CN110156237A - A kind of waste water water conservancy recovery method - Google Patents
A kind of waste water water conservancy recovery method Download PDFInfo
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- CN110156237A CN110156237A CN201910586602.2A CN201910586602A CN110156237A CN 110156237 A CN110156237 A CN 110156237A CN 201910586602 A CN201910586602 A CN 201910586602A CN 110156237 A CN110156237 A CN 110156237A
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- coking plant
- mother liquor
- plant wastewater
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- 239000002351 wastewater Substances 0.000 title claims abstract description 45
- 238000000034 method Methods 0.000 title claims abstract description 39
- 238000011084 recovery Methods 0.000 title claims abstract description 19
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 title description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 46
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 43
- 239000012452 mother liquor Substances 0.000 claims abstract description 36
- 238000004939 coking Methods 0.000 claims abstract description 35
- 239000007788 liquid Substances 0.000 claims abstract description 24
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000012028 Fenton's reagent Substances 0.000 claims abstract description 12
- 239000000701 coagulant Substances 0.000 claims abstract description 10
- 238000004821 distillation Methods 0.000 claims abstract description 9
- 238000005189 flocculation Methods 0.000 claims abstract description 9
- 230000016615 flocculation Effects 0.000 claims abstract description 9
- 230000001376 precipitating effect Effects 0.000 claims abstract description 9
- 239000006228 supernatant Substances 0.000 claims abstract description 9
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims abstract description 5
- 229910001628 calcium chloride Inorganic materials 0.000 claims abstract description 5
- 239000001110 calcium chloride Substances 0.000 claims abstract description 5
- 238000001704 evaporation Methods 0.000 claims description 18
- 230000008020 evaporation Effects 0.000 claims description 16
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 9
- 229910052760 oxygen Inorganic materials 0.000 claims description 9
- 239000001301 oxygen Substances 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- 239000004411 aluminium Substances 0.000 claims description 8
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 claims description 8
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 8
- 230000001105 regulatory effect Effects 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 7
- 229920002401 polyacrylamide Polymers 0.000 claims description 6
- 230000015271 coagulation Effects 0.000 claims description 4
- 238000005345 coagulation Methods 0.000 claims description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims 1
- 239000005864 Sulphur Substances 0.000 claims 1
- 239000000460 chlorine Substances 0.000 claims 1
- 229910052801 chlorine Inorganic materials 0.000 claims 1
- 238000006116 polymerization reaction Methods 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 8
- 150000003839 salts Chemical class 0.000 abstract description 5
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 238000004064 recycling Methods 0.000 abstract description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 abstract description 2
- 239000000498 cooling water Substances 0.000 abstract description 2
- 239000013589 supplement Substances 0.000 abstract description 2
- 230000001112 coagulating effect Effects 0.000 abstract 1
- 239000010908 plant waste Substances 0.000 abstract 1
- 238000004062 sedimentation Methods 0.000 abstract 1
- 238000005516 engineering process Methods 0.000 description 8
- -1 Hydroxyl radical free radical Chemical class 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 6
- 238000006385 ozonation reaction Methods 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000010612 desalination reaction Methods 0.000 description 4
- 239000005416 organic matter Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 238000001223 reverse osmosis Methods 0.000 description 3
- 239000010865 sewage Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000000909 electrodialysis Methods 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000011033 desalting Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 239000013505 freshwater Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 238000001471 micro-filtration Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 230000035764 nutrition Effects 0.000 description 1
- 235000016709 nutrition Nutrition 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Chemical group 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
-
- 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
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
- C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
-
- 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
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
- C02F1/5245—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents using basic salts, e.g. of aluminium and iron
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
-
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2201/00—Apparatus for treatment of water, waste water or sewage
- C02F2201/78—Details relating to ozone treatment devices
- C02F2201/782—Ozone generators
-
- 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
- C02F2209/06—Controlling or monitoring parameters in water treatment pH
-
- 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
- C02F2209/07—Alkalinity
-
- 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]
-
- 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
- C02F2209/19—SO4-S
-
- 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
- C02F2209/20—Total organic carbon [TOC]
-
- 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
- C02F2209/29—Chlorine 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
- C02F2301/00—General aspects of water treatment
- C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions
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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
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/023—Reactive oxygen species, singlet oxygen, OH radical
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/026—Fenton's reagent
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- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
The invention discloses a kind of Coking Plant Wastewater water conservancy recovery methods, belong to disposal of coking plant waste water technical field.Comprising: after coagulant and flocculation aid progress 40 ~ 50min of coagulating sedimentation is added, hydrogen peroxide is added in batches into clear liquid, and it is passed through ozone, react 50 ~ 70min, after the pH to 3-4 for adjusting clear liquid, Fenton reagent is added and reacts 50 ~ 70min under 20w-40w ultraviolet light, after adjusting pH to 5-6, calcium chloride is added and is stirred precipitating, and supernatant liquor is taken to carry out distillation processing.Coking Plant Wastewater water conservancy recovery method of the invention is easy to operate, process cycle is short, low energy consumption, secondary pollution will not be generated, it realizes and mother liquor harmless treatment is evaporated to Coking Plant Wastewater, it distills obtained condensate liquid water quality and meets national standard, it can be used as Open recirling cooling water system supplement water to recycle, the salt obtained after distillation can be used as Nacl recycling.
Description
Technical field
The present invention relates to oily coke-oven plant's technical field of waste water processing, and in particular to a kind of Coking Plant Wastewater water conservancy recycling side
Method.
Background technique
Biochemical treatment is generally passed through in the sewage treatment of coke-oven plant at present, and into micro-filtration, ultrafiltration, reverse osmosis units, clear water is used
Used in recirculated water, concentrated water out, generally enter efficient evaporative crystallization technique, crystallization processes using an effect evaporation technique,
Or multiple-effect evaporation technology (MED) or mechanical vapor recompression technology (MVR), investment is big, energy consumption is high, for this purpose, inside coke-oven plant
It merges, optimize in technique, form coking concentrated water New Process for Treatment.
Along with the promulgation of the rare of freshwater resources and more stringent environmental regulation, Technologies of Coke Plant Wastewater Treatment is general at present
All over based on biochemical processing or its improved technology, though saying from technological layer angle, waste water can be made to reach dirty after processing
Water comprehensive discharge primary standard, but since biological treatment is affected by condition elements such as load, poisonous substance, nutrition, it operates in addition
The limitation of personnel's operation level, in actual moving process, the Wastewater Pollutant over-standard phenomenon that often occurs that treated, such as useless
It is easy in the case that water inflow is big more than design flow or impact load exceeded.Therefore simple conventional treatment cannot be guaranteed whole
Wastewater to reach standard, it is necessary to be just able to achieve after further handling all it is up to standard.It is necessary to implement coking wastewater thus
Advanced treating engineering, to guarantee that treated that waste water is all up to standard, to realize the reuse of coking wastewater.
Waste water desalting technology has ion-exchange, electrodialysis, reverse osmosis membrane, Electro Sorb etc..It is de- using ion-exchange
A large amount of acid-base reagent is needed when salt, not only increases cost and serious pollution is caused to environment；Electrodialysis desalination technology
More gas can be generated at runtime, and technique is easily electrolysed；Reverse osmosis deaslination process equipment is expensive, and operating cost is higher,
And there is stringent control to influent quality and intake pressure.To sum up, the advanced desalination technique of coking wastewater concentrates on film at present
Processing aspect.Although more mature using embrane method desalinating process technique to coking wastewater, have the following problems: (1) place
Higher cost is managed, whether three embrane methods or bi-membrane method, desalination departmental cost is all at 15 yuan/ton or more；(2) embrane method producing water ratio is about
60%-70% generates the concentrated water of about 30%-40%, which will cause environmental pollution, according to evaporation and concentration pair
A series of problems, such as concentrated water is handled, and can not be utilized there is also energy consumption height, equipment burn into solid mixed salt residue.Therefore, it is necessary to
Further exploitation is suitable for the advanced desalination treatment process of coking wastewater.
Multiple-effect evaporation technology mainly passes through multiple evaporators and is evaporated to waste water, obtains the evaporation that can be recycled
Condensate liquid, but concentrated water-evaporation mother liquor can be also generated simultaneously.Evaporation mother liquor usually contains that some hydro carbons, condensed ring are nitrogenous, sulfur-bearing is organic
Compound and it largely is difficult to the suspended particulate substance of natural subsidence, belongs to that objectionable impurities is more, high saliferous, the difficult to degrade of high COD have
Machine waste water.Evaporation mother liquor water quality is unstable, and variation water quality is big, and existing coke-oven plant produces waste water evaporation mother liquid disposal technology with place
Manage at high cost, the problems such as effluent quality is poor.
Summary of the invention
The object of the present invention is to provide a kind of Coking Plant Wastewater water conservancy recovery methods, to solve existing Coking Plant Wastewater evaporation
Mother liquid disposal technical treatment is at high cost, the problem of effluent quality difference.
The technical scheme to solve the above technical problems is that
A kind of Coking Plant Wastewater water conservancy recovery method comprising:
(1) coagulant is added into Coking Plant Wastewater evaporation mother liquor and flocculation aid is stirred coagulation, taken after precipitating 40 ~ 50min
Supernatant liquor；
(2) hydrogen peroxide is added in batches into clear liquid, and is passed through ozone, reacts 50 ~ 70min；
(3) Fenton reagent is added in batches, and in 20w-40w ultraviolet light after the pH to 3-4 of clear liquid after regulating step (2) processing
Irradiation is lower to react 50 ~ 70min；
(4) calcium chloride is added and is stirred, is taken after precipitating 40 ~ 50min after the pH to 5-6 of clear liquid after regulating step (3) processing
Layer clear liquid；
(5) supernatant liquor in step (4) is subjected to 40 ~ 60min of distillation processing at 130 DEG C -145 DEG C；
Wherein, Fenton reagent is hydrogen peroxide and green vitriol, be added in mother liquor per ton hydrogen peroxide 5L-10L and
Green vitriol 5kg-8kg.
Wherein, coagulant is aluminium polychloride in step (1), and aluminium polychloride 1kg-3kg is added in mother liquor per ton；It helps
Solidifying agent is polyacrylamide, and polyacrylamide 0.1kg-0.2kg is added in mother liquor per ton.
Preferably, hydrogen peroxide 15L-25L is added in step (2) in mother liquor per ton.
Preferably, the mass fraction of hydrogen peroxide is 30%-35% in step (2).
Preferably, the ozone flow being passed through in step (2) is 0.5L/min-1.2L/min, and the ozone is by ozone
Generator is 60%-70% oxygen using purity to be generated as oxygen source.
Preferably, the mass fraction of the hydrogen peroxide used in Fenton reagent in step (3) is 25%-35%.
Preferably, in the Coking Plant Wastewater evaporation mother liquor in step (1), COD 8000mg/L-14000mg/L；TOC
For 1000mg/L-2000mg/L；Total alkalinity is 15000mg/L-22000mg/L；PH is 10-13；Sulfate is 30000mg/L-
100000mg/L；Chloride ion is 140000mg/L-170000mg/L.
Preferably, the processing water that the processing method obtains, COD are less than 10mg/L；TOC is less than 4mg/L；Total alkali
Degree is less than 70mg/L；PH is 7-8；Sulfate is less than 70mg/L；Chloride ion is less than 18mg/L.
The invention has the following advantages:
1, the present invention is directly added into coagulant and flocculation aid by evaporating in mother liquor in Coking Plant Wastewater, can hang to avoid in mother liquor
Floating particles block pipeline too much, while also improving treatment effeciency.This operation can remove 95% or more suspended matter, be subsequent
Good condition is created in catalytic ozonation and ultraviolet/Fenton processing.
2, the present invention by under hydrogen peroxide catalyzed effect occur catalytic ozonation reaction, reaction pH range with
The pH range of mother liquor is consistent, can directly carry out catalytic ozonation reaction adjusting without soda acid pond, be omitted and adjust pH
Operation shortens the processing time, has saved processing cost.
3, in catalytic ozonation of the invention reaction, ozone generates under hydrogen peroxide catalyzed effect has strong oxidizing property
Hydroxyl radical free radical, achieve the purpose that reduce useless Organic substance in water with this, improve biodegradability.
4, catalytic ozonation of the invention reaction can remove 80% or more organic matter in mother liquor.
5, in ultraviolet light of the invention/Fenton processing, Fenton reagent and ultraviolet cooperating generate the hydroxyl of strong oxidizing property certainly
It by base, is reacted by hydroxyl radical free radical and organic matter in mother liquor, is ultimately oxidized as water, carbon dioxide, inorganic salts etc.
Inorganic matter both accelerates reaction rate, at the same decrease subsequent recovery processing catalyst the step of, both shorten processing the time or
Processing cost is saved.Ultraviolet light of the invention/Fenton processing synergy ozone catalytic oxidation can remove 95% in mother liquor
The above organic matter.
6, in ultraviolet light of the invention/Fenton processing, be conducive to activation and generate greater number of hydroxyl radical free radical, while
Organic molecule mean kinetic energy is increased, to accelerate the reaction speed of organic matter in hydroxyl radical free radical and mother liquor, improves purple
Outer light/Fenton processing efficiency.
7, Coking Plant Wastewater water conservancy recovery method of the invention, operation plus it is simple, process cycle is short, low energy consumption, will not
Secondary pollution is generated, realizes and mother liquor harmless treatment is evaporated to Coking Plant Wastewater, the condensate liquid water quality distilled meets country
Standard can be used as Open recirling cooling water system supplement water and recycle, and the salt obtained after distillation can be used as Nacl recycling benefit
With.
Specific embodiment
Principles and features of the present invention are described with reference to embodiments, the given examples are served only to explain the present invention,
It is not intended to limit the scope of the present invention.The person that is not specified actual conditions in embodiment, according to normal conditions or manufacturer suggests
Condition carries out.Reagents or instruments used without specified manufacturer is the conventional products that can be obtained by commercially available purchase.
Embodiment 1:
The Coking Plant Wastewater water conservancy recovery method of the present embodiment includes:,
(1) coagulant is added into Coking Plant Wastewater evaporation mother liquor and flocculation aid is stirred coagulation, taken after precipitating 40min
Layer clear liquid；Wherein, coagulant is aluminium polychloride, and aluminium polychloride 1kg is added in mother liquor per ton；Flocculation aid is polypropylene
Amide, and polyacrylamide 0.1kg is added in mother liquor per ton.
(2) into clear liquid, hydrogen peroxide is added in point 2 batches, and is passed through ozone, reacts 50min；Matter is added in mother liquor per ton
Measure the hydrogen peroxide 15L that score is 30%；And the ozone flow being passed through is 0.5L/min, ozone is by ozone generator with pure
Degree is that 60% oxygen is that oxygen source generates.
(3) after regulating step (2) processing after the pH to 3 of clear liquid, Fenton reagent is added in point 2 batches, and in 20w ultraviolet light
Irradiation is lower to react 50min；Wherein, Fenton reagent includes hydrogen peroxide and green vitriol, and quality is added in mother liquor per ton
The hydrogen peroxide 5L and green vitriol 7kg that score is 25%.
(4) calcium chloride is added and is stirred, is taken after precipitating 40min after the pH to 5 of clear liquid after regulating step (3) processing
Supernatant liquor；
(5) supernatant liquor in step (4) is subjected to distillation processing 40min at 130 DEG C.
In the present embodiment in Coking Plant Wastewater evaporation mother liquor, COD 8000mg/L；TOC is 1000mg/L；Total alkalinity is
15000mg/L；PH is 10；Sulfate is 30000mg/L；Chloride ion is 140000mg/L.
In the processing water of Coking Plant Wastewater water conservancy recovery method processing through the present embodiment, COD 7mg/L；TOC is
3mg/L；Total alkalinity is 65mg/L；PH is 7；Sulfate is 60mg/L；Chloride ion is 10mg/L.Step (5) distillation obtains cold
Lime set water quality meets " urban sewage reutilization industry water standard " (GB/T 19923-2005) national standard.
Embodiment 2:
The Coking Plant Wastewater water conservancy recovery method of the present embodiment includes:,
(1) coagulant is added into Coking Plant Wastewater evaporation mother liquor and flocculation aid is stirred coagulation, taken after precipitating 50min
Layer clear liquid；Wherein, coagulant is aluminium polychloride, and aluminium polychloride 3kg is added in mother liquor per ton；Flocculation aid is polypropylene
Amide, and polyacrylamide 0.2kg is added in mother liquor per ton.
(2) into clear liquid, hydrogen peroxide is added in point 2 batches, and is passed through ozone, reacts 60min；Matter is added in mother liquor per ton
Measure the hydrogen peroxide 20L that score is 30%；And the ozone flow being passed through is 0.8L/min, ozone is by ozone generator with pure
Degree is that 66% oxygen is that oxygen source generates.
(3) after regulating step (2) processing after the pH to 3 of clear liquid, Fenton reagent is added in point 2 batches, and in 20w ultraviolet light
Irradiation is lower to react 60min；Wherein, Fenton reagent includes hydrogen peroxide and green vitriol, and quality is added in mother liquor per ton
The hydrogen peroxide 5L and green vitriol 7kg that score is 25%.
(4) calcium chloride is added and is stirred, is taken after precipitating 40min after the pH to 5 of clear liquid after regulating step (3) processing
Supernatant liquor；
(5) supernatant liquor in step (4) is subjected to distillation processing 60min at 140 DEG C.
In the present embodiment in Coking Plant Wastewater evaporation mother liquor, COD 14000mg/L；TOC is 2000mg/L；Total alkalinity
For 22000mg/L；PH is 13；Sulfate is 100000mg/L；Chloride ion is 170000mg/L.
In the processing water of Coking Plant Wastewater water conservancy recovery method processing through the present embodiment, COD 9mg/L；TOC is
3mg/L；Total alkalinity is 65mg/L；PH is 7.5；Sulfate is 65mg/L；Chloride ion is 15mg/L.Step (5) distillation obtains
Condensate liquid water quality meets " urban sewage reutilization industry water standard " (GB/T 19923-2005) national standard.
The foregoing is merely presently preferred embodiments of the present invention, is not intended to limit the invention, it is all in spirit of the invention and
Within principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (7)
1. a kind of Coking Plant Wastewater water conservancy recovery method, it is characterised in that:
(1) coagulant is added into Coking Plant Wastewater evaporation mother liquor and flocculation aid is stirred coagulation, taken after precipitating 40 ~ 50min
Supernatant liquor；
(2) hydrogen peroxide is added in batches into clear liquid, and is passed through ozone, reacts 50 ~ 70min；
(3) Fenton reagent is added in batches, and in 20w-40w ultraviolet light after the pH to 3-4 of clear liquid after regulating step (2) processing
Irradiation is lower to react 50 ~ 70min；
(4) calcium chloride is added and is stirred, is taken after precipitating 40 ~ 50min after the pH to 5-6 of clear liquid after regulating step (3) processing
Layer clear liquid；
(5) supernatant liquor in step (4) is subjected to 40 ~ 60min of distillation processing at 130 DEG C -145 DEG C；
Wherein, Fenton reagent is hydrogen peroxide and green vitriol, be added in mother liquor per ton hydrogen peroxide 5L-10L and
Green vitriol 5kg-8kg, wherein coagulant is aluminium polychloride in step (1), and polymerization chlorine is added in mother liquor per ton
Change aluminium 1kg-3kg；Flocculation aid is polyacrylamide, and polyacrylamide 0.1kg-0.2kg is added in mother liquor per ton.
2. Coking Plant Wastewater water conservancy recovery method according to claim 1, which is characterized in that mother liquor per ton in step (2)
Middle addition hydrogen peroxide 15L-25L.
3. Coking Plant Wastewater water conservancy recovery method according to claim 3, which is characterized in that hydrogen peroxide in step (2)
Mass fraction be 30%-35%.
4. Coking Plant Wastewater water conservancy recovery method according to claim 1, which is characterized in that be passed through in step (2) smelly
Oxygen flow is 0.5L/min-1.2L/min, and it using purity is 60%-70% oxygen as oxygen source that the ozone, which is by ozone generator,
It generates.
5. Coking Plant Wastewater water conservancy recovery method according to claim 1, which is characterized in that Fenton reagent in step (3)
The mass fraction of the middle hydrogen peroxide used is 25%-35%.
6. Coking Plant Wastewater water conservancy recovery method according to claim 1, which is characterized in that the coke-oven plant in step (1)
Waste water evaporates in mother liquor, COD 8000mg/L-14000mg/L；TOC is 1000mg/L-2000mg/L；Total alkalinity is
15000mg/L-22000mg/L；PH is 10-13；Sulfate is 30000mg/L-100000mg/L；Chloride ion is 140000mg/
L-170000mg/L。
7. Coking Plant Wastewater water conservancy recovery method according to claim 1-6, which is characterized in that the processing side
The processing water that method obtains, COD are less than 10mg/L；TOC is less than 4mg/L；Total alkalinity is less than 70mg/L；PH is 7-8；Sulphur
Hydrochlorate is less than 70mg/L；Chloride ion is less than 18mg/L.
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