CN109626677A - A kind of advanced treatment process of coking waste water - Google Patents

A kind of advanced treatment process of coking waste water Download PDF

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Publication number
CN109626677A
CN109626677A CN201910133901.0A CN201910133901A CN109626677A CN 109626677 A CN109626677 A CN 109626677A CN 201910133901 A CN201910133901 A CN 201910133901A CN 109626677 A CN109626677 A CN 109626677A
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coking
parts
waste water
coking wastewater
treatment process
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CN109626677B (en
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蔡思泉
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Jiangsu Tongrui Environmental Protection Co Ltd
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Jiangsu Tongrui Environmental Protection Co Ltd
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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
    • C02F1/001Processes for the treatment of water whereby the filtration technique is of importance
    • 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
    • C02F1/44Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • 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
    • C02F1/48Treatment of water, waste water, or sewage with magnetic or electric fields
    • C02F1/488Treatment of water, waste water, or sewage with magnetic or electric fields for separation of magnetic materials, e.g. magnetic flocculation
    • 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
    • C02F2103/00Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/34Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00Controlling or monitoring parameters in water treatment
    • C02F2209/08Chemical Oxygen Demand [COD]; Biological Oxygen Demand [BOD]
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00Controlling or monitoring parameters in water treatment
    • C02F2209/14NH3-N
    • 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

Abstract

The present invention relates to a kind of advanced treatment process of coking waste water comprising following steps: (1) filtering;(2) magnetically separating and purifying;(3) low temperature properties flocculation aid is added and carries out precipitation process;(4) electrocatalytic oxidation;(5) biological treatment;(6) membrane filter filters;Using low temperature properties flocculation aid, the coagulation effect of the lower coking wastewater of temperature can be improved, be conducive to the subsequent purification efficiency for improving coking wastewater;Electrocatalytic oxidation processing is carried out again, is produced the hydroxyl radical free radical with very high oxidation potential, in large area the organic matter in oxidized waste water, while being aerated generation stirring action, be may additionally facilitate the discharge of dross during electro-catalysis;Using the above-mentioned process coking wastewater of the application, water outlet COD and ammonia nitrogen can be prepared while coking wastewater up to standard.

Description

A kind of advanced treatment process of coking waste water
Technical field
The present invention relates to the technical fields of wastewater treatment, more particularly, to a kind of advanced treatment process of coking waste water.
Background technique
Coking wastewater is a kind of industrial wastewater of generally acknowledged difficult for biological degradation, and difficulty is that the biodegradability of waste water is poor, Except the inorganic pollutions beyond the region of objective existence such as ammonia, cyanogen and thiocyanate, also containing heterocycles and polycyclc aromatic compounds such as phenols, naphthalene, pyridine, quinoline (PAHS) it is difficult biodegrade, these substances can produce long-range effects to environment, and part has been studied and has turned out to be carcinogenic substance Matter, in addition ammonia nitrogen in high density has very strong inhibiting effect to microbial activity, and Nitrogen removal effect is bad.Currently, coking wastewater Processing generally use by A/O or based on the biological reinforced techniques such as A/O/O, A/A/O, O/A/O after A/O process modification Bioremediation, is often aided with coagulating kinetics after bioremediation, reaches discharge standard requirement reluctantly, in addition, by In advanced treating somewhat expensive, domestic many coke-oven plants is enabled to hang back, thus most coking wastewaters after two stage treatment just Direct emission, waste water pass through above-mentioned processing, and wherein poisonous and harmful substances (cyanide, COD and heterocyclic compound etc.) are still retained It is more, the discharge standard of country's permission is not achieved.
Currently, coking waste water treatment method can be divided into physical method and biochemical method.Physico-chemical process includes solvent extraction Phenol, lime or caustic soda distillation are removed except ammonia, alkali formula chloridising removes cyanogen and ammonia, and chemical oxidization method removes organic matter, wet oxidation And activated carbon adsorption etc..Physical chemistry method removal pollutant is high-efficient, stable and reliable operation, but the removal of various pollutants often needs Want several method to be used in combination, operating cost is also very high, therefore at present physico-chemical process be mainly used as biological treatment pretreatment or Subsequent processing.Biochemical rule is that multiple pollutant can be removed in single biological treatment system, and easy to operate, operation Expense is also more much lower than physico-chemical process, therefore biochemical processing method is always the main means of Treatment of Coking Effluent.
In recent years, biological denitrification process gradually attracts people's attention and becomes the main side of Treatment of Coking Effluent gradually Method generally uses anaerobic-aerobic or anaerobic- anoxic- oxic activated sludge process.These techniques are due to being utilized anaerobism, facultative aerobe And the different degradation characteristics of aerobic bacteria have in terms of removal COD and ammonia nitrogen and substantially change compared with conventional activated sludge process It is kind, but due to coking wastewater containing toxic organic compound type difficult to degrade more, water quality and quantity feature complicated and changeable, so that anoxic- Aerobic isoreactivity sludge processes, since generation time is long, restore vulnerable to impact, especially aerobic section Autotrophic nitrification bacterium after being hit Slowly, nitrification efficiency declines, so that the water outlet COD and ammonia nitrogen of the technique are difficult while up to standard.
Summary of the invention
The object of the present invention is to provide a kind of advanced treatment process of coking waste water, be conducive to coking wastewater water outlet COD and Ammonia nitrogen is up to standard simultaneously.
Foregoing invention purpose of the invention has the technical scheme that
A kind of advanced treatment process of coking waste water, includes the following steps:
(1) by coking wastewater put into mixed precipitation pond in, adjust coking wastewater pH value be 7.5 ~ 8, through more medium filter into Row filtering;
(2) it after filtering, is purified again using magnetic separation technique;
(3) low temperature properties flocculation aid is added and carries out precipitation process, the low temperature properties flocculation aid uses the component of following parts by weight: activation 80 ~ 85 parts of silicic acid, 3 ~ 7 parts of industrial aluminum sulphate, 1 ~ 5 part of two polyphosphate sodium, 10 ~ 15 parts of hydrogen peroxide and ammonium persulfate 1 ~ 5 Part;
(4) after precipitation, coking wastewater is put into electrocatalysis oxidation reaction pond, reaction bottom of pond portion is aerated, wherein electrode Surface is coated with ceramic conductive coating and using microwave heating;
(5) after being catalyzed, coking wastewater is discharged into biological regulation closed cell, the pH value for adjusting coking wastewater is 3.5 ~ 4.5, is adjusted Saving temperature in pond is 60 ~ 85 DEG C, stirs 1 ~ 3h using ultrasonic wave, stands at least 10h;
(6) after standing, coking wastewater is filtered using membrane filter, the membrane filter uses high activity fibrous material It is knitted to form.
By using above-mentioned technical proposal, basification is carried out to coking wastewater first, is conducive to occur in coking wastewater Flocculation, precipitating;By more medium filter, magnetic separation technique filtration, purification, silt, the impurity in coking wastewater are eliminated Grain;Using low temperature properties flocculation aid, the coagulation effect of the lower coking wastewater of temperature can be improved, be conducive to after improving coking wastewater Continuous purification efficiency;Electrocatalytic oxidation processing is carried out again, produces the hydroxyl radical free radical with very high oxidation potential, in large area oxygen Change the organic matter in waste water, while being aerated generation stirring action, may additionally facilitate the discharge of dross during electro-catalysis, microwave adds Heat significantly shortens the time of electrocatalytic oxidation process;Finally using biological regulation closed cell carry out biochemical treatment, adjust pH and Temperature is remarkably improved the efficiency of biochemical treatment;Using the above-mentioned process coking wastewater of the application, water outlet COD can be prepared The coking wastewater up to standard simultaneously with ammonia nitrogen.
The present invention is further arranged to: more medium filter includes the nothing being from top to bottom successively laid in the step (1) The partial size of bituminous coal layer, fine sand layer and coarse sands layer, the anthracite coal measure, fine sand layer and coarse sands layer is incremented by successively.
By using above-mentioned technical proposal, the partial size of anthracite coal measure, fine sand layer and coarse sands layer is sequentially increased, and coking can be given up The impurity of different-grain diameter is effectively filtered in water, to realize the primary filtration to coking wastewater.
The present invention is further arranged to: the electrode in the step (3) in electrocatalysis oxidation reaction pond uses titanium plate, titanium plate Surface is successively impregnated by ultrasonic alkali cleaning, the oxalic acid solution that mass concentration is 25% and deionized water is cleaned and it is pre- to dry multistep Treatment process.
By using above-mentioned technical proposal, basification is carried out to titanium plate first, ultrasonic alkali cleaning may additionally facilitate coking wastewater In foreign ion distribution it is more uniform;Then acidification is carried out to titanium plate, removes the passivating film on surface, is produced from titanium plate surface Life-stylize effect;It can be prepared by surface cleanliness height, the easy titanium plate base for adhering to coating using deionized water cleaning.
The present invention is further arranged to, and the ceramic conductive coating includes the component of following parts by weight:
70 ~ 75 parts of yttrium oxide, 10 ~ 12 parts of zircon sand ore, 1 ~ 5 part of carbon nanotube, 1 ~ 5 part of ceramic fibre, polyborosiloxane 1 ~ 3 part and 5 ~ 10 parts of hexamethyldisiloxane.
By using above-mentioned technical proposal, yttrium oxide (Y2O3) it is cubic structure, fusing point is high, chemical and photochemical stability Good, optical transparence wider range, refractive index is high, and theoretical transmission is higher, thermal conductivity also with higher, belongs to rare earth metal Oxide, polarizability is stronger, and the diversity of electron energy level and spectral line is higher, helps to drop the organic matter in waste water Solution;Zircon sand ore refractoriness is high, density is big, heat storage coefficient is big, anti-metal penetrating power is strong, any surface finish and can easily glue with various It ties agent to combine, there is excellent high temperature resistance;Carbon nanotube has excellent absorption property, and adsorption stuffing is in mixing process In, the absorption associativity with other components filler can be increased, the binding force with other fillers can be increased, make whole combination Property is more preferable;Ceramic fibre has excellent fire resisting, high temperature resistant and corrosion resistance, and the casting model powder can be improved in a small amount of addition High temperature resistance and corrosion resistance;It is carbonized after polyborosiloxane experience high temperature, there is excellent gluing characteristic after carbonization, Select partial size to be that the polyborosiloxane of 500 ~ 1000nm compares partial size with other fillers smaller, be conducive to fill other fillers it Between in the gap that generates, increase the associativity between each component;And partial size is less than the polyborosiloxane of 500nm, then is prepared into This is higher, and partial size is larger greater than the polyborosiloxane particle of 1000nm, shows that caking phenomenon occurs in synthesis process, heat-resisting quantity Energy and glueability are affected;Hexamethyldisiloxane is colourless transparent liquid, can promote each component in coating system Mutual wetting, have good dissolubility, foaming characteristic and resistance to hard water, dispersion of calcium soap, also have it is good biology drop Solve performance;The conductive coating prepared using above-mentioned each component, is increased the specific surface area and oxidation activity of coating, is conducive to mention Palliating degradation degree of the height to coking wastewater.
The present invention is further arranged to: the partial size of the yttrium oxide is 50 ~ 100nm.
By using above-mentioned technical proposal, nanoscale yttrium oxide be may be homogenously dispersed in the polyborosiloxane of molten state, With excellent dispersibility, the differential settlement of conductive coating is reduced.
The present invention is further arranged to, and the preparation method of the ceramic conductive coating includes the following steps:
(1) polyborosiloxane is heated and is melted, add hexamethyldisiloxane;
(2) yttrium oxide, zircon sand ore, carbon nanotube high speed dispersion are obtained into mixture in the polyborosiloxane of fusing;
(3) ceramic fibre is evenly mixed in mixture again, extruding pelletization;
(4) granulation is sintered, sintering temperature is 2200 ~ 2700 DEG C;
(5) it crushes and sprays.
By using above-mentioned technical proposal, hexamethyldisiloxane is slowly penetrated in polyborosiloxane first, is helped In the wetting, dissolution and infiltration of polyborosiloxane and other components, then again by yttrium oxide, zircon sand ore, carbon nanotube high speed Be dispersed in polyborosiloxane, then add ceramic fibre and be blended in the reaction system, it is to be mixed uniformly after, extruding pelletization powder again It is broken, it is prepared for the conductive coating that homogeneous, surface is easily adhered to.
The present invention is further arranged to: the addition time of the hexamethyldisiloxane is no less than 30min.
By using above-mentioned technical proposal, the addition time of hexamethyldisiloxane is limited, it is ensured that two silicon oxygen of hexamethyl Alkane is added slowly in reaction system, is conducive to uniformly penetrating in polyborosiloxane, facilitates the table for reducing polyborosiloxane Face tension guarantees the uniformity mixed with other components.
The present invention is further arranged to: the diameter of the ceramic fibre is 3 ~ 5 μm, and length is 15 ~ 25mm.
By using above-mentioned technical proposal, the diameter and length of ceramic fibre are limited, it is evenly dispersed to be conducive to ceramic fibre In the reaction system, high temperature resistant, the ablation resistance of conductive coating are improved.
The present invention is further arranged to: being evacuated in the step (5) to biological regulation closed cell, control vacuum degree is 10~30kpa。
By using above-mentioned technical proposal, set vacuum degree as 10 ~ 30kpa, it can be achieved that extract solid state floccule body, The foul odour in sewage can also be taken away, there is excellent treatment effect.
In conclusion advantageous effects of the invention are as follows:
1. adjusting coking wastewater is in alkalinity first, and adds the invention discloses a kind of advanced treatment process of coking wastewater Uniform settlement occurs for low temperature properties flocculation aid, the coking wastewater for facilitating lower temperature;
2. carrying out electrocatalytic oxidation to coking wastewater, the catalytic process catalytic efficiency is higher, is conducive to focus after primary filtration Change the depth degradation of waste water;
3. catalytic electrode surface sprays to form ceramic conductive coating, the specific surface area and oxidation activity of coating are increased, is had There is excellent catalytic activity;
4. in biological treatment process using negative pressure ventilation, the dross of catalytic electrode surface can be extracted, while also can remove electrolysis The smell generated is reacted, the practicability of electrocatalytic oxidation system is improved.
Specific embodiment
Invention is further described in detail with reference to embodiments.
Embodiment one:
A kind of low temperature properties flocculation aid, is prepared using following steps:
(1) according to parts by weight, 80 parts of activated silicic acid, 3 parts of industrial aluminum sulphate, 1 part of two polyphosphate sodium, peroxidating ingredient: are weighed 10 parts and 1 part of ammonium persulfate of hydrogen;
(2) industrial aluminum sulphate, two polyphosphate sodiums are added into activated silicic acid, are stirred evenly;
(3) hydrogen peroxide, ammonium persulfate are continuously added, to uniformly mix.
Embodiment two:
A kind of low temperature properties flocculation aid is that the constituent content of low temperature properties flocculation aid is different from the difference of embodiment one place, weighs 81 parts of activated silicic acid, 4 parts of industrial aluminum sulphate, 2 parts of two polyphosphate sodium, 11 parts of hydrogen peroxide and 2 parts of ammonium persulfate.
Embodiment three:
A kind of low temperature properties flocculation aid is that the constituent content of low temperature properties flocculation aid is different from the difference of embodiment one place, weighs 82 parts of activated silicic acid, 5 parts of industrial aluminum sulphate, 3 parts of two polyphosphate sodium, 12 parts of hydrogen peroxide and 3 parts of ammonium persulfate.
Example IV:
A kind of low temperature properties flocculation aid is that the constituent content of low temperature properties flocculation aid is different from the difference of embodiment one place, weighs 84 parts of activated silicic acid, 6 parts of industrial aluminum sulphate, 4 parts of two polyphosphate sodium, 14 parts of hydrogen peroxide and 4 parts of ammonium persulfate.
Embodiment five:
A kind of low temperature properties flocculation aid is that the constituent content of low temperature properties flocculation aid is different from the difference of embodiment one place, weighs 85 parts of activated silicic acid, 7 parts of industrial aluminum sulphate, 5 parts of two polyphosphate sodium, 15 parts of hydrogen peroxide and 5 parts of ammonium persulfate.
Embodiment six:
A kind of catalysis electrode, prepares with the following method:
(1) catalysis electrode uses titanium plate, and titanium plate surface carries out ultrasonic alkali cleaning first;
(2) after alkali cleaning, mass concentration is used to impregnate for 25% oxalic acid solution;
(3) it cleans and dries using deionized water;
(4) ceramic coatedization conductive coating: a) ingredient: in parts by weight, weigh 70 parts of yttrium oxide, 10 parts of zircon sand ore, 1 part of carbon nanotube, 1 part of ceramic fibre, 1 part of polyborosiloxane and 5 parts of hexamethyldisiloxane;B) polyborosiloxane is added Heat fusing adds hexamethyldisiloxane, and the addition time of hexamethyldisiloxane is no less than 30min;C) by yttrium oxide, zircon sand Ore, carbon nanotube high speed dispersion obtain mixture in the polyborosiloxane of fusing;D) ceramic fibre is evenly mixed in again In mixture, extruding pelletization;E) granulation is sintered, sintering temperature is 2200 ~ 2700 DEG C;F) it crushes and sprays.
Embodiment seven:
A kind of catalysis electrode is that the constituent content of conductive coating is different from the difference of embodiment six place, in parts by weight, Weigh 72 parts of yttrium oxide, 10 parts of zircon sand ore, 2 parts of carbon nanotube, 2 parts of ceramic fibre, 1 part of polyborosiloxane and pregnancy 7 parts of base disiloxane.
Embodiment eight:
A kind of catalysis electrode is that the constituent content of conductive coating is different from the difference of embodiment six place, in parts by weight, Weigh 73 parts of yttrium oxide, 11 parts of zircon sand ore, 3 parts of carbon nanotube, 3 parts of ceramic fibre, 2 parts of polyborosiloxane and pregnancy 7 parts of base disiloxane.
Embodiment nine:
A kind of catalysis electrode is that the constituent content of conductive coating is different from the difference of embodiment six place, in parts by weight, Weigh 74 parts of yttrium oxide, 12 parts of zircon sand ore, 4 parts of carbon nanotube, 4 parts of ceramic fibre, 3 parts of polyborosiloxane and hexamethyl Disiloxane 9.
Embodiment ten:
A kind of catalysis electrode is that the constituent content of conductive coating is different from the difference of embodiment six place, in parts by weight, Weigh 75 parts of yttrium oxide, 12 parts of zircon sand ore, 5 parts of carbon nanotube, 5 parts of ceramic fibre, 3 parts of polyborosiloxane and hexamethyl 10 parts of disiloxane.
Embodiment 11:
A kind of advanced treatment process of coking waste water, includes the following steps:
(1) coking wastewater is put into mixed precipitation pond, the pH value for adjusting coking wastewater is 7.5, is carried out through more medium filter Filtering, more medium filter includes the anthracite coal measure, fine sand layer and coarse sands layer being from top to bottom successively laid with;
(2) it after filtering, is purified again using magnetic separation technique;
(3) low temperature properties flocculation aid is added and carries out precipitation process, low temperature properties flocculation aid is prepared using embodiment one;
(4) after precipitation, coking wastewater is put into electrocatalysis oxidation reaction pond, reaction bottom of pond portion is aerated, wherein catalysis Electrode is formed using the preparation of embodiment six, and microwave heating is used in catalytic process;
(5) after being catalyzed, coking wastewater is discharged into biological regulation closed cell, while biological regulation closed cell is evacuated, Control vacuum degree is 10 ~ 30kpa, and the pH value for adjusting coking wastewater is 3.5, and temperature is 60 DEG C in conditioning tank, is stirred using ultrasonic wave 1h is mixed, 10h is stood;
(6) after standing, coking wastewater is filtered using membrane filter, the membrane filter uses high activity fibrous material It is knitted to form.
Embodiment 12:
A kind of advanced treatment process of coking waste water, includes the following steps:
(1) coking wastewater is put into mixed precipitation pond, the pH value for adjusting coking wastewater is 7.7, is carried out through more medium filter Filtering, more medium filter includes the anthracite coal measure, fine sand layer and coarse sands layer being from top to bottom successively laid with;
(2) it after filtering, is purified again using magnetic separation technique;
(3) low temperature properties flocculation aid is added and carries out precipitation process, low temperature properties flocculation aid is prepared using embodiment two;
(4) after precipitation, coking wastewater is put into electrocatalysis oxidation reaction pond, reaction bottom of pond portion is aerated, wherein catalysis Electrode is formed using the preparation of embodiment seven, and microwave heating is used in catalytic process;
(5) after being catalyzed, coking wastewater is discharged into biological regulation closed cell, while biological regulation closed cell is evacuated, Control vacuum degree is 10 ~ 30kpa, and the pH value for adjusting coking wastewater is 3.8, and temperature is 65 DEG C in conditioning tank, is stirred using ultrasonic wave 1.5h is mixed, 12h is stood;
(6) after standing, coking wastewater is filtered using membrane filter, the membrane filter uses high activity fibrous material It is knitted to form.
Embodiment 13:
A kind of advanced treatment process of coking waste water, includes the following steps:
(1) coking wastewater is put into mixed precipitation pond, the pH value for adjusting coking wastewater is 7.8, is carried out through more medium filter Filtering, more medium filter includes the anthracite coal measure, fine sand layer and coarse sands layer being from top to bottom successively laid with;
(2) it after filtering, is purified again using magnetic separation technique;
(3) low temperature properties flocculation aid is added and carries out precipitation process, low temperature properties flocculation aid is prepared using embodiment three;
(4) after precipitation, coking wastewater is put into electrocatalysis oxidation reaction pond, reaction bottom of pond portion is aerated, wherein catalysis Electrode is formed using the preparation of embodiment eight, and microwave heating is used in catalytic process;
(5) after being catalyzed, coking wastewater is discharged into biological regulation closed cell, while biological regulation closed cell is evacuated, Control vacuum degree is 10 ~ 30kpa, and the pH value for adjusting coking wastewater is 4.0, and temperature is 70 DEG C in conditioning tank, is stirred using ultrasonic wave 2h is mixed, 12h is stood;
(6) after standing, coking wastewater is filtered using membrane filter, the membrane filter uses high activity fibrous material It is knitted to form.
Embodiment 14:
A kind of advanced treatment process of coking waste water, includes the following steps:
(1) coking wastewater is put into mixed precipitation pond, the pH value for adjusting coking wastewater is 8, is carried out through more medium filter Filter, more medium filter includes the anthracite coal measure, fine sand layer and coarse sands layer being from top to bottom successively laid with;
(2) it after filtering, is purified again using magnetic separation technique;
(3) low temperature properties flocculation aid is added and carries out precipitation process, low temperature properties flocculation aid is prepared using example IV;
(4) after precipitation, coking wastewater is put into electrocatalysis oxidation reaction pond, reaction bottom of pond portion is aerated, wherein catalysis Electrode is formed using the preparation of embodiment nine, and microwave heating is used in catalytic process;
(5) after being catalyzed, coking wastewater is discharged into biological regulation closed cell, while biological regulation closed cell is evacuated, Control vacuum degree is 10 ~ 30kpa, and the pH value for adjusting coking wastewater is 4.2, and temperature is 75 DEG C in conditioning tank, is stirred using ultrasonic wave 2.5h is mixed, 14h is stood
(6) after standing, coking wastewater is filtered using membrane filter, the membrane filter uses high activity fibrous material It is knitted to form.
Embodiment 15:
A kind of advanced treatment process of coking waste water, includes the following steps:
(1) coking wastewater is put into mixed precipitation pond, the pH value for adjusting coking wastewater is 8, is carried out through more medium filter Filter, more medium filter includes the anthracite coal measure, fine sand layer and coarse sands layer being from top to bottom successively laid with;
(2) it after filtering, is purified again using magnetic separation technique;
(3) low temperature properties flocculation aid is added and carries out precipitation process, low temperature properties flocculation aid is prepared using embodiment five;
(4) after precipitation, coking wastewater is put into electrocatalysis oxidation reaction pond, reaction bottom of pond portion is aerated, wherein catalysis Electrode is formed using the preparation of embodiment ten, and microwave heating is used in catalytic process;
(5) after being catalyzed, coking wastewater is discharged into biological regulation closed cell, while biological regulation closed cell is evacuated, Control vacuum degree is 10 ~ 30kpa, and the pH value for adjusting coking wastewater is 4.5, and temperature is 85 DEG C in conditioning tank, is stirred using ultrasonic wave 3h is mixed, 15h is stood;
(6) after standing, coking wastewater is filtered using membrane filter, the membrane filter uses high activity fibrous material It is knitted to form.
Comparative example:
A kind of advanced treatment process of coking wastewater, includes the following steps:
(1) coking wastewater is put into mixed precipitation pond, the pH value for adjusting coking wastewater is 7.2, is carried out through more medium filter Filtering;
(2) after filtering, coking wastewater is put into electrocatalysis oxidation reaction pond, wherein catalysis electrode uses iron plate electrode;
(5) after being catalyzed, coking wastewater is discharged into biological regulating reservoir, the pH value for adjusting coking wastewater is 3, temperature in conditioning tank It is 25 DEG C, stands 15h;
(6) after standing, coking wastewater is filtered using membrane filter.
Detection method:
(1) COD is detected: according to GB/T 11914-1989, being detected using dichromate titration;
(2) it ammonia nitrogen removal frank: according to GB/T 7479-1987, is detected using reagent colorimetric method.
The testing result for being discharged COD and ammonia-nitrogen content is as shown in the table:
Sample COD removal rate (%) Ammonia nitrogen removal frank (%)
Embodiment 11 98.5 87.3
Embodiment 12 98.7 88.1
Embodiment 13 98.4 89.2
Embodiment 14 98.8 90.7
Embodiment 15 98.6 88.6
Comparative example 92.5 75.6
By upper table it is found that using the application advanced treatment process handle coking wastewater, compared to the processing work of comparative example Skill, while the advanced treating, it can be achieved that coking wastewater is improved to the removal rate of COD and ammonia nitrogen.
The embodiment of present embodiment is presently preferred embodiments of the present invention, not limits protection of the invention according to this Range, therefore: the equivalence changes that all structures under this invention, shape, principle are done, should all be covered by protection scope of the present invention it It is interior.

Claims (9)

1. a kind of advanced treatment process of coking waste water, which comprises the steps of:
(1) by coking wastewater put into mixed precipitation pond in, adjust coking wastewater pH value be 7.5 ~ 8, through more medium filter into Row filtering;
(2) it after filtering, is purified again using magnetic separation technique;
(3) low temperature properties flocculation aid is added and carries out precipitation process, the low temperature properties flocculation aid uses the component of following parts by weight: activation 80 ~ 85 parts of silicic acid, 3 ~ 7 parts of industrial aluminum sulphate, 1 ~ 5 part of two polyphosphate sodium, 10 ~ 15 parts of hydrogen peroxide and ammonium persulfate 1 ~ 5 Part;
(4) after precipitation, coking wastewater is put into electrocatalysis oxidation reaction pond, reaction bottom of pond portion is aerated, wherein electrode Surface is coated with ceramic conductive coating and using microwave heating;
(5) after being catalyzed, coking wastewater is discharged into biological regulation closed cell, the pH value for adjusting coking wastewater is 3.5 ~ 4.5, is adjusted Saving temperature in pond is 60 ~ 85 DEG C, stirs 1 ~ 3h using ultrasonic wave, stands at least 10h;
(6) after standing, coking wastewater is filtered using membrane filter, the membrane filter uses high activity fibrous material It is knitted to form.
2. a kind of advanced treatment process of coking waste water according to claim 1, it is characterised in that: more in the step (1) Medium filter includes the anthracite coal measure, fine sand layer and coarse sands layer being from top to bottom successively laid with, the anthracite coal measure, fine sand layer with The partial size of coarse sands layer is incremented by successively.
3. a kind of advanced treatment process of coking waste water according to claim 1, it is characterised in that: electric in the step (3) Electrode in catalytic oxidation pond uses titanium plate, and titanium plate surface is successively molten for 25% oxalic acid by ultrasonic alkali cleaning, mass concentration Liquid impregnates and deionized water cleans and dries multistep pretreating process.
4. a kind of advanced treatment process of coking waste water according to claim 1, which is characterized in that the ceramic conduction applies Layer includes the component of following parts by weight:
70 ~ 75 parts of yttrium oxide, 10 ~ 12 parts of zircon sand ore, 1 ~ 5 part of carbon nanotube, 1 ~ 5 part of ceramic fibre, polyborosiloxane 1 ~ 3 part and 5 ~ 10 parts of hexamethyldisiloxane.
5. a kind of advanced treatment process of coking waste water according to claim 4, it is characterised in that: the partial size of the yttrium oxide For 50 ~ 100nm.
6. a kind of advanced treatment process of coking waste water according to claim 5, which is characterized in that the ceramic conduction applies The preparation method of layer includes the following steps:
(1) polyborosiloxane is heated and is melted, add hexamethyldisiloxane;
(2) yttrium oxide, zircon sand ore, carbon nanotube high speed dispersion are obtained into mixture in the polyborosiloxane of fusing;
(3) ceramic fibre is evenly mixed in mixture again, extruding pelletization;
(4) granulation is sintered, sintering temperature is 2200 ~ 2700 DEG C;
(5) it crushes and sprays.
7. a kind of advanced treatment process of coking waste water according to claim 6, it is characterised in that: the two silicon oxygen of hexamethyl The addition time of alkane is no less than 30min.
8. a kind of advanced treatment process of coking waste water according to claim 6, it is characterised in that: the ceramic fibre it is straight Diameter is 3 ~ 5 μm, and length is 15 ~ 25mm.
9. a kind of advanced treatment process of coking waste water according to claim 1, it is characterised in that: right in the step (5) Biological regulation closed cell is evacuated, and control vacuum degree is 10 ~ 30kpa.
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