CN109626562A - A kind of coking wastewater processing system and method comprising biochemical recombiner unit - Google Patents
A kind of coking wastewater processing system and method comprising biochemical recombiner unit Download PDFInfo
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- CN109626562A CN109626562A CN201910120966.1A CN201910120966A CN109626562A CN 109626562 A CN109626562 A CN 109626562A CN 201910120966 A CN201910120966 A CN 201910120966A CN 109626562 A CN109626562 A CN 109626562A
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- 239000002351 wastewater Substances 0.000 title claims abstract description 99
- 238000004939 coking Methods 0.000 title claims abstract description 49
- 238000012545 processing Methods 0.000 title claims abstract description 48
- 238000000034 method Methods 0.000 title claims abstract description 35
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 98
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 89
- 230000003647 oxidation Effects 0.000 claims abstract description 78
- 238000007667 floating Methods 0.000 claims abstract description 50
- 239000012528 membrane Substances 0.000 claims abstract description 38
- 230000003197 catalytic effect Effects 0.000 claims abstract description 9
- AHEWZZJEDQVLOP-UHFFFAOYSA-N monobromobimane Chemical compound BrCC1=C(C)C(=O)N2N1C(C)=C(C)C2=O AHEWZZJEDQVLOP-UHFFFAOYSA-N 0.000 claims description 117
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 57
- 239000003054 catalyst Substances 0.000 claims description 37
- 238000011049 filling Methods 0.000 claims description 36
- 229910002804 graphite Inorganic materials 0.000 claims description 34
- 239000010439 graphite Substances 0.000 claims description 34
- 230000001112 coagulating effect Effects 0.000 claims description 25
- 238000004062 sedimentation Methods 0.000 claims description 24
- 238000005273 aeration Methods 0.000 claims description 23
- 239000000945 filler Substances 0.000 claims description 21
- 229920002635 polyurethane Polymers 0.000 claims description 20
- 239000004814 polyurethane Substances 0.000 claims description 20
- 238000001914 filtration Methods 0.000 claims description 17
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 14
- 230000008569 process Effects 0.000 claims description 14
- 238000005276 aerator Methods 0.000 claims description 13
- 239000007789 gas Substances 0.000 claims description 13
- 239000001301 oxygen Substances 0.000 claims description 12
- 229910052760 oxygen Inorganic materials 0.000 claims description 12
- 239000010802 sludge Substances 0.000 claims description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 11
- 238000003672 processing method Methods 0.000 claims description 9
- 230000005611 electricity Effects 0.000 claims description 7
- 239000002131 composite material Substances 0.000 claims description 6
- 230000036284 oxygen consumption Effects 0.000 claims description 6
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- 238000010926 purge Methods 0.000 claims description 4
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- 239000000126 substance Substances 0.000 abstract description 25
- 239000003245 coal Substances 0.000 description 17
- 230000000694 effects Effects 0.000 description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- 238000005516 engineering process Methods 0.000 description 9
- 239000004576 sand Substances 0.000 description 9
- 230000015556 catabolic process Effects 0.000 description 8
- 238000006731 degradation reaction Methods 0.000 description 8
- 239000005416 organic matter Substances 0.000 description 8
- 239000010865 sewage Substances 0.000 description 8
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 5
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- -1 heterocyclic arene Chemical class 0.000 description 5
- 244000005700 microbiome Species 0.000 description 5
- 230000009897 systematic effect Effects 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 239000003344 environmental pollutant Substances 0.000 description 4
- 239000002957 persistent organic pollutant Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 206010020852 Hypertonia Diseases 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 230000020477 pH reduction Effects 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000005728 strengthening Methods 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- 238000004065 wastewater treatment Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 238000011953 bioanalysis Methods 0.000 description 2
- 238000002306 biochemical method Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000001311 chemical methods and process Methods 0.000 description 2
- 238000002224 dissection Methods 0.000 description 2
- 238000003487 electrochemical reaction Methods 0.000 description 2
- 230000005518 electrochemistry Effects 0.000 description 2
- 238000006056 electrooxidation reaction Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000005189 flocculation Methods 0.000 description 2
- 230000016615 flocculation Effects 0.000 description 2
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 2
- 125000000623 heterocyclic group Chemical group 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- 239000010842 industrial wastewater Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- WQEPLUUGTLDZJY-UHFFFAOYSA-N pentadecanoic acid Chemical compound CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 239000011949 solid catalyst Substances 0.000 description 2
- 239000002910 solid waste Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- BLRBOMBBUUGKFU-SREVYHEPSA-N (z)-4-[[4-(4-chlorophenyl)-5-(2-methoxy-2-oxoethyl)-1,3-thiazol-2-yl]amino]-4-oxobut-2-enoic acid Chemical compound S1C(NC(=O)\C=C/C(O)=O)=NC(C=2C=CC(Cl)=CC=2)=C1CC(=O)OC BLRBOMBBUUGKFU-SREVYHEPSA-N 0.000 description 1
- SIXWIUJQBBANGK-UHFFFAOYSA-N 4-(4-fluorophenyl)-1h-pyrazol-5-amine Chemical compound N1N=CC(C=2C=CC(F)=CC=2)=C1N SIXWIUJQBBANGK-UHFFFAOYSA-N 0.000 description 1
- 239000012028 Fenton's reagent Substances 0.000 description 1
- TUNFSRHWOTWDNC-UHFFFAOYSA-N Myristic acid Natural products CCCCCCCCCCCCCC(O)=O TUNFSRHWOTWDNC-UHFFFAOYSA-N 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 235000021314 Palmitic acid Nutrition 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- RHZUVFJBSILHOK-UHFFFAOYSA-N anthracen-1-ylmethanolate Chemical compound C1=CC=C2C=C3C(C[O-])=CC=CC3=CC2=C1 RHZUVFJBSILHOK-UHFFFAOYSA-N 0.000 description 1
- 239000003830 anthracite Substances 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000010219 correlation analysis Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 230000003635 deoxygenating effect Effects 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000009851 ferrous metallurgy Methods 0.000 description 1
- 238000005243 fluidization Methods 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
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- 150000002500 ions Chemical class 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000002906 microbiologic effect Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- ZWLPBLYKEWSWPD-UHFFFAOYSA-N o-toluic acid Chemical compound CC1=CC=CC=C1C(O)=O ZWLPBLYKEWSWPD-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000010815 organic waste Substances 0.000 description 1
- 238000007415 particle size distribution analysis Methods 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 238000012958 reprocessing Methods 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 238000006250 specific catalysis Methods 0.000 description 1
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- 230000001988 toxicity Effects 0.000 description 1
- 241001148471 unidentified anaerobic bacterium Species 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000009279 wet oxidation reaction 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
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/02—Aerobic processes
- C02F3/12—Activated sludge processes
- C02F3/1236—Particular type of activated sludge installations
- C02F3/1268—Membrane bioreactor systems
-
- 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
- C02F3/28—Anaerobic digestion processes
- C02F3/2853—Anaerobic digestion processes using anaerobic membrane bioreactors
-
- 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
- C02F1/467—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
-
- 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
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
-
- 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
- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
- C02F2101/18—Cyanides
-
- 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
- C02F2101/32—Hydrocarbons, e.g. oil
-
- 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
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
-
- 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
- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
-
- 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
- C02F2209/10—Solids, e.g. total solids [TS], total suspended solids [TSS] or volatile solids [VS]
-
- 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
- C02F2209/14—NH3-N
-
- 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
- C02F3/34—Biological treatment of water, waste water, or sewage characterised by the microorganisms used
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/10—Biological treatment of water, waste water, or sewage
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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)
- Microbiology (AREA)
- Biodiversity & Conservation Biology (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
- Biological Treatment Of Waste Water (AREA)
Abstract
The invention discloses a kind of coking wastewater processing system and method comprising biochemical recombiner unit, pretreated waste water is introduced MBBR-MBR recombiner unit by the system, and preferably waste water is introduced into electrochemical catalytic oxidation unit before introducing MBBR-MBR recombiner unit and is handled.MBBR-MBR recombiner unit includes anaerobic pond, the anoxic pond containing floating stuffing, the aerobic tank containing floating stuffing and MBR membrane bioreactor.The system can effectively deal with the hardly degraded organic substance in coking wastewater, and water outlet COD, which stablizes, is lower than 40ppm, and most down to 8ppm, TOC removal rate is 60% or more.
Description
Technical field
The invention belongs to technical field of environmental science, be related to a kind of organic wastewater treating system and method, in particular to one
Organic wastewater treating system and method in kind coal chemical industry/coking industry.
Background technique
Coking wastewater be a kind of component for being generated in the chemical products production process such as gas purification and coke, benzene very
Complicated industrial wastewater, mainly contains sulfide, cyanide, ammonia nitrogen, phenolic compound, polycyclic aromatic hydrocarbon, heterocyclic arene etc., has
The features such as toxicity is big, organic pollutant concentration is high, difficult for biological degradation.China is to use coal big country, and 70% energy resource supply is needed by coal
It provides, there are a large amount of coking wastewaters to generate in a series of production processes of the industry such as coal chemical industry, Ferrous Metallurgy, pass through traditional biochemistry
Method processing qualified discharge difficult to realize.How advanced treatment on coking wastewater is allowed to qualified discharge to reduce its influence to environment,
The problem of always domestic and international field of waste water treatment.State Ministry of Environmental Protection has issued and implemented new " coking on October 1st, 2012
Learn emission of industrial pollutants standard " (GB16171-2012), more strict requirements: Suo Youqi are proposed to the discharge of coking wastewater
Industry enforced SS(Suspended Solids from January 1st, 2015)≤50 ppm, COD(Chemical Oxygen
Demand)≤80ppm, ammonia nitrogen≤10ppm, petroleum-type≤2.5ppm, cyanide≤0.2ppm, volatile phenol≤0.3ppm discharge
Standard.Specific regulation also proposed to the coking wastewater water quality for being used for coal washing, quenching and blast furnace slag flushing etc. after processing.
TREATMENT OF COKING technology belongs to an international problem at present, and the processing method of common coking wastewater includes
Chemical method, physical-chemical process and bioanalysis, chemical method include catalytic wet oxidation technology, electrochemical oxidation technology, photocatalysis
Oxidizing process；Physical-chemical process includes absorption method, Fenton reagent method etc., and bioanalysis includes activated sludge process, biofilm, biology
Fluidization and bio-denitrification technology etc..There is complicated, expensive, facility scale in existing coking waste water treatment process and equipment
Greatly, the residence time is long, investment cost is higher, requires the defects of stringent to the condition of water quality of waste water.Coal chemical industry high toxicity high concentration
Organic wastewater water outlet COD after conventional biochemical method processing is generally kept in 200~450ppm, and there are the parts in raw water to have
Machine object and the incomplete organic matter homologue of Partial digestion.The phenol generated according to correlation analysis testing result, coal pressure gasification technique
Ammonia waste water, altogether detect 244 kinds of organic pollutants, heterocyclic hardly degraded organic substance polycyclic containing phenols, naphthalene, quinoline, pyridine etc. and
Oxygen-containing, nitrogen, heterocyclic compound of carbon etc..After organic wastewater biochemical treatment, there is also more bio-refractories in water outlet
Substance, such as tetradecanoic acid, n- pentadecanoic acid, the isometric chain aliphatic hydrocarbon of hexadecanoic acid, anti-form-1,2,3,4- tetrahydro -6- methoxyl groups -
The heterocyclics such as bis- (8- Nonyl) esters of 2- (4- pentylcyclohexyl) naphthalene, diisooctyl phthalate, 1,2- benzoic acid, esters are dirty
Object is contaminated, these substances are the difficult points for restricting coal chemical industrial waste water biochemical treatment qualified discharge.
In addition, electrochemical oxidation technology is to generate oxidizing species using electrode reaction to make Pollutants in Wastewater that oxygen occur
Change reduction reaction, to achieve the purpose that purify waste water.Hardly degraded organic substance is on the electrode in highly toxic coking organic wastewater
Electrochemical reaction can directly occur or by generating OH, H at the electrode surface2O2Pollutant drops in equal strong oxidizers
Solution.
General described electro-catalytic oxidation technology refers to insertion electrode plate (anode, cathode) in waste water, then in electrode
Apply voltage between plate.Direct electrochemical reaction occurs on the electrode for pollutant: anodic oxidation makes organic matter and part inorganic matter
It is converted into innocuous substance；Cathodic reduction can remove nitrate anion and heavy metal ion, while can also generate hydroxyl radical free radical, in turn
Mineralising organic matter.It can be understood as usually said " electrolysis ".
Above-mentioned traditional electro-catalytic oxidation technology, effect depend on the material of electrode plate more, for example need in electrode plate
Surface is applied plus noble metal or rare metal coating.Rare precious metal and its applying for complexity add process, cause electrode plate cost very high,
And coating is more enervated, requires operating condition relatively harsh, the service life is short, is finally presented as at high cost, therefore practical industrialization
The case of application is seldom；
Meanwhile the aerobic section aeration quantity of MBBR is big, low energy consumption, and fouling membrane limits MBR in the application in many fields；
Therefore, it is badly in need of that a kind of high treating effect, at low cost, high efficiency, facility occupied area is small, wants to waste water quality condition at present
Ask low coking waste water treatment process, system or device.
Summary of the invention
In order to solve the problems, such as to exist in the prior art, the present invention provides a kind of coking wastewaters comprising biochemical recombiner unit
Processing system and method.
A kind of coking wastewater processing system comprising biochemical recombiner unit, comprising:
Pretreatment unit, for carrying out preliminary treatment to organic wastewater；
MBBR-MBR recombiner unit is connect with the pretreatment unit, for further processing the water outlet of the pretreatment unit；
The MBBR-MBR recombiner unit includes: the MBBR anaerobic pond being sequentially communicated, MBBR anoxic pond, MBBR aerobic tank, MBR unit；
In above-mentioned coking wastewater processing system, the MBR unit is MBR membrane biological reaction as a preferred implementation manner,
Device；
Preferably, the first blender is set in MBBR anaerobic pond, and the first blender is preferably blade agitators；
Preferably, the second blender is set in MBBR anoxic pond, and the second blender is preferably spiral agitator.It is highly preferred that
Floating stuffing is set in the MBBR anoxic pond, it is further preferred that the floating stuffing is the composite filling of polyurethane and sponge,
Wherein sponge is located in hollow polyurethane；It is further preferred that the floating stuffing is column；It is further preferred that the floating stuffing
Filling rate is 10% ~ 70%, and the rate that is preferably filled with is 25% ~ 35%；
Preferably, MBBR anoxic bottom of pond portion is additionally provided with circulation mixed liquor outlet, and the circulation mixed liquor outlet is detested with MBBR
The refluxing opening of oxygen tank bottom is connected to；
Preferably, the aerobic bottom of pond portion of the MBBR is provided with aerator and sludge outlet；It is highly preferred that good in the MBBR
Floating stuffing is set in oxygen pond, it is preferable that the floating stuffing is the composite filling of polyurethane and sponge, and wherein sponge is located at hollow
In polyurethane；It is further preferred that the filling rate that the floating stuffing is the column floating stuffing is 10% ~ 70%, the rate that is preferably filled with is 25%
~35%；
Preferably, it is provided with MBR film device in MBR membrane bioreactor, controls fibre curtain in the preferably PVDF in 0.03 μm of aperture
Formula component；It is highly preferred that the concentrated water outlet of the MBR film device is connect with the entrance of oxygen consumption of reactor, oxygen consumption is anti-
The outlet of device is answered to be connected to the MBBR anoxic pond.
In above-mentioned coking wastewater processing system, the pretreatment unit and MBBR- as a preferred implementation manner,
Electrocatalytic oxidation unit is additionally provided between MBR recombiner unit, the electrocatalytic oxidation unit is connect with the pretreatment unit, is used
In waste water of the processing from the pretreatment unit；
The MBBR-MBR recombiner unit is connect with the electrocatalytic oxidation unit, comes from the electrocatalytic oxidation list for handling
The waste water of member；
The electrocatalytic oxidation unit includes: electrocatalysis oxidation reaction device ontology, for providing the space of electrocatalysis oxidation reaction；
Multiple graphite electrodes at equal intervals and are vertically provided at the inside of the electrocatalysis oxidation reaction device ontology, and adjoining graphite electricity
The upper end of pole is connected with the anode and cathode of DC power supply respectively；Catalyst, the sky being set between the adjoining graphite electrodes
At gap；Aerator is set to the electrocatalysis oxidation reaction device body bottom portion, and the partly or entirely aeration spray of aerator
The gas emission direction of mouth is opposite with graphite electrode.
In above-mentioned coking wastewater processing system, the electrocatalytic oxidation unit is electricity as a preferred implementation manner,
Catalyst dosing tank is arranged in catalyst oxidation reactor, the electrocatalysis oxidation reaction device top.
In above-mentioned coking wastewater processing system, the electrocatalysis oxidation reaction device sheet as a preferred implementation manner,
Inlet and outlet are respectively set in the top two lateral walls of body；
Preferably, catalyst is set in the space between the electrocatalysis oxidation reaction device ontology bottom surface and the bottom end of graphite electrode
Support plate；
Preferably, the aeration nozzle is multiple rows of, and the aeration nozzle of part row is parallel with the bottom edge of graphite electrode；It is highly preferred that
The aeration nozzle is y-type structure, and fumarole is the crosspoint of y-type structure；
Preferably, the aeration nozzle expose into gas be ozone；
Preferably, back purge system is equipped with every piece of graphite electrode upper end.
In above-mentioned coking wastewater processing system, the spacing between adjoining graphite electrodes as a preferred implementation manner,
For 20 ~ 40cm, more preferably 25cm；Preferably, catalyst filling rate is 10% ~ 40%.
In above-mentioned coking wastewater processing system, the pretreatment unit includes: second level as a preferred implementation manner,
Biochemical treatment unit connect with secondary biochemical treatment unit and handles the coagulating sedimentation unit of secondary biochemical treatment unit water outlet；
The pretreatment unit further include: the multi-medium filtering list of coagulating sedimentation unit water outlet is connect and handled with coagulating sedimentation unit
Member.
A kind of processing method of coking wastewater, uses above system to complete, the treating method comprises:
Pre-treatment step: organic wastewater is introduced into pretreatment unit and carries out preliminary treatment；
MBBR-MBR recombiner unit processing step, the water outlet of pre-treatment step enter MBBR-MBR recombiner unit and carry out at biochemistry
Reason；
Preferably, in the MBBR-MBR recombiner unit processing step, the hydraulic detention time of MBBR anaerobic pond is 0.5 ~ 4h,
The hydraulic detention time of MBBR anoxic pond is 1 ~ 5h, and the hydraulic detention time of MBBR aerobic tank is 3 ~ 8h, MBR membrane bioreactor
Hydraulic detention time be 3 ~ 10h, the filling rate of the floating stuffing of MBBR anoxic pond and MBBR aerobic tank is 10 ~ 70%, preferably
The filling rate of floating stuffing is 25% ~ 35%.
In above-mentioned processing method, the floating stuffing is the poly- ammonia that inside is sponge as a preferred implementation manner,
Ester cylindrical body filler.
In above-mentioned processing method, the processing method as a preferred implementation manner, further include:
Electrocatalytic oxidation processing step: the water outlet of pre-treatment step enters electrocatalytic oxidation processing unit and carries out oxidation processes, electricity
The water outlet of catalytic oxidation treatment enters MBBR-MBR recombiner unit and carries out biochemical treatment；
Preferably, in the electrocatalytic oxidation processing step, catalyst filling rate is 10% ~ 40%, and the spacing between adjacent electrode is
20 ~ 40cm, water intake velocity are 1.5 ~ 2.5L/h, and 18 ~ 23V of voltage, aeration flow is 200 ~ 500L/h, hydraulic detention time 28
~32min。
The present invention has following technical effect:
Currently preferred organic wastewater treating system specifically include that multi-medium filtering unit, electrochemical catalytic oxidation unit with
And strengthen biochemical treatment unit (i.e. MBBR-MBR recombiner unit).Firstly, multi-medium filtering will be introduced by pretreated waste water
Unit, subsequently into electrochemical catalytic oxidation unit, enter strengthen biochemical treatment unit later.Strengthening biochemical unit includes anaerobism
The aerobic section and MBR membrane bioreactor of section, the anoxic section of the filler containing improved, the filler containing improved.Using
Present system and technique can effectively deal with the hardly degraded organic substance in coking wastewater, and whole system water outlet COD stabilization is lower than
40ppm, most down to 8ppm, TOC removal rate is 60% or more.
The present invention puts into floating stuffing, microorganism apposition growth on filler in the biological reaction pool for strengthening biochemical unit
Formed biomembrane, when sewage flows through biofilm surface, organic matter by biomembrane microorganism adsorption and degradation.Aerobic
In MBBR, the floating stuffing in moving condition can generate dissection to bubble, be evenly distributed dissolved oxygen can further
In reactor, to increase the utilization rate of oxygen, mass-transfer efficiency is improved, is made so as to reduce to a certain extent because being largely aerated
At the consumption of the energy.
In addition, system and technique of the invention are except the effect for reducing COD in waste water is obvious, (COD in processed waste water is remote
Outside lower than national standard GB16171-2012), also have at low cost, high efficiency, facility occupied area it is small, to the requirement of waste water quality condition
Low advantage.Present system can be with by the electrochemical catalytic oxidation of short time (the about hydraulic detention time of half an hour) processing
Make the organic pollutant open loop that phenyl ring class formation is had in waste water, to considerably increase the degradation of subsequent reinforced biochemical treatment unit
The ability of organic pollutant, while the short processing time of biochemical treatment unit of the invention (hydraulic detention time is no more than for 24 hours).
In general, to reach water outlet COD index same as the present invention, only need 2h's or more by Conventional electrochemical catalytic oxidation treatment
Hydraulic detention time, power consumption is big, catalyst amount is high.And it is organic that the phenyl ring class that is difficult to degrade is handled only with routine biochemistry
Object is discharged COD high, and hydraulic detention time is long, usually in 100h or more.Therefore, present system in the shortest possible time,
The efficient degradation of organic matter is realized, COD degradation efficiency is up to 90% or more, and the usage amount of catalyst is low, power consumption is low, effect
Rate is high.
Effluent SS (Suspended Solids)≤50ppm of system and technique of the invention, ammonia nitrogen≤10ppm, stone
Oils≤2.5ppm, cyanide≤0.1ppm, volatile phenol≤0.3ppm(can reach 0.1 ppm).
Detailed description of the invention
Fig. 1 is the structural schematic diagram of electrocatalytic oxidation unit of the invention；
Fig. 2 is the structural schematic diagram of MBBR-MBR recombiner unit；
Fig. 3 is the structural schematic diagram of optimum decision system of the present invention.
Wherein, appended drawing reference is as follows:
1- electrocatalytic oxidation unit；11- catalyst dosing tank；12- graphite electrode；13- catalyst；14- aeration nozzle；15- is urged
Agent support plate；16- water inlet；17- water outlet；2-MBBR-MBR recombiner unit；21- MBBR；211-MBBR anaerobic pond；
212-MBBR anoxic pond；213-MBBR aerobic tank；2111- anaerobic pond exhaust valve, 2121- anoxic pond exhaust valve, 2131- aerobic tank
Exhaust valve；2132- aerator；22-MBR membrane bioreactor；221-MBR membrane bioreactor exhaust valve；The consumption of 23- oxygen
Reactor；3- multi-medium filtering unit；4- coagulating sedimentation unit；41- flocculant dosing tank；5- sludge treating block.
Specific embodiment
To make the object, technical solutions and advantages of the present invention clearer, below in conjunction with attached drawing to embodiment party of the present invention
Formula is described in further detail.
The present invention provides a kind of organic wastewater treating system, the in particular to organic waste in a kind of coal chemical industry/coking industry
Water treatment system.According to water (flow) direction successively include: pretreatment unit in organic wastewater treating system provided by the invention, be used for
The electrocatalytic oxidation unit from pretreatment unit waste water is received and processed, system of the invention can also include for receiving simultaneously
Handle the MBBR-MBR recombiner unit from electrocatalytic oxidation unit.Below to each list of organic wastewater treating system of the present invention
Member and connection relationship are described in detail.
Pretreatment unit
Pretreatment unit mainly carries out preliminary treatment to the organic wastewater in coal chemical industry/coking industry, urges so that it meets electricity
Change the water inlet standard of oxidation unit, in general, the water quality for entering electrocatalytic oxidation unit of the present invention is COD in 80 ~ 500ppm.At this
In the embodiment of invention, pretreatment unit may include: coal chemical industry/chemical products waste water routine secondary biochemical treatment unit, with two
The connection of grade biochemical treatment unit and handle the coagulating sedimentation unit 4 of conventional secondary biochemical treatment unit water outlet and/or heavy with coagulation
The connection of shallow lake unit and the multi-medium filtering unit 3 for handling the water outlet of coagulating sedimentation unit.When electrocatalytic oxidation unit of the present invention into
When water water quality requirement is relatively high, pretreatment unit can also include: setting coagulating sedimentation unit and multi-medium filtering unit it
Between and the activated carbon filter (not shown) that is connect with the two.Pretreatment unit can also include: useless in coal chemical industry/chemical products
Hydrolysis acidification unit is set between water routine secondary biochemical treatment unit and coagulating sedimentation unit 4.
In pretreatment unit, conventional secondary biochemical treatment unit is the prior art, and activated carbon filter is also existing filter tank,
Hydrolysis acidification unit is the prior art, then this is not being repeated one by one.
In pretreatment unit, coagulating sedimentation unit 4 makes colloid in waste water and thin mainly under the action of flocculant
Micro suspension object is condensed into floccule body, is then separated off, to realize most of SS(Suspended Solids, suspends
Object) removal reduce the residence time to improve the degradation efficiency of subsequent advanced oxidation workshop section, improve efficiency.What the present invention used
Flocculant is aluminium polychloride or polyacrylamide flocculant.Flocculation is set above the coagulative precipitation tank of coagulating sedimentation unit
Agent dosing tank 41, so that the flocculant of specific metering is added into coagulative precipitation tank according to actual needs.
In pretreatment unit, multi-medium filtering unit 3 can be realized using conventional more medium filter, multimedium mistake
2 ~ 6 layers of filter packing of size grading are pressed in filter from bottom to top, all filler fillings account for the 50 ~ 70% of filter container inner capacities.
Optional filler has quartz sand, anthracite, magnetic iron ore, gangue, active carbon, haydite etc., is selected according to different filtration needs.At this
In the embodiment of invention, the filler in the more medium filter can be selected from coal chemical industry solid waste, including gangue, clinker
It is fixed for practical influent quality by particle size distribution analysis, pore structure study, hardness analysis etc. Deng, cheap filter medium of arranging in pairs or groups
Filter packing padding scheme processed realizes that solid wastes recycling utilizes and control the purpose of cost.Especially the present invention can use coal
The gangue waste material that charcoal exploits association replaces bottom bulk filler, and then waste utilization, and reduces costs.When handling waste water,
In order to guarantee that treatment effect, waste water are preferably 8 ~ 12m in the flow rate of liquid of the multi-medium filtering unit 33/h。
Electrocatalytic oxidation unit
Electrocatalytic oxidation unit of the invention is different from conventional plate type electrode and is electrolysed, and between electrode plate, fills specific catalysis
Then agent is uniformly distributed catalyst between plate type electrode by micro- aeration, and electrocatalytic oxidation unit of the present invention uses
Electrode is not that the high cost electrode plate for adding noble metal or rare metal coating, and the graphite electrode without any coating are applied in surface
Plate greatly reduces the cost of electrocatalytic oxidation unit, in addition, the present invention drops to increase the organic matter of electrocatalytic oxidation unit
Effect is solved, is preferably exposed into device into air or ozone, more preferably ozone.
The support type circular cylindrical solid catalyst that the present invention uses is resistant to general acid, alkaline environment, not because
Chemical reaction occurs to fall off, chemical lifetime is stable, lasting, substantially reduces catalyst usage amount, extends catalyst change week
Phase reduces operating cost.
(1) structure of electrocatalytic oxidation unit
The water inlet 16 of electrocatalytic oxidation unit 1 is connect with the water outlet of pretreatment unit, in an embodiment of the present invention, referring to
Fig. 1, electrocatalytic oxidation unit 1 are electrocatalysis oxidation reaction device, and catalyst dosing tank 11 is arranged in top, to facilitate if necessary
Required catalyst is added into electrocatalysis oxidation reaction device, electrocatalytic oxidation unit 1 includes: reactor body, for providing
The space of electrocatalysis oxidation reaction；Water inlet 16 and water outlet is respectively set in the top two lateral walls of reactor body
17；Multiple graphite electrodes 12 at equal intervals and are vertically provided at the inside of reactor body, the upper end point of adjoining graphite electrodes 12
Not with DC power supply anode and cathode be connected, i.e., adjoining graphite electrodes 12 charge difference, be consequently formed graphite electrode anode with
The structure that graphite electrode cathode is arranged alternately；It is set in space between the bottom surface of reactor body and the bottom end of graphite electrode 12
Catalyst support plate 15 is set, the catalyst being put into reactor body is used to support, catalyst support plate 15 can be with reactor
The bottom surface of ontology is arranged in parallel and is that the plate of porous structure, waste water can pass freely through the hole on catalyst support plate 15.?
Multiple rows of aeration nozzle, the gas of part aeration nozzle are set in the space between catalyst support plate 15 and the bottom end of graphite electrode 12
Body emission direction is preferably opposite with graphite electrode 12, so as to increase expose into air or ozone utilizing status.Catalyst
It is set in the space between adjoining graphite electrodes 12, before electrocatalysis oxidation reaction device operation, catalyst deposit is being catalyzed
In agent support plate 15, in the electrocatalysis oxidation reaction device operational process, catalyst can be blown afloat by the air or ozone that exposure enters, from
And it is suspended in waste water.
Preferably, the spacing between adjoining graphite electrodes 12 is 20 ~ 40cm, more preferably 25cm.In order to make aeration nozzle
14 gas emission direction is i.e. opposite with graphite electrode 12 upwards, and aeration nozzle 14 is y-type structure, and fumarole is y-type structure
Crosspoint, the structure can be such that aeration gas flow moves up in reactor body.
Aeration nozzle 14 occurs with the air compressor (or air storage cylinder) or ozone being set to outside reactor body
Device connection is used to provide air or ozone to the inside of reactor body.
The catalyst that the present invention uses is preferably support type circular cylindrical solid catalyst, and the catalytic mechanical of this kind of structure is strong
Degree is high, loss late is low, and the catalyst is the catalyst containing active metals one or more in Mn, Fe, Ni, Co and Cu.Catalysis
Agent filling rate (filling rate refers to that the stacking volume of catalyst accounts for the percentage of electrocatalysis oxidation reaction device inner space volume) is
10%~40%。
In order to increase the service life and using effect of graphite electrode plate 12, it is equipped with every piece of 12 upper end of graphite electrode plate
Back purge system.Back purge system can be used for removing bubble and carbon dust between electrode.
(2) application method of electrocatalytic oxidation unit of the present invention
Using electrocatalytic oxidation unit of the invention as described above, direct current is passed through to graphite electrode, passes through electrocatalytic oxidation list
First water inlet 16 introduces the water outlet of pretreatment unit in electrocatalytic oxidation unit, and waste water flows through reactor with the speed set,
Processed waste water is drained into except electrocatalytic oxidation unit by electrocatalytic oxidation unit water outlet 17, carries out the place of next step
Reason.
The water outlet of pretreatment unit is through electrocatalytic oxidation cell processing, wherein catalyst filling rate is 10% ~ 40%, adjacent
Interelectrode spacing is 20 ~ 40cm, and water intake velocity is 1.5 ~ 2.5L/h, 18 ~ 23V of voltage, and aeration flow is 200 ~ 500 L/h,
Hydraulic detention time is 30 ~ 120min；Specific hydraulic detention time is depending on the requirement of influent COD and effluent quality, usually
Influent COD in 500 ppm waste water below, in above-mentioned hydraulic detention time can be achieved water outlet COD degradation rate reach 85% with
On, even up to 90%.When being combined with lower section MBBR-MBR recombiner unit, preferably hydraulic detention time is 30min.
The embodiment using electrocatalytic oxidation cell processing coking wastewater is given below.Enter electro-catalysis in following embodiment
The waste water of oxidation unit is to locate the waste water of coke-oven plant's discharge in advance through conventional secondary biochemical treatment, hydrolysis acidification and flocculation sedimentation
It is obtained after reason, into water quality such as the following table 1 of the waste water of electrocatalytic oxidation unit:
Table 1
Embodiment 1
Waste water described in table 1 is handled using electrocatalytic oxidation unit, is divided into four groups of experiments, wherein in four groups of experiments, adjacent stone
Spacing between electrode ink 12 is 30 cm, expose into gas be ozone, ozone flow is 300 L/h, catalyst filling
Rate is respectively 10%, 20%, 30%, 40%, water intake velocity 2L/h, voltage 20V, and continuum micromeehanics ten hours, hydraulic detention time
For 30min, four groups of experiment effluent qualities are as follows: COD, which stablizes, is lower than 40ppm, and volatile phenol, which is stablized, is lower than 0.4ppm, and cyanide is stablized
Lower than 0.2 ppm, ammonia nitrogen, which is stablized, is lower than 8 ppm, and TOC removal rate, which is stablized, is higher than 30%；The effect that wherein filler is 40% is best.
Embodiment 2
The present embodiment is using waste water described in electrocatalytic oxidation cell processing table 1, wherein the spacing between adjoining graphite electrodes 12 is
30 cm, expose into gas be ozone, ozone flow be 300 L/h, catalyst filling rate is 40%, water intake velocity 2L/h,
Voltage is 20V, and continuum micromeehanics ten hours, hydraulic detention time 50min, effluent quality was as follows: COD, which stablizes, is lower than 30ppm, waves
It sends out phenol to stablize lower than 0.1ppm, cyanide, which is stablized, is lower than 0.1 ppm, and ammonia nitrogen, which is stablized, is lower than 5ppm, and TOC removal rate is stable to be higher than
60%。
Moving bed biofilm reactor-membrane bioreactor recombiner unit (MBBR-MBR recombiner unit)
Moving bed biofilm reactor MBBR(Moving Bed Biofilm Reactor) it is traditional activated sludge process and biology
The combination of embrane method.
The present invention will put into floating stuffing in biological reaction pool, and microorganism apposition growth on filler forms biomembrane,
When sewage flows through biofilm surface, organic matter by biomembrane microorganism adsorption and degradation.In aerobic MBBR, in shifting
The floating stuffing of dynamic state can generate dissection to bubble, be evenly distributed in dissolved oxygen can further in reactor, with
Increase the utilization rate of oxygen, mass-transfer efficiency is improved, so as to reduce the consumption for causing the energy because being largely aerated to a certain extent.
Simultaneously as fouling membrane limits MBR in the application in many fields, and the micro- dirt of removal that MBBR-MBR can be significant
Dye object and nutriment simultaneously reduce fouling.The quasi- filling suspension plastic carrier of the present invention is set up with MBR and is gone here and there in anoxic and aerobic stage
Connection processing waste water (Fig. 2) after electrocatalytic oxidation advanced treating.
The structure of recombiner unit
The water inlet of MBBR-MBR recombiner unit 2 is connect with the water outlet 17 of electrocatalytic oxidation unit 1, in the embodiment of the present invention
In, the structure of MBBR-MBR recombiner unit 2 is as shown in Fig. 2, the MBBR-MBR recombiner unit includes MBBR unit 21 and MBR mono-
Member, MBBR unit 21 include being sequentially communicated: MBBR anaerobic pond 211, MBBR anoxic pond 212, MBBR aerobic tank 213；MBR unit
Including the MBR membrane bioreactor 22 being connect with MBBR aerobic tank water outlet.
First blender is set in MBBR anaerobic pond 211, and the first blender is preferably blade agitators, and mixing speed is
100-200rpm, top are arranged anaerobic pond exhaust valve 2111, can open the exhaust valve when hypertonia in the pond, prevent pond
It is interior to generate excessive gas and cause danger.The top of pond body, electrocatalytic oxidation unit is arranged in the water inlet of MBBR anaerobic pond 211
1 water outlet passes through 211 water inlet of MBBR anaerobic pond first and enters MBBR anaerobic pond 211, the macromolecular in anaerobic pond, in waste water
Organic matter can be degraded to small molecule compound by anaerobic bacteria.
211 water outlet of MBBR anaerobic pond is connected to 212 water inlet of MBBR anoxic pond, and that treated is useless for MBBR anaerobic pond 211
Water drains into MBBR anoxic pond 212 through 211 water outlet of MBBR anaerobic pond.The second blender of setting in MBBR anoxic pond 212, second
Blender is preferably spiral agitator, and top is arranged anoxic pond exhaust valve 2121, can open this when hypertonia in the pond
Exhaust valve prevents from generating excessive gas in pond and causing danger.Floating stuffing is set in the MBBR anoxic pond 212, it is preferable that
The floating stuffing is the composite filling of polyurethane and sponge, and wherein sponge is located in hollow polyurethane；It is further preferred that the floating stuffing
Specification for column, such as the polyurethane positioned at outside is 20mm × 10mm, and (filling rate is i.e. outstanding for the filling rate of the floating stuffing
The stacking volume of floating filler accounts for the percentage of entire anoxic pond total volume) it is 10% ~ 70%, the rate that is preferably filled with is 25% ~ 35%, this hair
Biomembrane is more readily formed in bright filler, and membrane area is bigger, and filling rate should not be excessive, can cause to block, excessively few then to handle
Effect is limited.Under anaerobic environment, the microorganism of floating stuffing surface enrichment growth can be further organic in degrading waste water
Object.212 bottom of MBBR anoxic pond is additionally provided with circulation mixed liquor outlet, connects with the refluxing opening of 211 bottom of MBBR anaerobic pond
It is logical, the circulation mixed liquor from MBBR anoxic pond 212 is flowed back into MBBR anaerobic pond 211 and is continued in anaerobic pond
Reason.
212 water outlet of MBBR anoxic pond is connected to 213 water inlet of MBBR aerobic tank, and that treated is useless for MBBR anoxic pond 212
Water drains into MBBR aerobic tank 213 through 212 water outlet of MBBR anoxic pond.213 inner top of MBBR aerobic tank is arranged aerobic tank and is vented
Valve 2131, when hypertonia in the pond by the exhaust valve exhaust, 213 bottom of MBBR aerobic tank is provided with aerator 2132
And sludge outlet, for aerator 2132 for being passed through air into MBBR aerobic tank, aeration speed is preferably 300L/min.?
Floating stuffing is set in the MBBR aerobic tank 213, it is preferable that the floating stuffing is the composite filling of polyurethane and sponge, wherein
Sponge is located in hollow polyurethane；It is further preferred that the floating stuffing is column, for example is positioned at the specification of external polyurethane
20mm × 10mm, (filling rate, that is, floating stuffing stacking volume accounts for entire anoxic pond total volume to the filling rate of the floating stuffing
Percentage) it is 10% ~ 70%, the rate that is preferably filled with is 25% ~ 35%.In aerobic tank, aerobic microbiological plays to be polluted in Decomposition Wastewater
The effect of object.The waste sludge generated in MBBR aerobic tank 213 can be periodically discharged by sludge outlet.MBBR aerobic tank 213
It is run in a manner of the low sludge age of high load capacity.
If not adding the filler of structure of the invention in anoxic pond and aerobic tank or only adding conventional fillers such as poly- third
Alkene filler, in the conditions of the invention, water outlet COD are difficult up to standard.Filler of the invention is fairly simple without fixing, and hangs
Film effect is ideal.
213 water outlet of MBBR aerobic tank is connected to 22 water inlet of MBR membrane bioreactor, after the processing of MBBR aerobic tank 213
Waste water drained into MBR membrane bioreactor 22 through aerobic tank water outlet.
It is provided with MBR film device in MBR membrane bioreactor 22, controls fiber curtain in the preferably PVDF in 0.03 μm of aperture
Component is used for purified water, MBR membrane bioreactor exhaust valve 221 is arranged at the top of MBR membrane bioreactor, when pressure in the pond
More than it is excessively high when pass through the exhaust valve exhaust.MBR membrane bioreactor 22 is run in a manner of the high sludge age of underload.MBR film device
The water outlet of water outlet meet country to the discharge standard of the organic wastewater in coal chemical industry/coking industry.
The concentrated water outlet of the MBR film device other side is connect with the entrance of oxygen consumption of reactor 23, oxygen consumption of reactor
23 outlet is connected to MBBR anoxic pond 212.Concentrated water from MBR film device returns to the relaying of MBBR anoxic pond 212 after deoxygenating
It is continuous to be handled.
(2) application method of MBBR-MBR recombiner unit
The water outlet of electrocatalytic oxidation unit 1 is introduced into the MBBR anaerobic pond of MBBR-MBR recombiner unit, MBBR anaerobic pond goes out
Water is followed by MBBR anoxic pond, MBBR aerobic tank and MBR membrane bioreactor, wherein when the hydraulic retention of MBBR anaerobic pond
Between be 0.5 ~ 4h, the hydraulic detention time of MBBR anoxic pond is 1 ~ 5h, and the hydraulic detention time of MBBR aerobic tank is 3 ~ 8h, MBR
The hydraulic detention time of membrane bioreactor is 3 ~ 10h, and the filling rate of the floating stuffing of MBBR anoxic pond and MBBR aerobic tank is equal
It is 10 ~ 70%, preferably the filling rate of floating stuffing is 25% ~ 35%.Floating stuffing is that the polyurethane cylindrical body that inside is sponge is filled out
Material.
Several embodiments using coking wastewater of the MBBR-MBR recombiner unit processing from pretreatment unit are given below.
MBBR-MBR recombiner unit enters water water quality referring to table 2, i.e. water quality before processing in following embodiment.
Embodiment 1
Waste water sequentially enters anaerobic pond, MBBR anoxic pond, MBBR aerobic tank and MBR membrane bioreactor.The anaerobic pond and
It is furnished with blender in MBBR anoxic pond, the aerobic bottom of pond portion of MBBR is furnished with aerator, MBR film is arranged in MBR membrane bioreactor
Device or component.Be added to floating stuffing in MBBR anoxic pond, MBBR aerobic tank, filling rate 25%, floating stuffing be 20mm ×
The polyurethane of 10mm-sponge cylindrical body filler.MBBR anaerobic pond, MBBR anoxic pond, MBBR aerobic tank and MBR membrane bioreactor
Hydraulic detention time be respectively 1h, 2h, 4h, 4h.The effluent quality of MBR membrane bioreactor is referring to table 2.
Embodiment 2
Waste water sequentially enters anaerobic pond, MBBR anoxic pond, MBBR aerobic tank and MBR membrane bioreactor.The anaerobic pond and
It is furnished with blender in MBBR anoxic pond, the aerobic bottom of pond portion of MBBR is furnished with aerator, MBR film is arranged in MBR membrane bioreactor
Device or component.Be added to floating stuffing in MBBR anoxic pond, MBBR aerobic tank, filling rate 30%, floating stuffing be 20mm ×
The polyurethane of 10mm-sponge cylindrical body filler.MBBR anaerobic pond, MBBR anoxic pond, MBBR aerobic tank and MBR membrane bioreactor
Hydraulic detention time be respectively 2h, 3h, 5h, 6h.The effluent quality of MBR membrane bioreactor is referring to table 2.
Embodiment 3
Waste water sequentially enters anaerobic pond, MBBR anoxic pond, MBBR aerobic tank and MBR membrane bioreactor.The anaerobic pond and
It is furnished with blender in MBBR anoxic pond, the aerobic bottom of pond portion of MBBR is furnished with aerator, MBR film is arranged in MBR membrane bioreactor
Device or component.Be added to floating stuffing in MBBR anoxic pond, MBBR aerobic tank, filling rate 35%, floating stuffing be 20mm ×
The polyurethane of 10mm-sponge cylindrical body filler.MBBR anaerobic pond, MBBR anoxic pond, MBBR aerobic tank and MBR membrane bioreactor
Hydraulic detention time be respectively 3h, 4h, 6h, 8h.The effluent quality of MBR membrane bioreactor is referring to table 2.
Table 2
In organic wastewater treating system of the present invention, it can also be set between electrocatalytic oxidation unit and MBBR-MBR recombiner unit
Active sand filter is set, the catalyst fines brought out in drainage can be crossed.
Organic wastewater treating system of the invention is coking of coal/coal chemical industry organic wastewater proposition " EMAT " for high poison
(Enhanced Modular Advanced Treatment) modularization efficient treatment process system, comprising being based on electrochemistry
The core technology of (Electrochemistry, " E "), deep biochemical processing (Biological Membrane Technology,
" M ") including advanced waste water solution, the present invention also has adjusted treatment process, its advantage is that the function of each module is integrated
And function intensified, the not simple reprocessing of the strengthening effect being used in series between each component, but the strong association cooperateed with is made
With.
The geographical feature that place is generated according to sewage, discharge ground feature and sewage inclusion characteristics, dirty after sewage treatment
Water process demand is different, and the advantage purifying contaminated species type of different units is also different, and the aforementioned any unit of the present invention can be into
Row connection.The water outlet of one unit is connected to the water inlet of another unit, can form series connection.Two or more identical lists
The water inlet that the water outlet of member is connected to another unit simultaneously forms summarizing for preliminary treatment sewage.One unit water outlet connects
The water inlet for being connected to other two or more same unit then forms the shunting processing of preliminary treatment sewage.Same unit can
With two or more uses in parallel, it can also be integrated in whole system difference node and connect identical unit.
The structure chart of the sewage disposal system of a certain embodiment of the present invention is referring to Fig. 3.Coking wastewater is through secondary biochemical treatment
Water outlet flows through coagulating sedimentation unit 4 afterwards, passes through multi-medium filtering unit 3, and water outlet is then introduced electrocatalytic oxidation unit 1,
The water outlet of electrocatalytic oxidation unit 1 enters MBBR-MBR recombiner unit 2, what coagulating sedimentation unit 4 and multi-medium filtering unit 3 generated
Sludge enters sludge treating block 5.The embodiment of several systems and application method is given below.
First systematic example
System includes being sequentially communicated: conventional secondary biochemical treatment unit, coagulating sedimentation unit, activated carbon filter, electrocatalytic oxidation
Change unit and active sand filter.
In the system, spacing in electrocatalytic oxidation unit between adjoining graphite electrodes 12 is 30cm, expose into gas be
Ozone, ozone flow are 300L/h, and catalyst filling rate is 40%, voltage 20V, and continuum micromeehanics ten hours, water intake velocity was
1L/h handles water 10L, hydraulic detention time 30min.
Coking wastewater is handled using above-mentioned the first system, coking wastewater flows through conventional secondary biochemical treatment unit,
Coagulating sedimentation unit is passed through, activated carbon filter is passed through, passes through electrocatalytic oxidation unit, is discharged through active sand filter.The
One system before and after the processing water quality data referring to table 3.
Second system example
System includes being sequentially communicated: conventional secondary biochemical treatment unit, coagulating sedimentation unit, activated carbon filter, multimedium mistake
Filter unit, electrocatalytic oxidation unit and active sand filter.
In the system, the setting of electrocatalytic oxidation unit and technological parameter are identical as first systematic, are only in active carbon
Multi-medium filtering unit is increased between filter tank and electrocatalytic oxidation unit.
Coking wastewater is handled using above-mentioned second system, coking wastewater flows through conventional secondary biochemical treatment unit,
Coagulating sedimentation unit is passed through, activated carbon filter is passed through, multi-medium filtering unit is passed through, flows through electrocatalytic oxidation unit,
Water outlet is through active sand filter.Second system before and after the processing water quality data referring to table 3.Conventional secondary biochemical treatment in the system
Unit, coagulating sedimentation unit, activated carbon filter, the equipment of active sand filter and treatment process are identical as first systematic.It is more
The lowermost layer bulky grain of medium filtration unit is gangue.
Third system example
System includes being sequentially communicated: conventional secondary biochemical treatment unit, coagulating sedimentation unit, activated carbon filter, multimedium mistake
Filter unit, electrocatalytic oxidation unit, active sand filter, MBBR-MBR recombiner unit.
In the system, the setting of electrocatalytic oxidation unit and technological parameter are identical as first systematic.The MBBR- of the system
In MBR recombiner unit, waste water sequentially enters anaerobic pond, MBBR anoxic pond, MBBR aerobic tank and MBR membrane bioreactor.It is described
Anaerobic pond and MBBR anoxic pond in be furnished with blender, the aerobic bottom of pond portion of MBBR is furnished with aerator, in MBR membrane bioreactor
MBR film device is set.Floating stuffing, filling rate 25% are added in MBBR anoxic pond, MBBR aerobic tank, floating stuffing is
The polyurethane of 20mm × 10mm-sponge cylindrical body filler.MBBR anaerobic pond, MBBR anoxic pond, MBBR aerobic tank and MBR film biology
The hydraulic detention time of reactor is respectively 1h, 2h, 4h, 4h.
Coking wastewater is handled using above-mentioned third system, coking wastewater flows through conventional secondary biochemical treatment unit,
Coagulating sedimentation unit is passed through, activated carbon filter is passed through, multi-medium filtering unit is passed through, flows through electrocatalytic oxidation unit,
Water outlet enters back into MBBR-MBR recombiner unit through active sand filter.Third system before and after the processing water quality data referring to table 3.This is
The equipment and treatment process of conventional secondary biochemical treatment unit, coagulating sedimentation unit, activated carbon filter, active sand filter in system
It is identical as first systematic.The lowermost layer bulky grain of multi-medium filtering unit is gangue.
Table 3
As known by the technical knowledge, the present invention can by other implementation plans that do not depart from its spiritual essence or necessary characteristics come
It realizes.Therefore, embodiment disclosed above, in all respects are merely illustrative, not the only.It is all
It is included in the invention in the scope of the invention or in the change being equal in the scope of the present invention.
Claims (10)
1. a kind of coking wastewater processing system comprising biochemical recombiner unit characterized by comprising
Pretreatment unit, for carrying out preliminary treatment to organic wastewater；
MBBR-MBR recombiner unit is connect with the pretreatment unit, for further processing the water outlet of the pretreatment unit；
The MBBR-MBR recombiner unit includes: the MBBR anaerobic pond being sequentially communicated, MBBR anoxic pond, MBBR aerobic tank, MBR unit.
2. coking wastewater processing system according to claim 1, which is characterized in that the MBR unit is MBR membrane bioreaction
Answer device；
Preferably, the first blender is set in MBBR anaerobic pond, and the first blender is preferably blade agitators；
Preferably, the second blender is set in MBBR anoxic pond, and the second blender is preferably spiral agitator；
It is highly preferred that floating stuffing is arranged in the MBBR anoxic pond, it is further preferred that the floating stuffing be polyurethane with
The composite filling of sponge, wherein sponge is located in hollow polyurethane；It is further preferred that the floating stuffing is column；Further preferably
Ground, the filling rate of the floating stuffing are 10% ~ 70%, and the rate that is preferably filled with is 25% ~ 35%；
Preferably, MBBR anoxic bottom of pond portion is additionally provided with circulation mixed liquor outlet, and the circulation mixed liquor outlet is detested with MBBR
The refluxing opening of oxygen tank bottom is connected to；
Preferably, the aerobic bottom of pond portion of the MBBR is provided with aerator and sludge outlet；It is highly preferred that good in the MBBR
Floating stuffing is set in oxygen pond, it is preferable that the floating stuffing is the composite filling of polyurethane and sponge, and wherein sponge is located at hollow
In polyurethane；It is further preferred that the filling rate that the floating stuffing is the column floating stuffing is 10% ~ 70%, the rate that is preferably filled with is 25%
~35%；
Preferably, it is provided with MBR film device in MBR membrane bioreactor, controls fibre curtain in the preferably PVDF in 0.03 μm of aperture
Formula component；It is highly preferred that the concentrated water outlet of the MBR film device is connect with the entrance of oxygen consumption of reactor, oxygen consumption is anti-
The outlet of device is answered to be connected to the MBBR anoxic pond.
3. coking wastewater processing system according to claim 1, which is characterized in that the pretreatment unit and MBBR-MBR
Electrocatalytic oxidation unit is additionally provided between recombiner unit；
The electrocatalytic oxidation unit is connect with the pretreatment unit, for handling the waste water from the pretreatment unit；
The MBBR-MBR recombiner unit is connect with the electrocatalytic oxidation unit, comes from the electrocatalytic oxidation list for handling
The waste water of member；
The electrocatalytic oxidation unit includes: electrocatalysis oxidation reaction device ontology, for providing the space of electrocatalysis oxidation reaction；
Multiple graphite electrodes at equal intervals and are vertically provided at the inside of the electrocatalysis oxidation reaction device ontology, and adjoining graphite electricity
The upper end of pole is connected with the anode and cathode of DC power supply respectively；Catalyst, the sky being set between the adjoining graphite electrodes
At gap；Aerator is set to the electrocatalysis oxidation reaction device body bottom portion, and the partly or entirely aeration spray of aerator
The gas emission direction of mouth is opposite with graphite electrode.
4. coking wastewater processing system according to claim 3, which is characterized in that the electrocatalytic oxidation unit is urged for electricity
Catalyst dosing tank is arranged in oxidation device, the electrocatalysis oxidation reaction device top.
5. coking wastewater processing system according to claim 4, which is characterized in that the electrocatalysis oxidation reaction device ontology
Top two lateral walls on inlet and outlet are respectively set；
Preferably, catalyst is set in the space between the electrocatalysis oxidation reaction device ontology bottom surface and the bottom end of graphite electrode
Support plate；
Preferably, the aeration nozzle is multiple rows of, and the aeration nozzle of part row is parallel with the bottom edge of graphite electrode；It is highly preferred that
The aeration nozzle is y-type structure, and fumarole is the crosspoint of y-type structure；
Preferably, the aeration nozzle expose into gas be ozone；
Preferably, back purge system is equipped with every piece of graphite electrode upper end.
6. coking wastewater processing system according to claim 3, which is characterized in that the spacing between adjoining graphite electrodes is
20 ~ 40cm, more preferably 25cm；Preferably, catalyst filling rate is 10% ~ 40%.
7. coking wastewater processing system according to claim 1, which is characterized in that the pretreatment unit includes: second level
Biochemical treatment unit connect with secondary biochemical treatment unit and handles the coagulating sedimentation unit of secondary biochemical treatment unit water outlet；
The pretreatment unit further include: the multi-medium filtering list of coagulating sedimentation unit water outlet is connect and handled with coagulating sedimentation unit
Member.
8. a kind of processing method of coking wastewater, which is characterized in that it uses the described in any item systems of claim 1 ~ 7 complete
At the treating method comprises:
Pre-treatment step: organic wastewater is introduced into pretreatment unit and carries out preliminary treatment；
MBBR-MBR recombiner unit processing step, the water outlet of pre-treatment step enter MBBR-MBR recombiner unit and carry out at biochemistry
Reason；
Preferably, in the MBBR-MBR recombiner unit processing step, the hydraulic detention time of MBBR anaerobic pond is 0.5 ~ 4h,
The hydraulic detention time of MBBR anoxic pond is 1 ~ 5h, and the hydraulic detention time of MBBR aerobic tank is 3 ~ 8h, MBR membrane bioreactor
Hydraulic detention time be 3 ~ 10h, the filling rate of the floating stuffing of MBBR anoxic pond and MBBR aerobic tank is 10 ~ 70%, preferably
The filling rate of floating stuffing is 25% ~ 35%.
9. the processing method of coking wastewater according to claim 8, which is characterized in that the floating stuffing is that inside is sea
Continuous polyurethane cylindrical body filler.
10. the processing method of coking wastewater according to claim 8, which is characterized in that the processing method further include:
Electrocatalytic oxidation processing step: the water outlet of pre-treatment step enters electrocatalytic oxidation processing unit and carries out oxidation processes, electricity
The water outlet of catalytic oxidation treatment enters MBBR-MBR recombiner unit and carries out biochemical treatment；
Preferably, in the electrocatalytic oxidation processing step, catalyst filling rate is 10% ~ 40%, and the spacing between adjacent electrode is
20 ~ 40cm, water intake velocity are 1.5 ~ 2.5L/h, and 18 ~ 23V of voltage, aeration flow is 200 ~ 500L/h, hydraulic detention time 28
~32min。
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| CN115626748A (en) * | 2022-11-29 | 2023-01-20 | 深圳永清水务有限责任公司北京分公司 | Sewage treatment system of nitrogen and phosphorus removal |
| CN115626748B (en) * | 2022-11-29 | 2023-08-15 | 深圳永清水务有限责任公司 | Sewage treatment system for denitrification and dephosphorization |
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