 1- decyl -3- methylimidazole hexafluoro antimonate be added to reaction
In kettle, 40 DEG C of temperature control, nitrogen protection is added to react, 0.05 part of template and 5 parts of green vitriol, stirring is then added
Slowly the sodium borohydride solution of 10 parts of 0.05g/mL is added in reaction kettle after uniformly, is added in 30min；In sodium borohydride
When solution is added 30%, 0.15 part of graphene is added in reaction kettle, continues to be stirred to react 20min after charging, then
Filtering, is sealed after being washed with dehydrated alcohol, the modified graphene iron carbon material can be obtained.
The template is F127.
Microcosmic salt described in step 2 is sodium dihydrogen phosphate.
The COD value of waste water that A/O biochemical system is pumped into the step three can reach 5000ppm.
Production of propylene oxide waste water (COD content 12415ppm, inorganic salt content 13681ppm in waste water) is passed through into this work
COD content is 246ppm, inorganic salt content 1519ppm in skill processed waste water.
Embodiment 3
A kind of aerobic process wastewater treatment method using modified graphene iron carbon material of the present invention, technical solution is such as
Under:
Step 1: the hydrochloric acid of 1.0mol/L is added into HPPO propylene oxide industrial wastewater, by pH tune in pH value conditioning tank
It saves to 4, then waste liquid is pumped into cell reaction tower and carries out micro-electrolysis reaction, it is characterised in that have one in the reaction tower
Kind modified graphene iron carbon material；The uniform aeration 60min in the cell reaction tower is continuously added hydrochloric acid during aeration,
Waste liquid pH value is set to be maintained at 4 or less；
Step 2: the waste water that step 1 is come out imports biological regulating reservoir, sodium hydroxide is added, adjusting pH value is 8.5, then will
Microcosmic salt is added in waste water according to 0.7kg/t, urea according to the amount of 0.5kg/t, and stirring and dissolving is uniform；
Step 3: the waste water regulated is pumped into biochemical system, the biochemical system uses aerobic biochemical reactor, the reaction
Device is pressure biological reaction apparatus, is internally provided with biologic packing material, it is automatic that one is respectively provided at the top of the pressure biological reaction apparatus
Exhaust valve, the automatic exhaust steam valve and an ozone decomposer connection, device oxygen transmission efficiency with higher, high-solubility oxygen and
High-biomass is suitble to the wastewater treatment of high COD content.
Step 4: NaOH solution will be added in the waste water of biochemical treatment, adjust waste liquor PH to 10, according to 0.05kg/t plus
Enter polyaluminum sulfate aluminium flocculating agent, be pumped into sedimentation basin after mixing evenly, supernatant liquor is directly discharged into next processing step, lower layer's turbid
By filters pressing, precipitating is removed, filtrate is discharged into next processing step；
Step 5: the waste water of step 4 processing is sent into inorganic salts retarding system, one is used in the inorganic salts retarding system
Kind resin blocks filler, removes the purpose of inorganic salts, that is, completes the processing of waste water；Styrene monomer in the resin extender,
Acrylic monomers, methyl methacrylate monomer ratio be 2.5:1.5:0.5, using 2.5% ammonium persulfate be catalyst
15h is reacted at 90 DEG C, 0.05 part of dimethylamino gallium reaction 0.2-1.5h is added, the sodium carbonate liquor for being added 10% adjusts pH value
For neutrality, 30-60min is then stirred, is filtered, can be obtained after washes clean.
The modified graphene iron carbon material is prepared according to following scheme:
According to mass fraction, 100 parts of water and 150 parts of ethyl alcohol are added in reaction kettle and are uniformly mixed, then by 0.05
Polyoxy isobutylene/methylene urea the copolymer and 0.05 part of 1- decyl -3- methylimidazole hexafluoro antimonate of part are added to instead
It answers in kettle, 60 DEG C of temperature control, nitrogen protection is added to react, 0.05-0.2 parts of template and 5-10 parts of seven hydrated sulfuric acids are then added
The sodium borohydride solution of 20 parts of 0.25g/mL is slowly added in reaction kettle after mixing evenly, adds in 45min by ferrous iron；
When sodium borohydride solution is added 50%, 0.65 part of graphene is added in reaction kettle, continues to be stirred to react after charging
Then 30min is filtered, be sealed after being washed with dehydrated alcohol, and the modified graphene iron carbon material can be obtained.
The template is P123.
Microcosmic salt described in step 2 is potassium phosphate.
The COD value of waste water that A/O biochemical system is pumped into the step three can reach 5000ppm.
Production of propylene oxide waste water (COD content 12415ppm, inorganic salt content 13681ppm in waste water) is passed through into this work
COD content is 95ppm, inorganic salt content 681ppm in skill processed waste water.
Embodiment 4
A kind of aerobic process wastewater treatment method using modified graphene iron carbon material of the present invention, technical solution is such as
Under:
Step 1: the hydrochloric acid of 0.5mol/L is added into HPPO propylene oxide industrial wastewater, by pH tune in pH value conditioning tank
It saves to 2, then waste liquid is pumped into cell reaction tower and carries out micro-electrolysis reaction, it is characterised in that have one in the reaction tower
Kind modified graphene iron carbon material；The uniform aeration 30min in the cell reaction tower is continuously added hydrochloric acid during aeration,
Waste liquid pH value is set to be maintained at 4 or less；
Step 2: the waste water that step 1 is come out imports biological regulating reservoir, sodium hydroxide is added, adjusting pH value is 6.5, then will
Microcosmic salt is added in waste water according to 0.2kg/t, urea according to the amount of 0.1kg/t, and stirring and dissolving is uniform；
Step 3: the waste water regulated is pumped into biochemical system, the biochemical system uses aerobic biochemical reactor, the reaction
Device is pressure biological reaction apparatus, is internally provided with biologic packing material, it is automatic that one is respectively provided at the top of the pressure biological reaction apparatus
Exhaust valve, the automatic exhaust steam valve and an ozone decomposer connection, device oxygen transmission efficiency with higher, high-solubility oxygen and
High-biomass is suitble to the wastewater treatment of high COD content.
Step 4: NaOH solution will be added in the waste water of biochemical treatment, waste liquor PH is adjusted to 8, is added according to 0.01kg/t
Polyaluminum sulfate aluminium flocculating agent, is pumped into sedimentation basin after mixing evenly, and supernatant liquor is directly discharged into next processing step, lower layer's turbid warp
Filters pressing is crossed, precipitating is removed, filtrate is discharged into next processing step；
Step 5: the waste water of step 4 processing is sent into inorganic salts retarding system, one is used in the inorganic salts retarding system
Kind resin blocks filler, removes the purpose of inorganic salts, that is, completes the processing of waste water；Styrene monomer in the resin extender,
Acrylic monomers, methyl methacrylate monomer ratio be 1.5:0.8:0.1, using 0.8% ammonium persulfate be catalyst exist
10h to be reacted at 70 DEG C, 0.04 part of dimethylamino gallium reaction 0.2h is added, the sodium carbonate liquor adjusting pH value for being added 5% is neutrality,
Then 30min is stirred, is filtered, can be obtained after washes clean.
The modified graphene iron carbon material is prepared according to following scheme:
According to mass fraction, 100 parts of water and 150 parts of ethyl alcohol are added in reaction kettle and are uniformly mixed, then by 0.05
Polyoxy isobutylene/methylene urea the copolymer and 0.05 part of 1- decyl -3- methylimidazole hexafluoro antimonate of part are added to instead
It answers in kettle, 60 DEG C of temperature control, nitrogen protection is added to react, 0.05-0.2 parts of template and 5-10 parts of seven hydrated sulfuric acids are then added
The sodium borohydride solution of 20 parts of 0.25g/mL is slowly added in reaction kettle after mixing evenly, adds in 45min by ferrous iron；
When sodium borohydride solution is added 50%, 0.65 part of graphene is added in reaction kettle, continues to be stirred to react after charging
Then 30min is filtered, be sealed after being washed with dehydrated alcohol, and the modified graphene iron carbon material can be obtained.
The template is quinuclidine hydrochloride.
Microcosmic salt described in step 2 is sodium phosphate.
The COD value of waste water that A/O biochemical system is pumped into the step three can reach 5000ppm.
Production of propylene oxide waste water (COD content 12415ppm, inorganic salt content 13681ppm in waste water) is passed through into this work
COD content is 140ppm, inorganic salt content 845ppm in skill processed waste water.
Comparative example 1
Polyoxy isobutylene/methylene urea copolymer, the other the same as in Example 1 is not added in preparation component.
Production of propylene oxide waste water (COD content 12415ppm, inorganic salt content 13681ppm in waste water) is passed through into this work
COD content is 441ppm, inorganic salt content 1772ppm in skill processed waste water.
Comparative example 2
1- decyl -3- methylimidazole hexafluoro antimonate, the other the same as in Example 1 is not added in preparation component.
Production of propylene oxide waste water (COD content 12415ppm, inorganic salt content 13681ppm in waste water) is passed through into this work
COD content is 482ppm, inorganic salt content 1841ppm in skill processed waste water.
Comparative example 3
Dimethylamino gallium, the other the same as in Example 1 is not added in preparation component.
Production of propylene oxide waste water (COD content 12415ppm, inorganic salt content 13681ppm in waste water) is passed through into this work
COD content is 421ppm, inorganic salt content 1904ppm in skill processed waste water.
Comparative example 4
Pressure biological reaction apparatus, the other the same as in Example 1 are not used.
Production of propylene oxide waste water (COD content 12415ppm, inorganic salt content 13681ppm in waste water) is passed through into this work
COD content is 871ppm, inorganic salt content 2416ppm in skill processed waste water.
Comparative example 5
Without micro-electrolysis reaction, the other the same as in Example 1.
Production of propylene oxide waste water (COD content 12415ppm, inorganic salt content 13681ppm in waste water) is passed through into this work
COD content is 734ppm, inorganic salt content 2249ppm in skill processed waste water.
Claims (5)
1. a kind of aerobic process wastewater treatment method using modified graphene iron carbon material, its technical solution is as follows:
Step 1: the hydrochloric acid of 0.5-1.0mol/L is added into HPPO propylene oxide industrial wastewater, by pH in pH value conditioning tank
2-4 is adjusted, then waste liquid is pumped into cell reaction tower and carries out micro-electrolysis reaction, it is characterised in that in the reaction tower
There is a kind of modified graphene iron carbon material；The uniform aeration 30-60min in the cell reaction tower, during aeration constantly plus
Enter hydrochloric acid, waste liquid pH value is made to be maintained at 4 or less；
Step 2: the waste water that step 1 is come out imports biological regulating reservoir, sodium hydroxide is added, adjusting pH value is 6.5-8.5, so
Microcosmic salt is added in waste water according to 0.2-0.7kg/t, urea according to the amount of 0.1-0.5kg/t afterwards, stirring and dissolving is uniform；
Step 3: the waste water regulated is pumped into biochemical system, the biochemical system uses aerobic biochemical reactor, the reaction
Device is pressure biological reaction apparatus, is internally provided with biologic packing material, it is automatic that one is respectively provided at the top of the pressure biological reaction apparatus
Exhaust valve, the automatic exhaust steam valve and an ozone decomposer connection, device oxygen transmission efficiency with higher, high-solubility oxygen and
High-biomass is suitble to the wastewater treatment of high COD content；
Step 4: NaOH solution will be added in the waste water of biochemical treatment, waste liquor PH is adjusted to 8-10, according to 0.01-0.05kg/t
Polyaluminum sulfate aluminium flocculating agent is added, is pumped into sedimentation basin after mixing evenly, supernatant liquor is directly discharged into next processing step, and lower layer is turbid
Liquid passes through filters pressing, removes precipitating, and filtrate is discharged into next processing step；
Step 5: the waste water of step 4 processing is sent into inorganic salts retarding system, one is used in the inorganic salts retarding system
Kind resin blocks filler, removes the purpose of inorganic salts, that is, completes the processing of waste water；Styrene monomer in the resin extender,
Acrylic monomers, methyl methacrylate monomer ratio be 1.5-2.5:0.8-1.5:0.1-0.5, use 0.8%-2.5%'s
Ammonium persulfate is that catalyst reacts 10-15h at 70-90 DEG C, and 0.01-0.05 parts of dimethylamino galliums are added and react 0.2-1.5h,
It is neutrality that the sodium carbonate liquor that 5%-10% is added, which adjusts pH value, then stirs 30-60min, filters, can obtain after washes clean
It arrives.
2. a kind of aerobic process wastewater treatment method using modified graphene iron carbon material according to claim 1,
Be characterized in that: the modified graphene iron carbon material is prepared according to following scheme:
According to mass fraction, the ethyl alcohol of 50-100 parts of water and 100-150 part, which is added in reaction kettle, to be uniformly mixed, then
By 0.01-0.05 parts of polyoxy isobutylene/methylene urea copolymer and 0.01-0.05 parts of 1- decyl -3- methylimidazole six
Fluorine antimonate is added in reaction kettle, 40-60 DEG C of temperature control, nitrogen protection is added to react, and 0.05-0.2 parts of template is then added
With 5-10 parts of green vitriol, after mixing evenly slowly by the sodium borohydride solution of 10-20 parts of 0.05-0.25g/mL
It is added in reaction kettle, is added in 30-45min；When 30%-50% is added in sodium borohydride solution, by 0.15-0.65 parts of graphite
Alkene is added in reaction kettle, is continued to be stirred to react 20-30min after charging, then be filtered, seals after being washed with dehydrated alcohol
It saves, the modified graphene iron carbon material can be obtained.
3. a kind of aerobic process wastewater treatment method using modified graphene iron carbon material according to claim 2,
Be characterized in that: the template is Tri-n-Propylamine or F127 or P123 or tetrapropyl amine or quinuclidine hydrochloride.
4. a kind of aerobic process wastewater treatment method using modified graphene iron carbon material according to claim 1,
Be characterized in that: microcosmic salt described in step 2 is potassium dihydrogen phosphate or sodium dihydrogen phosphate or sodium phosphate or potassium phosphate.
5. a kind of aerobic process wastewater treatment method using modified graphene iron carbon material according to claim 1,
Be characterized in that: the COD value of waste water that A/O biochemical system is pumped into the step three can reach 5000ppm.
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