CN109626677B - Coking wastewater advanced treatment process - Google Patents
Coking wastewater advanced treatment process Download PDFInfo
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F9/00—Multistage treatment of water, waste water or sewage
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- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
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- 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
- C02F1/4672—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation
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- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/48—Treatment of water, waste water, or sewage with magnetic or electric fields
- C02F1/488—Treatment of water, waste water, or sewage with magnetic or electric fields for separation of magnetic materials, e.g. magnetic flocculation
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- 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
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
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- 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
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- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
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- 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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- C02F2209/14—NH3-N
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- C02F2301/00—General aspects of water treatment
- C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions
Abstract
The invention relates to a coking wastewater advanced treatment process, which comprises the following steps: (1) filtering; (2) magnetic separation and purification; (3) adding a low-temperature coagulant aid for precipitation treatment; (4) electrocatalytic oxidation; (5) biological treatment; (6) filtering by a membrane filter; the low-temperature coagulant aid is adopted, so that the coagulation effect of the coking wastewater with lower temperature can be improved, and the subsequent purification efficiency of the coking wastewater can be improved; then carrying out electrocatalytic oxidation treatment to generate hydroxyl free radicals with high oxidation potential, oxidizing organic matters in the wastewater in a large area, simultaneously aerating to generate stirring effect, and promoting the discharge of scum in the electrocatalytic process; by adopting the process to treat the coking wastewater, the coking wastewater with effluent COD and ammonia nitrogen reaching standards can be prepared.
Description
Technical Field
The invention relates to the technical field of wastewater treatment, in particular to a coking wastewater advanced treatment process.
Background
Coking wastewater is a recognized industrial wastewater difficult to biodegrade, the difficulty lies in poor biodegradability of the wastewater, and the wastewater contains phenols, naphthalene, pyridine, quinoline and other heterocyclic rings and polycyclic aromatic compounds (PAHS) besides inorganic pollutants such as ammonia, cyanogen, thiocyanate and the like, and is difficult to biodegrade, the substances can generate long-term influence on the environment, and part of the substances are researched and proved to be carcinogenic substances, in addition, high-concentration ammonia nitrogen has strong inhibition effect on microbial activity, and the biological denitrification effect is poor. At present, the coking wastewater treatment generally adopts a biological treatment method based on biological strengthening processes such as A/O or A/O/O, A/A/O, O/A/O and the like after the A/O process is improved, coagulating sedimentation treatment is often adopted after the biological treatment method, the requirement of emission standard is met, in addition, the deep treatment cost is high, a plurality of domestic coking plants are forbidden, most coking wastewater is directly discharged after secondary treatment, and toxic and harmful substances (cyanide, COD, heterocyclic compounds and the like) in the wastewater are still more remained after the treatment, and the discharge standard which is allowed by the state cannot be met.
At present, coking wastewater treatment methods can be divided into physical methods and biochemical methods. The physical and chemical methods include solvent extraction to remove phenol, lime or caustic soda distillation to remove ammonia, basic chlorination to remove cyanogen and ammonia, chemical oxidation to remove organic matter, wet oxidation and activated carbon adsorption. The physicochemical method has high pollutant removal efficiency and stable and reliable operation, but the removal of various pollutants usually needs combined use of a plurality of methods and has high operation cost, so the prior physicochemical method is mainly used for pretreatment or subsequent treatment of biological treatment. The biochemical method is a main means for treating the coking wastewater, and can remove various pollutants in a single biological treatment system, and has the advantages of simple operation and much lower operation cost than the biochemical method.
In recent years, biological denitrification processes have attracted more attention and become the main method for treating coking wastewater, and an anoxic-aerobic or anaerobic-anoxic-aerobic activated sludge process is generally adopted. The processes utilize different degradation characteristics of anaerobic bacteria, facultative bacteria and aerobic bacteria, and compared with a common activated sludge method, the process has great improvement on COD (chemical oxygen demand) and ammonia nitrogen removal, but because coking wastewater contains various refractory toxic organic matters and has the characteristics of complex and changeable water quality and water quantity, the anoxic-aerobic activated sludge process is easy to impact, and particularly because autotrophic nitrifying bacteria in an aerobic section have long generation time, the autotrophic nitrifying bacteria are slowly recovered after being impacted, the nitrifying efficiency is reduced, and the COD and ammonia nitrogen in effluent of the process are difficult to reach the standard at the same time.
Disclosure of Invention
The invention aims to provide a coking wastewater advanced treatment process which is beneficial to the effluent COD and ammonia nitrogen of the coking wastewater to reach the standard simultaneously.
The above object of the present invention is achieved by the following technical solutions:
a coking wastewater advanced treatment process comprises the following steps:
(1) putting the coking wastewater into a mixed precipitation tank, adjusting the pH value of the coking wastewater to 7.5-8, and filtering through a multi-media filter;
(2) after filtering, purifying again by adopting a magnetic separation technology;
(3) adding a low-temperature coagulant aid for precipitation treatment, wherein the low-temperature coagulant aid comprises the following components in parts by weight: 80-85 parts of activated silicic acid, 3-7 parts of industrial aluminum sulfate, 1-5 parts of sodium dimeric phosphate, 10-15 parts of hydrogen peroxide and 1-5 parts of ammonium persulfate;
(4) after precipitation, putting the coking wastewater into an electrocatalytic oxidation reaction tank, and aerating the bottom of the reaction tank, wherein a ceramic conductive coating is sprayed on the surface of an electrode and is heated by microwaves;
(5) discharging the coking wastewater into a biological regulation closed tank after catalysis, regulating the pH value of the coking wastewater to 3.5-4.5, regulating the temperature in the tank to 60-85 ℃, stirring for 1-3 h by adopting ultrasonic waves, and standing for at least 10 h;
(6) after standing, filtering the coking wastewater by using a membrane filter, wherein the membrane filter is formed by weaving high-activity fiber materials.
By adopting the technical scheme, firstly, the coking wastewater is subjected to alkalization treatment, which is beneficial to flocculation and precipitation in the coking wastewater; the sediment and impurity particles in the coking wastewater are removed through the filtration and purification of a multi-medium filter and a magnetic separation technology; the low-temperature coagulant aid is adopted, so that the coagulation effect of the coking wastewater with lower temperature can be improved, and the subsequent purification efficiency of the coking wastewater can be improved; then carrying out electrocatalytic oxidation treatment to generate hydroxyl free radicals with high oxidation potential, oxidizing organic matters in the wastewater in a large area, simultaneously aerating to generate stirring effect, promoting the discharge of scum in the electrocatalytic process, heating by microwave and obviously shortening the time of the electrocatalytic oxidation process; finally, biochemical treatment is carried out by utilizing a biological regulation closed tank, and the pH and the temperature are regulated, so that the efficiency of the biochemical treatment can be obviously improved; by adopting the process to treat the coking wastewater, the coking wastewater with effluent COD and ammonia nitrogen reaching standards can be prepared.
The invention is further configured to: the multi-media filter in the step (1) comprises a smokeless coal bed, a fine sand layer and a coarse sand layer which are sequentially paved from top to bottom, and the particle sizes of the smokeless coal bed, the fine sand layer and the coarse sand layer are sequentially increased.
Through adopting above-mentioned technical scheme, the particle size in smokeless coal seam, fine sand layer and coarse sand layer increases in proper order, can carry out effective filtration with the impurity of different particle sizes in the coking wastewater to the realization is to the prefilter of coking wastewater.
The invention is further configured to: and (3) adopting a titanium plate as an electrode in the electrocatalytic oxidation reaction tank in the step (3), and sequentially performing ultrasonic alkali washing, oxalic acid solution soaking with the mass concentration of 25%, deionized water washing and drying on the surface of the titanium plate.
By adopting the technical scheme, the titanium plate is firstly subjected to alkalization treatment, and the ultrasonic alkali washing can also promote the impurity ions in the coking wastewater to be distributed more uniformly; then, carrying out acidification treatment on the titanium plate to remove a passivation film on the surface and generate an activation effect on the surface of the titanium plate; and cleaning with deionized water to obtain the titanium plate base layer with high surface cleanliness and easy coating adhesion.
The invention is further configured that the ceramic conductive coating comprises the following components in parts by weight:
70-75 parts of yttrium oxide, 10-12 parts of zircon sand ore, 1-5 parts of carbon nano tube, 1-5 parts of ceramic fiber, 1-3 parts of polyborosiloxane and 5-10 parts of hexamethyldisiloxane.
By adopting the technical scheme, the yttrium oxide (Y)2O3) The material has a cubic structure, high melting point, good chemical and photochemical stability, wide optical transparency range, high refractive index, high theoretical transmittance and high thermal conductivity, belongs to rare earth metal oxide, has strong polarization capability and high diversity of electronic energy level and spectral line, and is beneficial to degrading organic matters in wastewater; the zircon sand ore has high refractoriness, high density, large heat storage coefficient, strong metal penetration resistance, smooth surface, easy combination with various binders and excellent high-temperature resistance; the carbon nano tube has excellent adsorption performance, and the adsorption binding property of the adsorption filler with other component fillers can be increased in the material mixing process, the binding force with other fillers can be increased, and the integral binding property is better; the ceramic fiber has excellent fire resistance, high temperature resistance and corrosion resistance, and the high temperature resistance and the corrosion resistance of the casting sand can be improved by adding a small amount of the ceramic fiber; the polyborosiloxane is carbonized after high temperature, has excellent adhesive property after carbonization, has smaller grain size compared with other fillers, is favorable for filling gaps generated among other fillers, and increases the associativity among components; the polyborosiloxane with the particle size of less than 500nm has higher preparation cost, and the polyborosiloxane with the particle size of more than 1000nm has larger particles, which indicates that the agglomeration phenomenon, the high temperature resistance and the adhesive property are influenced in the synthesis process; hexamethyldisiloxane is colorless transparent liquid, can promote mutual wetting of all components in a coating system, and has good solubility, foamability, hard water resistance, lime soap dispersibility and good biodegradability; the conductive coating prepared by adopting the components increases the specific surface area and the oxidation activity of the coating, and is beneficial to improving the degradation degree of coking wastewater.
The invention is further configured to: the particle size of the yttrium oxide is 50-100 nm.
By adopting the technical scheme, the nanoscale yttrium oxide can be uniformly dispersed in the molten polyborosiloxane, has excellent dispersibility, and reduces the uneven settlement of the conductive coating.
The invention further provides that the preparation method of the ceramic conductive coating comprises the following steps:
(1) heating and melting polyborosiloxane, and adding hexamethyldisiloxane;
(2) dispersing yttrium oxide, zircon sand ore and carbon nano tubes in molten polyborosiloxane at a high speed to obtain a blend;
(3) then uniformly mixing the ceramic fibers in the blend, and extruding and granulating;
(4) sintering the granules at 2200-2700 ℃;
(5) pulverizing and spraying.
By adopting the technical scheme, firstly hexamethyldisiloxane slowly permeates into polyborosiloxane, which is helpful for wetting, dissolving and permeating polyborosiloxane and other components, then yttrium oxide, zircon sand ore and carbon nano tubes are dispersed in polyborosiloxane at a high speed, then ceramic fibers are added and blended in a reaction system, and after uniform mixing, extrusion granulation and crushing are carried out, thus preparing the conductive coating with uniform texture and easy adhesion on the surface.
The invention is further configured to: the addition time of the hexamethyldisiloxane is not less than 30 min.
By adopting the technical scheme, the adding time of the hexamethyldisiloxane is limited, the hexamethyldisiloxane can be ensured to be slowly added into a reaction system, the hexamethyldisiloxane can be uniformly permeated into the polyborosiloxane, the surface tension of the polyborosiloxane can be reduced, and the uniformity of mixing with other components can be ensured.
The invention is further configured to: the ceramic fiber has a diameter of 3-5 μm and a length of 15-25 mm.
By adopting the technical scheme, the diameter and the length of the ceramic fiber are limited, the ceramic fiber is favorably and uniformly dispersed in a reaction system, and the high temperature resistance and the ablation resistance of the conductive coating are improved.
The invention is further configured to: and (5) exhausting the biological regulation closed tank, and controlling the vacuum degree to be 10-30 kpa.
Through adopting above-mentioned technical scheme, set for vacuum degree and be 10~30kpa, can realize extracting the flocculating constituent of solid state, still can take away the foul smell in the sewage, have excellent treatment effect.
In conclusion, the beneficial technical effects of the invention are as follows:
1. the invention discloses an advanced treatment process of coking wastewater, which comprises the steps of firstly adjusting the coking wastewater to be alkaline, and adding a low-temperature coagulant aid to facilitate uniform sedimentation of the coking wastewater at a lower temperature;
2. after the primary filtration, the coking wastewater is subjected to electrocatalytic oxidation, and the catalytic process has high catalytic efficiency and is beneficial to deep degradation of the coking wastewater;
3. the surface of the catalytic electrode is sprayed to form a ceramic conductive coating, so that the specific surface area and the oxidation activity of the coating are increased, and the catalytic electrode has excellent catalytic activity;
4. in the biological treatment process, the negative pressure air extraction is adopted, so that scum on the surface of the catalytic electrode can be extracted, and meanwhile, the smell generated by the electrolytic reaction can be removed, thereby improving the practicability of the electrocatalytic oxidation system.
Detailed Description
The present invention will be described in further detail with reference to examples.
The first embodiment is as follows:
a low-temperature coagulant aid is prepared by the following steps:
(1) preparing materials: weighing 80 parts of activated silicic acid, 3 parts of industrial aluminum sulfate, 1 part of sodium dimeric phosphate, 10 parts of hydrogen peroxide and 1 part of ammonium persulfate according to parts by weight;
(2) adding industrial aluminum sulfate and sodium dimeric phosphate into activated silicic acid, and uniformly stirring;
(3) continuously adding the hydrogen peroxide and the ammonium persulfate, and uniformly mixing.
Example two:
a low-temperature coagulant aid is different from the first embodiment in the component content of the low-temperature coagulant aid, and 81 parts of activated silicic acid, 4 parts of industrial aluminum sulfate, 2 parts of sodium dimeric phosphate, 11 parts of hydrogen peroxide and 2 parts of ammonium persulfate are weighed.
Example three:
a low-temperature coagulant aid is different from the first embodiment in the component content of the low-temperature coagulant aid, and 82 parts of activated silicic acid, 5 parts of industrial aluminum sulfate, 3 parts of sodium dimeric phosphate, 12 parts of hydrogen peroxide and 3 parts of ammonium persulfate are weighed.
Example four:
a low-temperature coagulant aid is different from the first embodiment in the component content of the low-temperature coagulant aid, and 84 parts of activated silicic acid, 6 parts of industrial aluminum sulfate, 4 parts of sodium dimeric phosphate, 14 parts of hydrogen peroxide and 4 parts of ammonium persulfate are weighed.
Example five:
a low-temperature coagulant aid is different from the first embodiment in the component content of the low-temperature coagulant aid, and 85 parts of activated silicic acid, 7 parts of industrial aluminum sulfate, 5 parts of sodium dimeric phosphate, 15 parts of hydrogen peroxide and 5 parts of ammonium persulfate are weighed.
Example six:
a catalytic electrode is prepared by the following method:
(1) the catalytic electrode adopts a titanium plate, and the surface of the titanium plate is firstly subjected to ultrasonic alkali washing;
(2) after alkali washing, soaking the substrate in an oxalic acid solution with the mass concentration of 25%;
(3) cleaning with deionized water and drying;
(4) spraying a ceramic conductive coating: a) preparing materials: weighing 70 parts of yttrium oxide, 10 parts of zircon sand ore, 1 part of carbon nanotube, 1 part of ceramic fiber, 1 part of polyborosiloxane and 5 parts of hexamethyldisiloxane according to parts by weight; b) heating and melting polyborosiloxane, and adding hexamethyldisiloxane for no less than 30 min; c) dispersing yttrium oxide, zircon sand ore and carbon nano tubes in molten polyborosiloxane at a high speed to obtain a blend; d) then uniformly mixing the ceramic fibers in the blend, and extruding and granulating; e) sintering the granules at 2200-2700 ℃; f) pulverizing and spraying.
Example seven:
a catalytic electrode was distinguished from example six in that the conductive coating had different component contents by weighing 72 parts of yttrium oxide, 10 parts of zircon sand ore, 2 parts of carbon nanotubes, 2 parts of ceramic fibers, 1 part of polyborosiloxane and 7 parts of hexamethyldisiloxane in parts by weight.
Example eight:
a catalytic electrode was distinguished from example six in that the conductive coating had different content of components, and 73 parts by weight of yttrium oxide, 11 parts by weight of zircon sand ore, 3 parts by weight of carbon nanotubes, 3 parts by weight of ceramic fibers, 2 parts by weight of polyborosiloxane and 7 parts by weight of hexamethyldisiloxane were weighed.
Example nine:
a catalytic electrode distinguished from example six in the content of the conductive coating by the composition, in parts by weight, of yttrium oxide 74 parts, zircon sand ore 12 parts, carbon nanotubes 4 parts, ceramic fibers 4 parts, polyborosiloxane 3 parts, and hexamethyldisiloxane 9.
Example ten:
a catalytic electrode was distinguished from example six in that the conductive coating had different content of components, and 75 parts by weight of yttrium oxide, 12 parts by weight of zircon sand ore, 5 parts by weight of carbon nanotubes, 5 parts by weight of ceramic fibers, 3 parts by weight of polyborosiloxane and 10 parts by weight of hexamethyldisiloxane were weighed.
Example eleven:
a coking wastewater advanced treatment process comprises the following steps:
(1) putting the coking wastewater into a mixed sedimentation tank, adjusting the pH value of the coking wastewater to 7.5, and filtering by a multi-media filter, wherein the multi-media filter comprises a smokeless coal layer, a fine sand layer and a coarse sand layer which are sequentially paved from top to bottom;
(2) after filtering, purifying again by adopting a magnetic separation technology;
(3) adding a low-temperature coagulant aid for precipitation treatment, wherein the low-temperature coagulant aid is prepared by adopting the first embodiment;
(4) after precipitation, the coking wastewater is put into an electrocatalytic oxidation reaction tank, aeration is carried out on the bottom of the reaction tank, wherein a catalytic electrode is prepared by the sixth embodiment, and microwave heating is adopted in the catalytic process;
(5) after catalysis, discharging the coking wastewater into a biological regulation closed tank, simultaneously exhausting the biological regulation closed tank, controlling the vacuum degree to be 10-30 kpa, regulating the pH value of the coking wastewater to be 3.5, regulating the temperature in the tank to be 60 ℃, stirring for 1h by adopting ultrasonic waves, and standing for 10 h;
(6) after standing, filtering the coking wastewater by using a membrane filter, wherein the membrane filter is formed by weaving high-activity fiber materials.
Example twelve:
a coking wastewater advanced treatment process comprises the following steps:
(1) putting the coking wastewater into a mixed sedimentation tank, adjusting the pH value of the coking wastewater to 7.7, and filtering by a multi-media filter, wherein the multi-media filter comprises a smokeless coal layer, a fine sand layer and a coarse sand layer which are sequentially paved from top to bottom;
(2) after filtering, purifying again by adopting a magnetic separation technology;
(3) adding a low-temperature coagulant aid for precipitation treatment, wherein the low-temperature coagulant aid is prepared by adopting the second embodiment;
(4) after precipitation, the coking wastewater is put into an electrocatalytic oxidation reaction tank, aeration is carried out on the bottom of the reaction tank, wherein a catalytic electrode is prepared by the preparation method of the seventh embodiment, and microwave heating is adopted in the catalytic process;
(5) after catalysis, discharging the coking wastewater into a biological regulation closed tank, simultaneously exhausting the biological regulation closed tank, controlling the vacuum degree to be 10-30 kpa, regulating the pH value of the coking wastewater to be 3.8, regulating the temperature in the tank to be 65 ℃, stirring for 1.5h by adopting ultrasonic waves, and standing for 12 h;
(6) after standing, filtering the coking wastewater by using a membrane filter, wherein the membrane filter is formed by weaving high-activity fiber materials.
Example thirteen:
a coking wastewater advanced treatment process comprises the following steps:
(1) putting the coking wastewater into a mixed sedimentation tank, adjusting the pH value of the coking wastewater to 7.8, and filtering by a multi-media filter, wherein the multi-media filter comprises a smokeless coal layer, a fine sand layer and a coarse sand layer which are sequentially paved from top to bottom;
(2) after filtering, purifying again by adopting a magnetic separation technology;
(3) adding a low-temperature coagulant aid for precipitation treatment, wherein the low-temperature coagulant aid is prepared by adopting the third embodiment;
(4) after precipitation, the coking wastewater is put into an electrocatalytic oxidation reaction tank, aeration is carried out on the bottom of the reaction tank, wherein a catalytic electrode is prepared by adopting the embodiment eight, and microwave heating is adopted in the catalytic process;
(5) after catalysis, discharging the coking wastewater into a biological regulation closed tank, simultaneously exhausting the biological regulation closed tank, controlling the vacuum degree to be 10-30 kpa, regulating the pH value of the coking wastewater to be 4.0, regulating the temperature in the tank to be 70 ℃, stirring for 2 hours by adopting ultrasonic waves, and standing for 12 hours;
(6) after standing, filtering the coking wastewater by using a membrane filter, wherein the membrane filter is formed by weaving high-activity fiber materials.
Example fourteen:
a coking wastewater advanced treatment process comprises the following steps:
(1) putting the coking wastewater into a mixed sedimentation tank, adjusting the pH value of the coking wastewater to be 8, and filtering the coking wastewater by a multi-medium filter, wherein the multi-medium filter comprises a smokeless coal layer, a fine sand layer and a coarse sand layer which are sequentially paved from top to bottom;
(2) after filtering, purifying again by adopting a magnetic separation technology;
(3) adding a low-temperature coagulant aid for precipitation treatment, wherein the low-temperature coagulant aid is prepared by adopting the fourth embodiment;
(4) after precipitation, the coking wastewater is put into an electrocatalytic oxidation reaction tank, aeration is carried out on the bottom of the reaction tank, wherein a catalytic electrode is prepared by adopting the ninth embodiment, and microwave heating is adopted in the catalytic process;
(5) discharging the coking wastewater into a biological regulation closed tank after catalysis, simultaneously exhausting the biological regulation closed tank, controlling the vacuum degree to be 10-30 kpa, regulating the pH value of the coking wastewater to be 4.2, regulating the temperature in the tank to be 75 ℃, stirring for 2.5h by adopting ultrasonic waves, and standing for 14h
(6) After standing, filtering the coking wastewater by using a membrane filter, wherein the membrane filter is formed by weaving high-activity fiber materials.
Example fifteen:
a coking wastewater advanced treatment process comprises the following steps:
(1) putting the coking wastewater into a mixed sedimentation tank, adjusting the pH value of the coking wastewater to be 8, and filtering the coking wastewater by a multi-medium filter, wherein the multi-medium filter comprises a smokeless coal layer, a fine sand layer and a coarse sand layer which are sequentially paved from top to bottom;
(2) after filtering, purifying again by adopting a magnetic separation technology;
(3) adding a low-temperature coagulant aid for precipitation treatment, wherein the low-temperature coagulant aid is prepared by adopting the fifth embodiment;
(4) after precipitation, the coking wastewater is put into an electrocatalytic oxidation reaction tank, aeration is carried out on the bottom of the reaction tank, wherein a catalytic electrode is prepared by adopting the embodiment ten, and microwave heating is adopted in the catalytic process;
(5) after catalysis, discharging the coking wastewater into a biological regulation closed tank, simultaneously exhausting the biological regulation closed tank, controlling the vacuum degree to be 10-30 kpa, regulating the pH value of the coking wastewater to be 4.5, regulating the temperature in the tank to be 85 ℃, stirring for 3 hours by adopting ultrasonic waves, and standing for 15 hours;
(6) after standing, filtering the coking wastewater by using a membrane filter, wherein the membrane filter is formed by weaving high-activity fiber materials.
Comparative example:
an advanced treatment process of coking wastewater, comprising the following steps:
(1) putting the coking wastewater into a mixed precipitation tank, adjusting the pH value of the coking wastewater to 7.2, and filtering by a multi-medium filter;
(2) after filtering, putting the coking wastewater into an electrocatalytic oxidation reaction tank, wherein a catalytic electrode adopts an iron plate electrode;
(5) after catalysis, discharging the coking wastewater into a biological regulating tank, regulating the pH value of the coking wastewater to 3, regulating the temperature in the tank to 25 ℃, and standing for 15 hours;
(6) after standing, the coking wastewater is filtered by a membrane filter.
The detection method comprises the following steps:
(1) and (3) COD detection: according to GB/T11914-1989, the dichromate method is adopted for detection;
(2) ammonia nitrogen removal: according to GB/T7479-1987, the detection is carried out by adopting a Nassner reagent colorimetric method.
The detection results of COD and ammonia nitrogen content of the effluent are shown in the following table:
| sample (I) | COD removal Rate (%) | Ammonia nitrogen removal (%) |
| EXAMPLE eleven | 98.5 | 87.3 |
| Example twelve | 98.7 | 88.1 |
| EXAMPLE thirteen | 98.4 | 89.2 |
| Example fourteen | 98.8 | 90.7 |
| Example fifteen | 98.6 | 88.6 |
| Comparative example | 92.5 | 75.6 |
As can be seen from the table above, compared with the treatment process of the comparative example, the coking wastewater treated by the advanced treatment process provided by the application has the advantages that the removal rate of COD and ammonia nitrogen is improved, and the advanced treatment of the coking wastewater can be realized.
The embodiments of the present invention are preferred embodiments of the present invention, and the scope of the present invention is not limited by these embodiments, so: all equivalent changes made according to the structure, shape and principle of the invention are covered by the protection scope of the invention.
Claims (7)
1. The advanced treatment process of the coking wastewater is characterized by comprising the following steps:
(1) putting the coking wastewater into a mixed precipitation tank, adjusting the pH value of the coking wastewater to 7.5-8, and filtering through a multi-media filter;
(2) after filtering, purifying again by adopting a magnetic separation technology;
(3) adding a low-temperature coagulant aid for precipitation treatment, wherein the low-temperature coagulant aid comprises the following components in parts by weight: 80-85 parts of activated silicic acid, 3-7 parts of industrial aluminum sulfate, 1-5 parts of sodium dimeric phosphate, 10-15 parts of hydrogen peroxide and 1-5 parts of ammonium persulfate;
(4) after precipitation, putting the coking wastewater into an electrocatalytic oxidation reaction tank, and aerating the bottom of the reaction tank, wherein a ceramic conductive coating is sprayed on the surface of an electrode and is heated by microwaves, and the ceramic conductive coating comprises the following components in parts by weight: 70-75 parts of yttrium oxide, 10-12 parts of zircon sand ore, 1-5 parts of carbon nano tube, 1-5 parts of ceramic fiber, 1-3 parts of polyborosiloxane and 5-10 parts of hexamethyldisiloxane; the preparation method of the ceramic conductive coating comprises the following steps: heating and melting polyborosiloxane, and adding hexamethyldisiloxane; dispersing yttrium oxide, zircon sand ore and carbon nano tubes in molten polyborosiloxane at high speed to obtain a blended body; thirdly, uniformly mixing the ceramic fibers in the blend, and extruding and granulating; sintering the granules, wherein the sintering temperature is 2200-2700 ℃; crushing and spraying;
(5) discharging the coking wastewater into a biological regulation closed tank after catalysis, regulating the pH value of the coking wastewater to 3.5-4.5, regulating the temperature in the tank to 60-85 ℃, stirring for 1-3 h by adopting ultrasonic waves, and standing for at least 10 h;
(6) after standing, filtering the coking wastewater by using a membrane filter, wherein the membrane filter is formed by weaving high-activity fiber materials.
2. The coking wastewater advanced treatment process of claim 1, which is characterized in that: the multi-media filter in the step (1) comprises a smokeless coal bed, a fine sand layer and a coarse sand layer which are sequentially paved from top to bottom, and the particle sizes of the smokeless coal bed, the fine sand layer and the coarse sand layer are sequentially increased.
3. The coking wastewater advanced treatment process of claim 1, which is characterized in that: and (4) adopting a titanium plate as an electrode in the electrocatalytic oxidation reaction tank in the step (4), and sequentially performing ultrasonic alkali washing, oxalic acid solution soaking with the mass concentration of 25%, deionized water washing and drying on the surface of the titanium plate.
4. The coking wastewater advanced treatment process of claim 1, which is characterized in that: the particle size of the yttrium oxide is 50-100 nm.
5. The coking wastewater advanced treatment process of claim 1, which is characterized in that: the addition time of the hexamethyldisiloxane is not less than 30 min.
6. The coking wastewater advanced treatment process of claim 1, which is characterized in that: the ceramic fiber has a diameter of 3-5 μm and a length of 15-25 mm.
7. The coking wastewater advanced treatment process of claim 1, which is characterized in that: and (5) exhausting the biological regulation closed tank, and controlling the vacuum degree to be 10-30 kPa.
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