CN108892309A - A kind of high-efficient treatment method being suitble to coking wastewater difficult to degrade - Google Patents
A kind of high-efficient treatment method being suitble to coking wastewater difficult to degrade Download PDFInfo
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- CN108892309A CN108892309A CN201810662006.3A CN201810662006A CN108892309A CN 108892309 A CN108892309 A CN 108892309A CN 201810662006 A CN201810662006 A CN 201810662006A CN 108892309 A CN108892309 A CN 108892309A
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- 239000002351 wastewater Substances 0.000 title claims abstract description 96
- 238000000034 method Methods 0.000 title claims abstract description 80
- 238000004939 coking Methods 0.000 title claims abstract description 51
- 238000011282 treatment Methods 0.000 title claims abstract description 46
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 84
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 78
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 37
- 230000003647 oxidation Effects 0.000 claims abstract description 35
- 238000005189 flocculation Methods 0.000 claims abstract description 30
- 230000016615 flocculation Effects 0.000 claims abstract description 30
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- 238000006477 desulfuration reaction Methods 0.000 claims abstract description 25
- 230000023556 desulfurization Effects 0.000 claims abstract description 25
- 238000004062 sedimentation Methods 0.000 claims abstract description 25
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 24
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910017112 Fe—C Inorganic materials 0.000 claims abstract description 21
- 238000004140 cleaning Methods 0.000 claims abstract description 18
- 229910000027 potassium carbonate Inorganic materials 0.000 claims abstract description 15
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 11
- 239000010802 sludge Substances 0.000 claims description 34
- 239000000945 filler Substances 0.000 claims description 25
- 238000005273 aeration Methods 0.000 claims description 15
- 230000003197 catalytic effect Effects 0.000 claims description 12
- 230000001376 precipitating effect Effects 0.000 claims description 12
- 239000006228 supernatant Substances 0.000 claims description 12
- 238000012545 processing Methods 0.000 claims description 10
- 239000000571 coke Substances 0.000 claims description 9
- 239000007789 gas Substances 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 9
- 238000011084 recovery Methods 0.000 claims description 9
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 239000008188 pellet Substances 0.000 claims description 7
- 239000010865 sewage Substances 0.000 claims description 7
- 239000000725 suspension Substances 0.000 claims description 7
- QMQXDJATSGGYDR-UHFFFAOYSA-N methylidyneiron Chemical compound [C].[Fe] QMQXDJATSGGYDR-UHFFFAOYSA-N 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 5
- 239000002699 waste material Substances 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- 239000007800 oxidant agent Substances 0.000 claims description 3
- 230000001590 oxidative effect Effects 0.000 claims description 3
- 206010021143 Hypoxia Diseases 0.000 claims description 2
- 125000000129 anionic group Chemical group 0.000 claims description 2
- 230000007954 hypoxia Effects 0.000 claims description 2
- 238000006386 neutralization reaction Methods 0.000 claims description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 12
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 6
- 230000002829 reductive effect Effects 0.000 abstract description 6
- 239000000654 additive Substances 0.000 abstract description 3
- 230000000996 additive effect Effects 0.000 abstract description 3
- 238000006073 displacement reaction Methods 0.000 abstract description 2
- 238000011221 initial treatment Methods 0.000 abstract description 2
- 239000002910 solid waste Substances 0.000 abstract description 2
- 231100000331 toxic Toxicity 0.000 abstract description 2
- 230000002588 toxic effect Effects 0.000 abstract description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 29
- 238000011068 loading method Methods 0.000 description 20
- 239000000126 substance Substances 0.000 description 11
- 230000000694 effects Effects 0.000 description 10
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 8
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 8
- 229910052742 iron Inorganic materials 0.000 description 7
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000003756 stirring Methods 0.000 description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- 239000000919 ceramic Substances 0.000 description 4
- 239000003344 environmental pollutant Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 239000011574 phosphorus Substances 0.000 description 4
- 231100000719 pollutant Toxicity 0.000 description 4
- 230000001105 regulatory effect Effects 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 3
- 230000001112 coagulating effect Effects 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 238000005188 flotation Methods 0.000 description 3
- 238000011835 investigation Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 2
- 239000012028 Fenton's reagent Substances 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 230000003750 conditioning effect Effects 0.000 description 2
- 230000005518 electrochemistry Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 230000036647 reaction Effects 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000013049 sediment Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 208000036142 Viral infection Diseases 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000000701 coagulant Substances 0.000 description 1
- 239000010786 composite waste Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
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- 230000002708 enhancing effect Effects 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 229910001448 ferrous ion Inorganic materials 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 125000001477 organic nitrogen group Chemical group 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- RECVMTHOQWMYFX-UHFFFAOYSA-N oxygen(1+) dihydride Chemical compound [OH2+] RECVMTHOQWMYFX-UHFFFAOYSA-N 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 238000007781 pre-processing Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 231100000167 toxic agent Toxicity 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46176—Galvanic cells
-
- 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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/18—Nature of the water, waste water, sewage or sludge to be treated from the purification of gaseous effluents
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/30—Aerobic and anaerobic processes
- C02F3/302—Nitrification and denitrification treatment
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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)
- Water Treatment By Electricity Or Magnetism (AREA)
Abstract
The invention discloses a kind of high-efficient treatment methods for being suitble to coking wastewater difficult to degrade, after high S, highly toxic vacuum potassium carbonate desulfurization wastewater are pre-processed, it is mixed with distilled ammonia wastewater and carries out water quantity and quality adjusting, oil removing and suspended matter, two-stage Fe-C light electrolysis, Fenton catalysis oxidation, neutralizes flocculation sedimentation, A/O biological cleaning nitrogen removal step, waste water is successively advanced reaction along each process flow.The present invention is using Fe-C light electrolysis and Fenton catalysis oxidation as the strenuous primary treatment system of A/O biological treatment, reduce biological load, biological treatment efficiency is enhanced, the new water additive amount of biological treatment is effectively reduced, it can be achieved that Treatment of Coking Effluent qualified discharge and reducing a ton afocal displacement.Present invention process process is compact, and while making coking wastewater qualified discharge, the solid waste of generation can also be used again, and does not generate secondary pollution.
Description
Technical field
The invention belongs to field of environment engineering technology, and in particular to a kind of efficient process side for being suitble to coking wastewater difficult to degrade
Method.
Background technique
Coking wastewater is the composite waste generated during coal oven dithio-gas recovery of chemical products, wherein containing a large amount of volatilization
The heterocyclic compounds such as phenol, polycyclic aromatic hydrocarbon and oxygen, sulphur, nitrogen have the characteristics that high COD, high nitrogen, high chroma, difficult to degrade, mainly come
Derived from ammonia still process process, one waste liquid in addition can be generated during vacuum potassium carbonate desulfurization process alkali cleaning, includes a large amount of vulcanizations
Object, cyanide, phenol etc., although wastewater flow rate is little, pollutant concentration is high, this causes subsequent biochemical treatment biggish
It influences, and S2-Sulphur simple substance may be generated by light electrolysis oxidation, filler is adversely affected, therefore this effluent part need to be passed through
Pretreatment, reduces its S, CN-And follow-up system is entered back into after COD concentration.
A/O method（Anoxic/aerobic method）It is bio sewage treating process commonplace at present.Because its treatment process is simple
Single, denitrification effect is good and has many applications in terms of Treatment of Coking Effluent.Since the macromolecular contained in coking wastewater is difficult to degrade
Even if substance is still unable to fully degrade under the anoxic section very long residence time, this leads to whole treatment effect and pays no attention to
Think, or even the method for the new water for adding processing water 30-80% must also be taken to reduce aerobic zone load, just can guarantee technique just
Often operation results in the waste consumption of a large amount of new water, increases operating cost.
Fe-C micro-electrolysis method is that a kind of process field in wastewater from chemical industry difficult to degrade studies more electrochemical techniques, former
Reason is similar to Principles of Metal Erosion, and using the potential difference between Fe-C, using iron as anode, carbonaceous material is cathode, in waste water
Ion be electrolyte, generate countless micro-electrolysis reactions, the Fe that simultaneous reactions generate2+Also there is certain reproducibility, by micro-
Cell reaction carries out redox to some hard-degraded substances, can be by the pollution difficult to degrade and virose of the macromolecular in waste water
Object is degraded to small molecule, degradable substance, reduces negative effect of the toxicant to biological respinse, improves the biochemistry of waste water
Property, enhance biodegradable efficiency.
Biological respinse efficiency can be effectively improved using Fe-C light electrolysis as the pre-treating technology of biological treatment, makes biological treatment
It no longer needs to add new water, reduces ton afocal displacement.Meanwhile Fe-C light electrolysis is as preposition treatment process, Fe2+Production quantity compared with
Greatly, subsequent that appropriate H is added2O2, can not additionally add Fe2+In the case where occur Fenton reaction, reach and further go to decontaminate
Contaminate the purpose of object.Aoxidize the Fe generated3+It is extraordinary flocculant, can be realized mixed in the case where a small amount of PAM of addition helps solidifying
Retrogradation is formed sediment, and mud-water separation, whole process Fe is fully utilized, and substantially reduces added amount of chemical.
Chinese patent CN102267771A discloses a kind of preprocess method of coking wastewater, mainly by conditioning tank, interior electricity
Reaction, Fenton catalytic oxidation, coagulating sedimentation composition are solved, waste water enters Inner electrolysis after conditioning tank adjusts acidity first
Reaction, then adds FeSO4Solid and hydrogen peroxide reach the condition of Fenton reaction, and it is quiet to add flocculation aid progress after reaction
Precipitating is set, preprocessing process is completed.The system is although simple and compact, but it does not consider that oil-containing and suspended matter will in coking wastewater
The internal cell reaction of meeting makes a big impact, and can be adsorbed on filler surface when oil-containing in water, and light electrolysis effect can be greatly reduced
Rate, suspended matter height be easy to cause filler to block, and the micro-electrolysis stuffing which uses is iron filings（Anode）With particle charcoal（Cathode）
Mixed fillers, efficiency is extremely low, and is easy hardened.Because the reaction efficiency of the filler is low, it is unable to get after the reaction enough
Fe2+Concentration carries out Fenton reaction, which still needs to additionally add Fe2+It is supplemented.
Chinese patent CN103936225A discloses a kind of catalyzed internal electrocatalysis coupling two-stage biofilter advanced treatment on coking
The method of waste water, the technique are process object with the water outlet after coking wastewater biochemical treatment, and waste water enters iron after being adjusted to acidity
Carbon Pall ring filler carries out micro-electrolysis reaction, adds PAM progress coagulating sedimentation after adjusting pH value to alkalinity using limewash later,
Supernatant sequentially enters anaerobic biofilter and aerobic biofilter carries out biological cleaning.Depth of the technique to coking wastewater
Reason works well, but as advanced treatment process, process is excessively complicated, if adding the biochemical treatment work of coking wastewater leading portion
Skill, whole flow process will be very tediously long, take up a large area.Biological treatment using Inner electrolysis as the technique of advanced treating, to leading portion
It does not have an impact, the load of leading portion biological treatment can not be reduced, so the additive amount of new water can not be reduced.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of high-efficient treatment methods for being suitble to coking wastewater difficult to degrade.This hair
The bright deficiency in current Technologies of Coke Plant Wastewater Treatment, it is difficult to degrade, toxicity is big in conjunction with coking wastewater the features such as, propose a kind of dirt
Dye object strengthen materialization degrade in advance coupled biological purification denitrogenation efficient Technologies of Coke Plant Wastewater Treatment.
In order to solve the above technical problems, the technical solution adopted by the present invention is that：A kind of height being suitble to coking wastewater difficult to degrade
Processing method is imitated, the high-efficient treatment method includes the following steps：
（1）Wastewater Pretreatment：To COD, CN of coking raw coke oven gas recovery stage vacuum potassium carbonate desulfurization process waste water-And S2-Into
Row pretreatment, after pretreatment, it is desirable that it is as follows that water outlet reaches technical indicator：COD≤10000mg/L,CN-≤400mg/L、S2-≤
200mg/L；
（2）Water quality and quantity is adjusted：Pretreated vacuum potassium carbonate desulfurization wastewater is mixed with distilled ammonia wastewater, and carries out water quality and quantity
It adjusts；
（3）Oil removing, suspended matter：Remove the oil and suspended matter in waste water；
（4）Fe-C light electrolysis：After oil content and suspended matter are met the requirements, into two-stage micro-electrolysis reaction, light electrolysis uses two-stage
The mode of acid is adjusted to adjust two-stage reaction water inlet pH value respectively；
（5）Fenton catalysis oxidation：Micro-electrolysis reaction water outlet adds hydrogen peroxide, carries out Fenton catalysis oxidation；
（6）Neutralize flocculation sedimentation：The water outlet of Fenton catalytic oxidation is added alkaline conditioner and adjusts pH value, and flocculation aid is added
Neutralization flocculation sedimentation is carried out, the sludge containing Fe of precipitating is sintered ore matching；
（7）A/O biological cleaning denitrogenation：Supernatant enters A/O biological cleaning denitrification system, sewage qualified discharge, sludge after processing
Carry out coal-blending coking.
Step of the present invention（1）Vacuum potassium carbonate desulfurization process waste water main indicator is as follows：COD：12000~
15000mg/L、CN-：3000~4000mg/L, S2-：2000~3000mg/L.
Step of the present invention（2）After water quality and quantity is adjusted, COD is 3400~3900mg/L, BOD5/ COD be 0.16~
0.20, pH value 8.0-9.0.
Step of the present invention（3）It removes oil in waste water and is discharged oil content≤5mg/L, concentration of suspension with after suspended matter
≤50mg/L。
Step of the present invention（4）Two-stage micro-electrolysis reaction controls its pH value of intaking respectively by the way of two sections of tune acid,
First order control water inlet pH value is 3~4, and it is 2~3 that the second level, which controls inlet flow-patterm,；Two-stage micro-electrolysis reaction, first order light electrolysis are anti-
It is 60~120min between seasonable, the second level micro-electrolysis reaction time is the 1/2 of the first order.
Step of the present invention（4）Two-stage micro-electrolysis reaction, aeration quantity are different, and first order aeration quantity is big, and gas-water ratio is 3~
4:1, second level aeration quantity is small, and gas-water ratio is 1~1.5:1.
Step of the present invention（4）With（5）Two-stage micro-electrolysis reaction, reaction filler are integrated iron-carbon pellets filler, are filled out
Fill voidage 0.7~0.9.
Step of the present invention（5）Fenton catalytic oxidation, catalytic oxidant are the H of concentration quality 50%2O2Solution,
Dosage is 1500~3000mg/L, and the reaction time is 60~120min.
Step of the present invention（6）Flocculation sedimentation is neutralized, control inlet flow-patterm is 8~9, and flocculation aid is anionic PAM, is thrown
Dosage is 0.4~0.6mg/m3.
Step of the present invention（7）A/O biological cleaning denitrification system, hypoxia response HRT are 12~18h, aerobic reaction
HRT is 8~12h；Soft-filler, mixed liquid recycle ratio 300%, return sludge ratio 60% are filled in the pond A.
Mentality of designing of the invention：
It is mixed after being pre-processed to vacuum potassium carbonate desulfurization wastewater in coal oven dithio-gas recovery of chemical products process with distilled ammonia wastewater, into
Row water quality and runoff investigation pass through the materializations such as micro-electrolysis reaction plus Fenton catalysis oxidation after then carrying out oil removing, oil removal
Difficult to degrade, the high toxic material in pre- treatment of Coking Wastewater are strengthened in effect, to improve wastewater biodegradability, reduce waste water to life
The murder by poisoning inhibiting effect of object improves subsequent biochemical treatment effeciency, reduces the biochemical residence time.
Specific mentality of designing is as follows：
（1）Sulfide, cyanide to the high concentration contained in vacuum potassium carbonate desulfurization wastewater in raw coke oven gas recovery of chemical products process
It is mixed after being pre-processed with COD with distilled ammonia wastewater, reduces it and subsequent technique is impacted.
（2）Water quality and quantity is adjusted：Guarantee system water inlet uniformly continuous, prevents water fluctuation from causing to subsequent biosystem
Load impact.
（3）Oil removing, suspended matter：By in waste water oil and the removal of partially hydrophobic suspended matter, meet light electrolysis water inlet to containing
The requirement of oil mass and suspended matter.
（4）Fe-C light electrolysis：Iron carbon one pellet filler is used in micro-electrolysis reactor, utilizes micro-electrolysis stuffing itself
The potential difference of generation forms countless primary batteries in equipment, using waste water as electrolyte, forms electrochemistry by the electric discharge of anode and cathode
Reaction carries out electrochemical treatments to waste water.In order to guarantee treatment effect, two-stage micro-electrolysis reaction is set, and control respectively its into
Water pH value, so that micro-electrolysis reaction carries out within the scope of suitable pH always, it is ensured that higher degradation efficiency, and react
It is discharged pH value and Fe afterwards2+Concentration can meet the condition of Fenton reaction, without additionally adding Fe2+。
Under the collective effects such as electrochemistry, oxidationreduction, to useless Organic substance in water, especially macromolecular difficult for biological degradation
Organic matter carries out materialization degradation, and COD and coloration can be greatly lowered, make phenyl ring class open loop chain rupture, it is biochemical to greatly improve waste water
Property.
（5）Fenton catalysis oxidation：It is the extension to Fe-C micro-electrolysis reaction, in micro-electrolysis reactor, iron is as sun
Oxidation reaction (Fe-2e → Fe occurs for pole2+) generate a large amount of Fe2+, it is stronger under the action of hydrogen peroxide is added can to form oxidability
Fenton reagent, with the decomposition of oxidant, the extremely strong HO of a large amount of oxidisability can be generated under the catalytic action of ferrous ion
, oxidation removal is carried out to organic matter using the HO of nascent state.It is equipped with aerating system in this device, H can be reduced by aeration2O2
Dosage, reduce operating cost, secondly can also play stirring action.
（6）Neutralize flocculation sedimentation：After catalysis oxidation, the Fe of light electrolysis formation in waste water2+It is oxidized to Fe3+, add alkali
Property substance make its generate Fe（OH）3The removal of suspended matter is realized in flocculent deposit in the case where adding a small amount of PAM.In sediment
The content of Fe is very high, and without other objectionable impurities, can be used for Iron Ore Matching in Sintering, carry out resource utilization.
（7）A/O system：It is divided into anoxic zone（The area A）The aerobic zone and（The area O）And secondary settling tank.Preceding, aerobic zone exists for anoxic zone
Afterwards, followed by secondary settling tank is sequentially connected between three by pipeline, sludge reflux is equipped between secondary settling tank and anoxic pond, aerobic
Area and anoxic section are flowed back equipped with nitrification liquid.Anoxic zone main function is to by above procedure treated the further water of waste water
Solution acidification, improves biodegradability.It is completed at the same time the ammonifying process of organic nitrogen, to the nitre state in a large amount of nitrification liquids of aerobic zone reflux
Nitrogen carries out denitrification removing, achievees the purpose that remove total nitrogen.Aerobic zone main function is the further purification to waste water, and reaching has
The purpose of machine pollutant discharge in compliance with the standard is completed at the same time the nitrification of ammonia nitrogen, removal of ammonia and nitrogen.It is connected after aerobic zone with secondary settling tank,
Sludge settling is completed in sedimentation basin, realizes mud-water separation.Supernatant is the discharge of final process water, and sludge a part of precipitating is returned
Anoxic section is flow to supplement the pond A, O biomass, excess sludge carries out coal-blending coking after dehydration, reaches nearest recycling
The purpose utilized.
Treated that qualified waste water meets by the present invention《Coking chemistry emission of industrial pollutants standard》GB16171-2012.
Generated beneficial effect is by adopting the above technical scheme：1, the technology of the present invention set Fe-C light electrolysis,
A variety of effects such as Fenton catalysis oxidation, coagulating sedimentation, A/O biological cleaning+denitrogenation, can efficient process coking wastewater.2, this hair
Bright light electrolysis, Fenton catalysis oxidation neutralize pretreatment of the flocculation sedimentation as biological treatment, can make the biochemical of coking wastewater
Property greatly improves, and facilitates the stable operation in subsequent biochemical stage.3, the unique two-stage micro-electrolysis reaction design of the present invention, can have
Effect enhancing micro-electrolysis reaction efficiency, improves Fe in subsequent catalyst oxidation reaction2+Specific gravity, reach without additional addition Fe2+Effect
Fruit, and ensure that subsequent Fenton reacts suitable pH value in reaction.4, present invention process process is compact, makes coking wastewater row up to standard
While putting, the solid waste of generation can also be used again, and not generate secondary pollution.5, the iron warp that Fe-C light electrolysis of the present invention uses
Cross light electrolysis raw material（Fe）- Fenton reagent catalyst（Fe2+）- coagulant（Fe3+）Conversion process, in materializing strategy rank
Section whole process participates in pollutant removal, and service efficiency greatly improves, and reduces medicament input amount.6, the present invention is with Fe-C light electrolysis
Strenuous primary treatment system with Fenton catalysis oxidation as A/O biological treatment, reduces biological load, enhances biological treatment
The new water additive amount of biological treatment is effectively reduced, it can be achieved that Treatment of Coking Effluent qualified discharge and reducing the draining of ton afocal in efficiency
Amount.
Detailed description of the invention
Fig. 1 is process flow chart of the invention.
Specific embodiment
The present invention will be further described in detail in the following with reference to the drawings and specific embodiments.
Embodiment 1
A kind of high-efficient treatment method for being suitble to coking wastewater difficult to degrade of the present embodiment include Wastewater Pretreatment, water quality and quantity adjust,
Oil removing oil removal, Fenton catalysis oxidation, neutralizes flocculation sedimentation, A/O biological cleaning denitrogenation, concrete technology at Fe-C light electrolysis
It is described that steps are as follows：
（1）Wastewater Pretreatment：The vacuum potassium carbonate desulfurization process waste water of coking raw coke oven gas recovery stage（COD：12000mg/L,
CN-：3000mg/L,S2-：2300mg/L）It is handled through desulfurization, cyanogen and COD, takes waste water 5L after desulfurization process, measure its COD, CN-
And S2—Concentration is respectively 9800mg/L, 365mg/L and 160mg/L；
（2）Water quality and quantity is adjusted：Waste water mixes with 45L distilled ammonia wastewater and carries out water quality and quantity adjusting after desulfurization process, measures COD
For 3900mg/L, BOD5/ COD is 0.18, pH value 8.0；
（3）Oil removing, suspended matter：After regulating water quality water, by air-flotation process, oil and suspended matter in waste water are removed, measurement contains
Oil mass is 3.2mg/L, concentration of suspension 40mg/L；
（4）Fe-C light electrolysis：Oil content and suspended matter enter two-stage micro-electrolysis reaction after meeting the requirements, and adjust the using the concentrated sulfuric acid
Level-one water inlet pH value is 3.0, injects first order micro-electrolysis reactor, blast aeration, gas-water ratio 3:1, residence time 60min, instead
Should after adjust pH value be 2.0；Reaction solution injects second level micro-electrolysis reactor, a small amount of blast aerations, gas-water ratio 1:1, when stop
Between 30min；Used micro-electrolysis reaction filler is integrated iron-carbon pellets filler, fills voidage 0.8；
（5）Fenton catalysis oxidation：50% H is added in micro-electrolysis reaction water outlet2O2Solution 1500mg/L, catalysis oxidation time is
60min；
（6）Neutralize flocculation sedimentation：Fenton catalytic oxidation water outlet NaOH solution adjusts pH value to 8.0, while stirring plus
Enter flocculation aid PAM, additional amount 0.4mg/m3 is staticly settled, and supernatant is taken to measure COD, BOD5/ COD be respectively 2183mg/L,
0.51, COD removal rate is 43.0%, and biodegradability improves 183%；
（7）A/O biological cleaning denitrogenation：Neutralize flocculation sedimentation supernatant and enter A/O system, the HRT in the pond A and the pond O be respectively 12h,
Soft-filler is filled in the pond 8h, A, and the pond O sludge concentration is in 2000-4000mg/L, COD volumetric loading 0.5-1.02kgCOD/（m3·
d）；COD sludge loading 0.45-0.65kgCOD/（kgMLVSS·d）；NH3- N volumetric loading 0.14-0.19kgNH3-N/（m3·
d）；NH3- N sludge loading 0.45-0.65kgNH3-N/（kgMLVSS.d）；Return current ratio of the mixed liquid 300% between the pond A and the pond O；Two precipitatings
Tank waterpower residence time 1.5h；Surface loading 1.5m3/（m2·h）；Return sludge ratio 60%；
Final outflow water COD is 74mg/L, NH3- N is 5mg/L, TN 28mg/L, total phosphorus 1mg/L, volatile phenol 0.6mg/L.This reality
Sewage qualified discharge after example is handled is applied, sludge carries out coal-blending coking, and the sludge containing Fe of precipitating is sintered ore matching.
Embodiment 2
A kind of high-efficient treatment method for being suitble to coking wastewater difficult to degrade of the present embodiment include Wastewater Pretreatment, water quality and quantity adjust,
Oil removing oil removal, Fenton catalysis oxidation, neutralizes flocculation sedimentation, A/O biological cleaning denitrogenation, concrete technology at Fe-C light electrolysis
It is described that steps are as follows：
（1）Wastewater Pretreatment：The vacuum potassium carbonate desulfurization process waste water of coking raw coke oven gas recovery stage（COD：13000mg/L,
CN-：3500mg/L,S2-2000mg/L）It is handled through desulfurization, cyanogen and COD, takes waste water 5L after desulfurization process, measure its COD, CN-With
S2—Concentration is respectively 9860mg/L, 380mg/L and 175mg/L；
（2）Water quality and quantity is adjusted：Waste water mixes with 45L distilled ammonia wastewater and carries out water quality and quantity adjusting after desulfurization process, measures COD
For 3600mg/L, BOD5/ COD is 0.20, pH value 9.0；
（3）Oil removing, suspended matter：After regulating water quality water, by air-flotation process, oil and suspended matter in waste water are removed, measurement contains
Oil mass is 2.8mg/L, concentration of suspension 35mg/L；
（4）Fe-C light electrolysis：Oil content and suspended matter enter two-stage micro-electrolysis reaction after meeting the requirements, and adjust the using the concentrated sulfuric acid
Level-one water inlet pH value is 4.0, injects first order micro-electrolysis reactor, blast aeration, gas-water ratio 4:1, residence time 60min, instead
Should after adjust pH value be 3.0；Reaction solution injects second level micro-electrolysis reactor, a small amount of blast aerations, gas-water ratio 1.5:1, it stops
Time 30min；Used micro-electrolysis reaction filler is integrated iron-carbon pellets filler, fills voidage 0.8；
（5）Fenton catalysis oxidation：50% H is added in micro-electrolysis reaction water outlet2O2Solution 3000mg/L, catalysis oxidation time is
120min；
（6）Neutralize flocculation sedimentation：Fenton catalytic oxidation water outlet NaOH solution adjusts pH value to 8.5, while stirring plus
Enter flocculation aid PAM, additional amount 0.6mg/m3 is staticly settled, and supernatant is taken to measure COD, BOD5/ COD be respectively 1550mg/L,
0.54, COD removal rate is 55.7%, and biodegradability improves 218%；
（7）A/O biological cleaning denitrogenation：Neutralize flocculation sedimentation supernatant and enter A/O system, the HRT in the pond A and the pond O be respectively 15h,
Soft-filler is filled in the pond 10h, A, and the pond O sludge concentration is in 2000-4000mg/L, COD volumetric loading 0.5-1.02kgCOD/（m3·
d）；COD sludge loading 0.45-0.65kgCOD/（kgMLVSS·d）；NH3- N volumetric loading 0.14-0.19kgNH3-N/（m3·
d）；NH3- N sludge loading 0.45-0.65kgNH3-N/（kgMLVSS.d）；Return current ratio of the mixed liquid 300% between the pond A and the pond O；Two precipitatings
Tank waterpower residence time 1.5h；Surface loading 1.5m3/（m2·h）；Return sludge ratio 60%；
Final outflow water COD is 62mg/L, NH3- N is 4.5mg/L, TN 24mg/L, total phosphorus 0.7mg/L, volatile phenol 0.25mg/L.
Sewage qualified discharge after the present embodiment processing, sludge carry out coal-blending coking, and the sludge containing Fe of precipitating is sintered ore matching.
Embodiment 3
A kind of high-efficient treatment method for being suitble to coking wastewater difficult to degrade of the present embodiment, by pre-micro-electrolysis disposal and A/O biological treatment
It connects the test of laggard Mobile state, technique includes Wastewater Pretreatment, dynamic water quality runoff investigation, ceramic filter processing, Fe-C micro-
Electrolysis, neutralizes flocculation sedimentation, A/O biological cleaning denitrogenation at Fenton catalysis oxidation, and specific process step is as described below：
（1）Wastewater Pretreatment：The vacuum potassium carbonate desulfurization process waste water of coking raw coke oven gas recovery stage（COD：14000mg/L,
CN-：3800mg/L,S2-：2600mg/L）After desulfurization, cyanogen and COD processing, COD, CN are measured-And S2—Concentration is respectively
9900mg/L, 370mg/L and 185mg/L；
（2）Dynamic water quality runoff investigation：By pretreated vacuum potassium carbonate desulfurization waste liquor and distilled ammonia wastewater with 1:9 ratio is in tune
Mixing in slot is saved, measuring COD is 3400mg/L, BOD5/ COD is 0.16, pH value 9.0, flow of inlet water 50L/h；
（3）Ceramic filter processing：It after regulating water quality water, is handled by ceramic filter, removes the oil in waste water and suspension
Object, measurement oil content be 3.8mg/L, concentration of suspension 42mg/L；
（4）Fe-C light electrolysis：Enter two-stage micro-electrolysis reaction after ceramic filter processing, adjusts the first order using the concentrated sulfuric acid and intake
PH value is 3.5, injects first order micro-electrolysis reactor, blast aeration, gas-water ratio 3:1, residence time 120min are adjusted after reaction
PH value is 2.5；Reaction solution injects second level micro-electrolysis reactor, a small amount of blast aerations, gas-water ratio 1.5:1, the residence time
60min；Used micro-electrolysis reaction filler is integrated iron-carbon pellets filler, fills voidage 0.7；
（5）Fenton catalysis oxidation：50% H is added in micro-electrolysis reaction water outlet2O2Solution 2000mg/L, catalysis oxidation time is
120min；
（6）Neutralize flocculation sedimentation：Ca is used in the water outlet of Fenton catalytic oxidation（OH）2Solution adjusts pH value to 9.0, while stirring
Flocculation aid PAM is added, additional amount 0.6mg/m3 is staticly settled, and supernatant is taken to measure COD, BOD5/ COD be respectively 1815mg/L,
0.55, COD removal rate is 48.1%, and biodegradability improves 206%；
（7）A/O biological cleaning denitrogenation：Neutralize flocculation sedimentation supernatant and enter A/O system, the HRT in the pond A and the pond O be respectively 12h,
Soft-filler is filled in the pond 8h, A, and the pond O sludge concentration is in 2000-4000mg/L, COD volumetric loading 0.5-1.02kgCOD/（m3·
d）；COD sludge loading 0.45-0.65kgCOD/（kgMLVSS·d）；NH3- N volumetric loading 0.14-0.19kgNH3-N/（m3·
d）；NH3- N sludge loading 0.45-0.65kgNH3-N/（kgMLVSS.d）；Return current ratio of the mixed liquid 300% between the pond A and the pond O；Two precipitatings
Tank waterpower residence time 1.5h；Surface loading 1.5m3/（m2·h）；Return sludge ratio 60%；
Final outflow water COD is 79mg/L, NH3- N is 5mg/L, TN 30mg/L, total phosphorus 0.9mg/L, volatile phenol 0.25mg/L.This
Sewage qualified discharge after embodiment processing, sludge carry out coal-blending coking, and the sludge containing Fe of precipitating is sintered ore matching.
Embodiment 4
A kind of high-efficient treatment method for being suitble to coking wastewater difficult to degrade of the present embodiment include Wastewater Pretreatment, water quality and quantity adjust,
Oil removing oil removal, Fenton catalysis oxidation, neutralizes flocculation sedimentation, A/O biological cleaning denitrogenation, concrete technology at Fe-C light electrolysis
It is described that steps are as follows：
（1）Wastewater Pretreatment：The vacuum potassium carbonate desulfurization process waste water of coking raw coke oven gas recovery stage（COD： 15000mg/L,
CN-：4000mg/L,S2-：3000mg/L）It is handled through desulfurization, cyanogen and COD, takes waste water 5L after desulfurization process, measure its COD, CN-
And S2—Concentration is respectively 10000mg/L, 400mg/L, 200mg/L；
（2）Water quality and quantity is adjusted：Waste water mixes with 45L distilled ammonia wastewater and carries out water quality and quantity adjusting after desulfurization process, measures COD
For 3500mg/L, BOD5/ COD is 0.18, pH value 8.9；
（3）Oil removing, suspended matter：After regulating water quality water, by air-flotation process, oil and suspended matter in waste water are removed, measurement contains
Oil mass is 5mg/L, concentration of suspension 50mg/L；
（4）Fe-C light electrolysis：Oil content and suspended matter enter two-stage micro-electrolysis reaction after meeting the requirements, and adjust the using the concentrated sulfuric acid
Level-one water inlet pH value is 4.0, injects first order micro-electrolysis reactor, blast aeration, gas-water ratio 4:1, residence time 100min, instead
Should after adjust pH value be 2.0；Reaction solution injects second level micro-electrolysis reactor, a small amount of blast aerations, gas-water ratio 1:1, when stop
Between 50min；Used micro-electrolysis reaction filler is integrated iron-carbon pellets filler, fills voidage 0.9；
（5）Fenton catalysis oxidation：50% H is added in micro-electrolysis reaction water outlet2O2Solution 2500mg/L, catalysis oxidation time is
80min；
（6）Neutralize flocculation sedimentation：Ca is used in the water outlet of Fenton catalytic oxidation（OH）2Solution adjusts pH value to 8.5, while stirring
Flocculation aid PAM is added, additional amount 0.5mg/m3 is staticly settled, and supernatant is taken to measure COD, BOD5/ COD be respectively 1650mg/L,
0.52, COD removal rate is 53.8%, and biodegradability improves 208%；
（7）A/O biological cleaning denitrogenation：Neutralize flocculation sedimentation supernatant and enter A/O system, the HRT in the pond A and the pond O be respectively 18h,
Soft-filler is filled in the pond 12h, A, and the pond O sludge concentration is in 2000-4000mg/L, COD volumetric loading 0.5-1.02kgCOD/（m3·
d）；COD sludge loading 0.45-0.65kgCOD/（kgMLVSS·d）；NH3- N volumetric loading 0.14-0.19kgNH3-N/（m3·
d）；NH3- N sludge loading 0.45-0.65kgNH3-N/（kgMLVSS.d）；Return current ratio of the mixed liquid 300% between the pond A and the pond O；Two precipitatings
Tank waterpower residence time 1.5h；Surface loading 1.5m3/（m2·h）；Return sludge ratio 60%；
Final outflow water COD is 70mg/L, NH3- N is 4.8mg/L, TN 29mg/L, total phosphorus 0.8mg/L, volatile phenol 0.25mg/L.
Sewage qualified discharge after the present embodiment processing, sludge carry out coal-blending coking, and the sludge containing Fe of precipitating is sintered ore matching.
The above embodiments are only used to illustrate and not limit the technical solutions of the present invention, although referring to above-described embodiment to this hair
It is bright to be described in detail, those skilled in the art should understand that：Still the present invention can be modified or be waited
With replacement, without departing from the spirit or scope of the invention, or any substitutions, should all cover in power of the invention
In sharp claimed range.
Claims (10)
1. a kind of high-efficient treatment method for being suitble to coking wastewater difficult to degrade, which is characterized in that the high-efficient treatment method include with
Lower step：
（1）Wastewater Pretreatment：To COD, CN of coking raw coke oven gas recovery stage vacuum potassium carbonate desulfurization process waste water-And S2-Into
Row pretreatment, after pretreatment, it is desirable that it is as follows that water outlet reaches technical indicator：COD≤10000mg/L,CN-≤400mg/L、S2-≤
200mg/L；
（2）Water quality and quantity is adjusted：Pretreated vacuum potassium carbonate desulfurization wastewater is mixed with distilled ammonia wastewater, and carries out water quality and quantity
It adjusts；
（3）Oil removing, suspended matter：Remove the oil and suspended matter in waste water；
（4）Fe-C light electrolysis：After oil content and suspended matter are met the requirements, into two-stage micro-electrolysis reaction, light electrolysis uses two-stage
The mode of acid is adjusted to adjust two-stage reaction water inlet pH value respectively；
（5）Fenton catalysis oxidation：Micro-electrolysis reaction water outlet adds hydrogen peroxide, carries out Fenton catalysis oxidation；
（6）Neutralize flocculation sedimentation：The water outlet of Fenton catalytic oxidation is added alkaline conditioner and adjusts pH value, and flocculation aid is added
Neutralization flocculation sedimentation is carried out, the sludge containing Fe of precipitating is sintered ore matching；
（7）A/O biological cleaning denitrogenation：Supernatant enters A/O biological cleaning denitrification system, sewage qualified discharge, sludge after processing
Carry out coal-blending coking.
2. a kind of high-efficient treatment method for being suitble to coking wastewater difficult to degrade according to claim 1, which is characterized in that described
Step（1）Vacuum potassium carbonate desulfurization process waste water main indicator is as follows：COD：12000~15000mg/L, CN-：3000~
4000mg/L、S2-：2000~3000mg/L.
3. a kind of high-efficient treatment method for being suitble to coking wastewater difficult to degrade according to claim 1, which is characterized in that described
Step（2）After water quality and quantity is adjusted, COD is 3400~3900mg/L, BOD5/ COD is 0.16~0.20, pH value 8.0-9.0.
4. a kind of high-efficient treatment method for being suitble to coking wastewater difficult to degrade according to claim 1, which is characterized in that described
Step（3）It removes oil in waste water and is discharged oil content≤5mg/L, concentration of suspension≤50mg/L with after suspended matter.
5. a kind of high-efficient treatment method for being suitble to coking wastewater difficult to degrade according to any one of claims 1-4, special
Sign is, the step（4）Two-stage micro-electrolysis reaction controls its pH value of intaking, the first order respectively by the way of two sections of tune acid
Control water inlet pH value is 3~4, and it is 2~3 that the second level, which controls inlet flow-patterm,；Two-stage micro-electrolysis reaction, first order micro-electrolysis reaction time
For 60~120min, the second level micro-electrolysis reaction time is the 1/2 of the first order.
6. a kind of high-efficient treatment method for being suitble to coking wastewater difficult to degrade according to any one of claims 1-4, special
Sign is, the step（4）Two-stage micro-electrolysis reaction, aeration quantity is different, and first order aeration quantity is big, and gas-water ratio is 3~4:1, the
Second level aeration quantity is small, and gas-water ratio is 1~1.5:1.
7. a kind of high-efficient treatment method for being suitble to coking wastewater difficult to degrade according to any one of claims 1-4, special
Sign is, the step（4）With（5）Two-stage micro-electrolysis reaction, reaction filler are integrated iron-carbon pellets filler, fill voidage
0.7~0.9.
8. a kind of high-efficient treatment method for being suitble to coking wastewater difficult to degrade according to any one of claims 1-4, special
Sign is, the step（5）Fenton catalytic oxidation, catalytic oxidant are the H of concentration quality 50%2O2Solution, dosage
For 1500~3000mg/L, the reaction time is 60~120min.
9. a kind of high-efficient treatment method for being suitble to coking wastewater difficult to degrade according to any one of claims 1-4, special
Sign is, the step（6）Flocculation sedimentation is neutralized, control inlet flow-patterm is 8~9, and flocculation aid is anionic PAM, and dosage is
0.4~0.6mg/m3.
10. a kind of high-efficient treatment method for being suitble to coking wastewater difficult to degrade according to any one of claims 1-4, special
Sign is, the step（7）A/O biological cleaning denitrification system, hypoxia response HRT are 12~18h, the HRT of aerobic reaction is 8~
12h；Soft-filler, mixed liquid recycle ratio 300%, return sludge ratio 60% are filled in the pond A.
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| CN112079524B (en) * | 2020-08-28 | 2024-04-05 | 陕西创源石油科技有限公司 | Oily sewage treatment system and treatment process |
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