CN109264931A - A kind of waste water reuse treatment method and system - Google Patents
A kind of waste water reuse treatment method and system Download PDFInfo
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- CN109264931A CN109264931A CN201811299842.6A CN201811299842A CN109264931A CN 109264931 A CN109264931 A CN 109264931A CN 201811299842 A CN201811299842 A CN 201811299842A CN 109264931 A CN109264931 A CN 109264931A
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- waste water
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- 239000002351 wastewater Substances 0.000 title claims abstract description 50
- 238000000034 method Methods 0.000 title claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 84
- 239000011347 resin Substances 0.000 claims abstract description 53
- 229920005989 resin Polymers 0.000 claims abstract description 53
- 238000001179 sorption measurement Methods 0.000 claims abstract description 48
- 238000001223 reverse osmosis Methods 0.000 claims abstract description 47
- 238000006243 chemical reaction Methods 0.000 claims abstract description 44
- 239000012528 membrane Substances 0.000 claims abstract description 42
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 41
- 238000001914 filtration Methods 0.000 claims abstract description 39
- 230000003197 catalytic effect Effects 0.000 claims abstract description 29
- 238000006385 ozonation reaction Methods 0.000 claims abstract description 27
- 238000005189 flocculation Methods 0.000 claims abstract description 24
- 230000016615 flocculation Effects 0.000 claims abstract description 24
- 239000000126 substance Substances 0.000 claims abstract description 24
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims abstract description 10
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 28
- 238000001764 infiltration Methods 0.000 claims description 23
- 238000007254 oxidation reaction Methods 0.000 claims description 21
- 230000003647 oxidation Effects 0.000 claims description 19
- 238000001704 evaporation Methods 0.000 claims description 14
- 230000008595 infiltration Effects 0.000 claims description 14
- 238000002425 crystallisation Methods 0.000 claims description 13
- 230000008025 crystallization Effects 0.000 claims description 13
- 230000008020 evaporation Effects 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 12
- 238000011084 recovery Methods 0.000 claims description 11
- 230000004907 flux Effects 0.000 claims description 9
- 239000003480 eluent Substances 0.000 claims description 8
- 238000009292 forward osmosis Methods 0.000 claims description 8
- 230000008929 regeneration Effects 0.000 claims description 7
- 238000011069 regeneration method Methods 0.000 claims description 7
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 6
- 239000011790 ferrous sulphate Substances 0.000 claims description 6
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 6
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 238000004064 recycling Methods 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 5
- 238000005273 aeration Methods 0.000 claims description 4
- 235000012489 doughnuts Nutrition 0.000 claims description 4
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 4
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 4
- 239000002808 molecular sieve Substances 0.000 claims description 4
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 4
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 3
- 229920002472 Starch Polymers 0.000 claims description 3
- 239000004411 aluminium Substances 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 3
- 239000001099 ammonium carbonate Substances 0.000 claims description 3
- 125000002091 cationic group Chemical group 0.000 claims description 3
- 239000011148 porous material Substances 0.000 claims description 3
- 238000009287 sand filtration Methods 0.000 claims description 3
- 235000019698 starch Nutrition 0.000 claims description 3
- 239000008107 starch Substances 0.000 claims description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- 230000008859 change Effects 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- 239000012466 permeate Substances 0.000 claims description 2
- 238000004062 sedimentation Methods 0.000 claims description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 229910001882 dioxygen Inorganic materials 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 5
- 150000003839 salts Chemical class 0.000 abstract description 5
- 238000005842 biochemical reaction Methods 0.000 abstract description 3
- 238000005261 decarburization Methods 0.000 abstract description 3
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 239000010802 sludge Substances 0.000 abstract description 2
- 239000003245 coal Substances 0.000 description 14
- 239000010842 industrial wastewater Substances 0.000 description 12
- 238000004519 manufacturing process Methods 0.000 description 10
- 239000012141 concentrate Substances 0.000 description 5
- 238000004140 cleaning Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 229920002401 polyacrylamide Polymers 0.000 description 4
- 239000013078 crystal Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000005416 organic matter Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000009298 carbon filtering Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- -1 nitrogen-containing heterocycle compound Chemical class 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003034 coal gas Substances 0.000 description 1
- 239000011280 coal tar Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 231100001240 inorganic pollutant Toxicity 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N thiocyanic acid Chemical class SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 1
- 238000004065 wastewater treatment 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
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
-
- 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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
-
- 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
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
-
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- 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
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/02—Aerobic processes
Landscapes
- 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 Sorption (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
The present invention provides a kind of waste water reuse treatment method and system, and this method includes successively carrying out flocculation reaction, filtering, ozone catalytic reaction, MBR reaction, activated carbon adsorption, resin adsorption, reverse osmosis to waste water.While the present invention is using the decarburization of catalytic ozonation process efficient rate and decoloration; salt content in waste water is not increased; MBR reaction tank integrates activated sludge biochemical reaction and filters with film; do not generate concentrated water; further remove the COD in waste water; activated carbon adsorption and resin adsorption are further ensured that the influent quality of reverse osmosis membrane, protect reverse osmosis membrane not contaminated, realize the efficient reuse of wastewater from chemical industry.
Description
Technical field
The present invention relates to technical field of waste water processing, more particularly to a kind of waste water reuse treatment method and system.
Background technique
Coal chemical industrial waste water is that steel and iron industry coke-oven plant and City Gas Plant are produced in production coke, coal gas, tar and coking
The waste water generated during product, complicated component and color heavy, containing there are many organic and inorganic pollutant, cyanides, thiocyanic acid
Salt, phenolic compound, polycyclic aromatic hydrocarbon (PAHs), nitrogen-containing heterocycle compound, oxygen-containing or sulfur heterocyclic compound and long-chain rouge
Fat compounds of group etc..
Coal chemical industry processing generallys use pretreatment → biochemical treatment → advanced treating process flow.Wherein, pretreatment master
The substances such as oils, ammonia nitrogen and the phenols in waste water are removed, biochemical treatment mainly removes COD, ammonia nitrogen and total nitrogen in waste water.It is deep
Degree processing is the organic matter etc. further gone in water removal, and water outlet is made to reach the standard of discharge.And coal chemical industry be it is typical it is highly water intensive,
High pollution industry, develop Chemical Industry with preserve the ecological environment it is particularly thorny；Therefore, coal chemical industrial waste water reuse skill is researched and developed
Art not only can promote the development of Chemical Industry, reduce environmental pollution, and can also water resource be made to be fully used, be conducive to reality
The target of existing sustainable development.
Currently, embrane method technology is applied to industrial wastewater recycling field more and more widely, and always exist Membrane cleaning frequency
How the problems such as rate height, producing water ratio uses reasonable technology not only to achieve the purpose that effluent reuse, but also can be further improved clear
The problem of water rate of recovery is current urgent need to resolve.
Summary of the invention
In view of the foregoing deficiencies of prior art, the purpose of the present invention is to provide a kind of waste water reuse treatment method and
The problems such as system, cleaning frequency membrane is high when for solving wastewater treatment in the prior art, producing water ratio is low.
In order to achieve the above objects and other related objects, first aspect present invention provides a kind of waste water reuse treatment method,
Including successively carrying out flocculation reaction, filtering, ozone catalytic reaction, MBR reaction, activated carbon adsorption, resin adsorption, reverse osmosis to waste water
Thoroughly.
In some embodiments of the invention, COD≤500mg/L of the waste water, preferably 200~500mg/L.
In some embodiments of the invention, the waste water is biochemical treated coal chemical industrial waste water.
In some embodiments of the invention, when flocculation reaction, the flocculant of use includes the first flocculant, the second flocculation
Agent, first flocculant are selected from least one of bodied ferric sulfate, aluminium polychloride, poly-ferric chloride, second wadding
Solidifying agent is selected from least one of PAM (polyacrylamide), cationic starch.
In some embodiments of the invention, when flocculation reaction, the dosage of first flocculant is 300~500mg/
The first flocculant of 300~500mg, preferably 300mg/L are added in i.e. every liter of waste water by L.
In some embodiments of the invention, when flocculation reaction, the dosage of second flocculant is 10~20mg/L,
The second flocculant of 15mg is added in i.e. every liter of waste water by preferably 15mg/L.
In some embodiments of the invention, when flocculation reaction, the reaction time is 5~30min, preferably 10min.
In some embodiments of the invention, after flocculation reaction, 30~60min, preferably 30min are precipitated.
In some embodiments of the invention, when filtering, using sand filtration, multi-medium filtering, fibre-ball filtration or active carbon
Filtering.
In some embodiments of the invention, when filtering, filtering velocity is 2~15m/h.
In some embodiments of the invention, controlling filtered delivery turbidity is 5~8.
In some embodiments of the invention, it when catalytic ozonation, carries out, reacts in catalytic ozonation reactor
Molecular sieve catalyst is loaded in device.
In some embodiments of the invention, when catalytic ozonation, ozone dosage is 30~350mg/L, preferably
100~250mg/L, more preferably 100~200mg/L.
In some embodiments of the invention, when catalytic ozonation, the reaction time is 0.5~2h.Reaction time is
Hydraulic detention time.
In some embodiments of the invention, it when MBR reacts, is carried out in MBR reaction tank, doughnut is loaded in pond
MBR film.
In some embodiments of the invention, when MBR reacts, gas-water ratio is (5~15) in pond in MBR reaction tank: 1.
In some embodiments of the invention, when MBR reacts, MBR membrane aperture is 0.02~0.05 μm.
In some embodiments of the invention, when MBR reacts, film average flux is 12~20L/m2*h。
In some embodiments of the invention, MBR be discharged COD be 50~70mg/L, 30~50 times of coloration.
In some embodiments of the invention, when activated carbon adsorption, filtering velocity is 5~10m/h.
In some embodiments of the invention, when resin adsorption, resin is non-polar macroporous resin.
In some embodiments of the invention, the specific surface area of the resin is 700~1000m2/ g, average pore size 8
~15nm.
In some embodiments of the invention, when resin adsorption, 2~10BV/h of filtering velocity.
In some embodiments of the invention, when resin adsorption, the cycle of operation of resin is 100~150h, that is, runs 100
Resin regeneration is carried out after~150h.
In some embodiments of the invention, Fenton oxidation is carried out to the resulting eluent of resin regeneration, is discharged after oxidation
Wastewater biochemical system is returned to be handled.
In some embodiments of the invention, when Fenton oxidation reacts, reacting liquid pH value control is 3~4.
In some embodiments of the invention, when Fenton oxidation reacts, hydrogen peroxide, hydrogen peroxide and influent COD quality are added
The ratio between be (0.5~8): 1, preferably 4:1.Hydrogen peroxide mass concentration herein is 27.5%, is industrial hydrogen peroxide.
In some embodiments of the invention, when Fenton oxidation reacts, ferrous sulfate, hydrogen peroxide and ferrous sulfate object are added
The ratio between amount of matter is (1~5): 1.Hydrogen peroxide herein does not include aqueous solvent.
In some embodiments of the invention, when reverse osmosis, it is anti-that the permeable membrane is selected from disc tube reverse osmosis (dt-ro) film, fiber type
At least one of permeable membrane, coiled reverse osmosis membrane, plate and frame reverse osmosis membrane.
In some embodiments of the invention, when reverse osmosis, operating pressure is 0.5~5Mpa, preferably 4Mpa.
In some embodiments of the invention, the clean water rate of recovery of reverse osmosis membrane is 70~75% (v/v), and clean water is returned
For producing.It is 70~75% across the percentage that the water outlet volume of reverse osmosis membrane accounts for feed water by reverse osmosis volume.
In some embodiments of the invention, the membrane flux of reverse osmosis membrane is 13~30LMH, LMH, that is, L/m2*h。
In some embodiments of the invention, the cycle of operation of reverse osmosis membrane is 6~7 months.That is the every operation 6 of reverse osmosis membrane
It is once cleaned within~7 months.
In some embodiments of the invention, reverse osmosis resulting dope enters positive infiltration.Dope, which refers to, to be not passed through instead
The liquid of permeable membrane.
In some embodiments of the invention, the clean water rate of recovery of forward osmosis membrane is 50% (v/v)~75% (v/v),
Preferably 60% (v/v).
In some embodiments of the invention, the membrane flux of forward osmosis membrane is 25~30LMH.
In some embodiments of the invention, it when positive infiltration, intakes and draws after liquid mix, then through forward osmosis membrane.
In some embodiments of the invention, the liquid that draws is selected from ammonium carbonate solution.
In some embodiments of the invention, it is just permeating resulting dope and is entering evaporation and crystallization system, evaporating resulting liquid
Body is back to production, realizes wastewater zero discharge, and resulting crystal salt outward transport is used for other industrial uses.
Second aspect of the present invention provides a kind of waste water recycling treatment system, including sequentially connected flocculation tank, filtering
System, catalytic ozonation system, MBR reaction tank, activated carbon adsorption system, resin adsorption system, counter-infiltration system；
The flocculation tank is used to carry out flocculation sedimentation to waste water；
The filtration system is for being filtered processing to the water outlet of the flocculation tank；
The catalytic ozonation system is used for the water outlet to the filtration system and carries out catalytic ozonation processing；
The MBR reaction tank is used to carry out the water outlet of the catalytic ozonation system aeration membrane biological reaction processing；
The activated carbon adsorption system is used for the water outlet to the MBR reaction tank and carries out adsorption treatment；
The resin adsorption system is used for the water outlet to the activated carbon adsorption system and carries out resin adsorption processing；
The counter-infiltration system is used for the water outlet to the resin adsorption system and carries out reverse osmosis treatment.
In some embodiments of the invention, the water inlet end of the flocculation tank is connected to biochemical treatment system.
In some embodiments of the invention, the filtration system includes more medium filter.
In some embodiments of the invention, the catalytic ozonation system includes catalytic ozonation reactor, instead
It answers and loads molecular sieve catalyst in device.
In some embodiments of the invention, doughnut MBR film is loaded in the MBR reaction tank.
In some embodiments of the invention, the resin of the resin adsorption system is non-polar macroporous resin.
In some embodiments of the invention, the specific surface area of the resin is 700~1000m2/ g, average pore size 8
~15nm.
In some embodiments of the invention, the counter-infiltration system includes disc tube reverse osmosis (dt-ro) film, the reverse osmosis system
The clean water outlet of system is to the production equipment for needing water.
It in some embodiments of the invention, further include resin regeneration system, for being regenerated to resin.
It in some embodiments of the invention, further include Fenton oxidation system, for being generated to the resin regeneration system
Eluent carry out Fenton oxidation, the water outlet after oxidation enters biochemical treatment system.
It in some embodiments of the invention, further include positive osmosis system, it is dense for being generated to the counter-infiltration system
Liquid carries out positive infiltration processing, the clean water outlet of the positive osmosis system to the production equipment for needing water.
It in some embodiments of the invention, further include evaporation and crystallization system, for what is generated to the positive osmosis system
Dope is evaporated crystallization treatment.
In some embodiments of the invention, the evaporation and crystallization system includes MVR multi-effect evaporator.
In some embodiments of the invention, the distilled water outlet of the evaporation and crystallization system, which is connected to, needs the production of water to set
It is standby.
As described above, a kind of waste water reuse treatment method of the invention and system, have the advantages that the present invention adopts
While with catalytic ozonation process efficient rate decarburization and decoloration, salt content in waste water is not increased, MBR reaction tank collection activity is dirty
Mud biochemical reaction and film are filtered in one, do not generate concentrated water, further remove the COD in waste water, and activated carbon adsorption and resin are inhaled
The attached influent quality for being further ensured that reverse osmosis membrane, protects reverse osmosis membrane not contaminated, realizes the efficient reuse of wastewater from chemical industry.
Detailed description of the invention
Fig. 1 is shown as the waste water recycling treatment system schematic diagram of the embodiment of the present invention 1.
Specific embodiment
Illustrate embodiments of the present invention below by way of specific specific example, those skilled in the art can be by this specification
Other advantages and efficacy of the present invention can be easily understood for disclosed content.The present invention can also pass through in addition different specific realities
The mode of applying is embodied or practiced, the various details in this specification can also based on different viewpoints and application, without departing from
Various modifications or alterations are carried out under spirit of the invention.
It is as shown in Figure 1 coal chemical industrial waste water recycling processing system schematic diagram, including sequentially connected flocculation tank, filtering
System, catalytic ozonation device, MBR reaction tank, activated carbon adsorption system, resin adsorption system, counter-infiltration system, positive infiltration system
System, evaporation and crystallization system.
It is comprised the concrete steps that using what above system progress coal chemical industrial waste water was handled:
1) coal chemical industrial waste water after biochemical treatment initially enters flocculation tank, is equipped with blender in reaction tank, promotes
The mixing of first flocculant, the second flocculant and waste water, the first flocculant select bodied ferric sulfate, aluminium polychloride, polymerization
One of iron chloride, the second flocculant select PAM or cationic starch.Reaction tank water outlet is separated by solid-liquid separation, and supernatant introduces
Filtration system.
2) one kind of sand filtration, multi-medium filtering, fibre-ball filtration or active carbon filtering, 2~15m/ of filtering velocity can be used in filtering
H can adjust filtering filtering velocity according to delivery turbidity.Filtration system water outlet introduces catalytic ozonation reactor.
3) catalytic ozonation reactor loading catalyst puts into ozone.According to influent COD, ozone dosage 30~
350mg/L.h, 0.5~2h of effective reaction time.Hardly degraded organic substance open loop in the reactor, larger molecular organics are oxidized to small
Molecular organic improves the B/C value of waste water；Chromophoric group is broken simultaneously, plays decolorizing effect.
4) catalytic ozonation reactor water outlet enters MBR reaction tank, further degradation of organic substances.The operation of MBR reaction tank
Parameter: reaction tank gas-water ratio 5:1~15:1, air blower aeration；12~20L/m of film average flux2* h, membrane aperture 0.02~0.05
μm.MBR water outlet introduces activated carbon adsorption system.
5) 5~10m/h of activated carbon adsorption system filtering velocity.
6) resin adsorption system: resin selects polarity or nonpolar macroporous adsorption resin, 2~10BV/h of the rate of filtration.Tree
Rouge operation a cycle (100~150h) is eluted, and elutes frequency depending on effluent quality.Elution is using in acid, alkali
A kind of or joint eluent is reacted through fenton improves B/C value, then introduces coal chemical industrial waste water biochemical system and is reprocessed.
Fenton reacts operating parameter: solution ph 3~4, hydrogen peroxide dosage: hydrogen peroxide and solution C OD ratio 0.5:1~8:1, double
Oxygen water and ferrous sulfate the mass ratio of the material 1:1~5:1.Resin water outlet introduces counter-infiltration system.
7) counter-infiltration system: reverse osmosis operating pressure is 0.5~5Mpa.The clear water of reverse osmosis outflow accounts for feed water by reverse osmosis
Ratio about 70~75% (v/v) is back to production, the concentrate of surplus (volume ratio for accounting for feed water by reverse osmosis is about 25~30%)
It is enriched with concentration again into positive infiltration.
8) further enrichment method reverse osmosis concentrated water is just being permeated, the clear water of positive infiltration outflow accounts for the ratio of positive infiltration water inlet about
50~75% (v/v), are back to production, and the concentrate for accounting for 25%~50% (v/v) of positive infiltration water inlet enters evaporation and crystallization system.
9) evaporative crystallization selects MVR multi-effect evaporator, and the recycling condensing water of evaporation is in production, crystal salt outward transport processing.
The present invention at least has the advantages that
1, salt content in waste water can not be increased while high efficiency decarburization and decoloration using catalytic ozonation technique,
And the B/C value of water outlet can be improved.When intaking pollutant concentration COD≤200mg/L, coloration≤500 times, water energy is stably reached out
COD≤80mg/L, coloration≤50 times.
2, MBR reaction tank integrates activated sludge biochemical reaction and filters with film, does not generate concentrated water, further removes waste water
In COD, be discharged COD≤50mg/L, coloration≤30.
3, activated carbon adsorption and resin adsorption further increase the subsequent influent quality that will enter reverse osmosis membrane, protect reverse osmosis
Permeable membrane is not contaminated, and the eluent of resin is mostly organic matter, and COD higher, after Fenton reacts, B/C value is improved, and can be introduced
The biochemical system of coal chemical industrial waste water is reprocessed.
4, reverse osmosis dope can reduce by about 50%~75% solution again into evaporation and crystallization system after positive infiltration thickening
Amount, energy saving reduce operating cost.
Embodiment 1
Using processing system as shown in Figure 1, first by the coal chemical industrial waste water Jing Guo biochemical treatment (selected from certain coke-oven plant
Bio-chemical effluent, COD:290mg/L, 600 times of coloration) from flocculation tank is flowed into, bodied ferric sulfate 300mg/L is added, PAM is (poly-
Acrylamide) 15mg/L, reacts 10 minutes, precipitates 30 minutes；Water outlet enters more medium filter, filtering velocity 8m/h；Filtering water outlet
Introducing catalytic ozonation reactor, reactor filling molecular sieve catalyst, ozone dosage 200mg/L.h, after reacting 1h, out
Water enters MBR reaction tank, and doughnut MBR film, gas-water ratio 10:1 (volume ratio) in pond, air blower aeration, fenestra are loaded in pond
0.03 μm of diameter；The water outlet of MBR film introduces activated carbon adsorption system, filtering velocity 8m/h；Activated carbon adsorption water outlet introduces resin adsorption system,
Resin selects non-polar macroporous resin, and filtering velocity 4BV/h, after running 130h, soda acid combining and regenerating liquid is selected in resin regeneration；Resin
Water outlet entrance is reverse osmosis, and eluent uses Fenton oxidation, Fenton oxidation pH value in reaction 3.5, hydrogen peroxide and influent COD ratio
4:1 (mass ratio), hydrogen peroxide and ferrous sulfate the mass ratio of the material 3:1, water outlet introduces coal chemical industrial waste water biochemical system after oxidation.Instead
Infiltration uses disc tube reverse osmosis (dt-ro) film, and the rate of recovery of film is 70~75% (v/v), 13~30L/m of membrane flux2.h, operating pressure
4Mpa, the clean water rate of recovery 75% (v/v), is back to production.(volume of the concentrated liquid accounts for reverse osmosis and penetrates into reverse osmosis resulting concentrate
The 25% of water volume) enter positive infiltration, it is added into concentrate after drawing liquid (ammonium carbonate solution) and mixing, mixed liquor penetrates
Forward osmosis membrane, forward osmosis membrane 25~30LMH of water flux is positive to permeate the clean water rate of recovery 60% (v/v), i.e. the body of clean water water outlet
Product, which is positive, penetrates into the 60% of water volume, and 40% (v/v) concentrated water enters MVR multi-effect evaporator.The whole system clean water rate of recovery
90% (v/v), i.e. clean water water outlet total volume account for the 90% of feed water by reverse osmosis volume, and the water of only 10% (v/v) enters evaporation
Crystal system, distillation water outlet are back to production, realize wastewater zero discharge.
In conclusion the present invention gives a kind of new group technology for coal chemical industry wastewater zero emission, by ozone catalytic
Oxidation, MBR, resin adsorption, reverse osmosis carry out efficient combination can also be further combined positive infiltration and multiple-effect evaporation crystallization；It utilizes
Catalytic ozonation removes the hardly degraded organic substance in waste water, opens chromophoric group, and in conjunction with MBR, further removal water outlet is outstanding
Floating object or colloid purify effluent quality, reduce water outlet COD.By catalytic ozonation and MBR, remaining organic matter in water outlet
It again through activated carbon adsorption and resin adsorption, is discharged COD and further decreases, mitigate reverse osmosis burden, reduce reverse osmosis membrane cleaning frequency
Rate.And resin eluent is after Fenton oxidation, B/C value improves, and can reprocess into the biochemical system of coal chemical industrial waste water.It is reverse osmosis
The concentrated water of the rate of recovery 70~75%, 25~30% is after positive infiltration enrichment concentration, then into evaporation and crystallization system.Relative to traditional
Membrane process craft, the rate of recovery for cleaning recycle-water is higher, entire process system water rate about 90%, and only 10% concentrate enters
Evaporation and crystallization system.
The above-described embodiments merely illustrate the principles and effects of the present invention, and is not intended to limit the present invention.It is any ripe
The personage for knowing this technology all without departing from the spirit and scope of the present invention, carries out modifications and changes to above-described embodiment.Cause
This, institute is complete without departing from the spirit and technical ideas disclosed in the present invention by those of ordinary skill in the art such as
At all equivalent modifications or change, should be covered by the claims of the present invention.
Claims (10)
1. a kind of waste water reuse treatment method, which is characterized in that including successively urging waste water progress flocculation reaction, filtering, ozone
Change reaction, MBR reaction, activated carbon adsorption, resin adsorption, reverse osmosis.
2. waste water reuse treatment method according to claim 1, it is characterised in that: when flocculation reaction, the flocculant of use
Including the first flocculant, the second flocculant, first flocculant is selected from bodied ferric sulfate, aluminium polychloride, poly-ferric chloride
At least one of, second flocculant is selected from least one of PAM, cationic starch.
3. waste water reuse treatment method according to claim 2, it is characterised in that: the dosage of first flocculant is
300~500mg/L, the dosage of second flocculant are 10~20mg/L.
4. waste water reuse treatment method according to claim 1, it is characterised in that: COD≤500mg/L of the waste water；
And/or when flocculation reaction, the reaction time is 5~30min；
And/or after flocculation reaction, 30~60min is precipitated；
And/or when filtering, filtered using sand filtration, multi-medium filtering, fibre-ball filtration or active carbon；
And/or when filtering, filtering velocity is 2~15m/h；
And/or controlling filtered delivery turbidity is 5~8；
And/or when catalytic ozonation, carried out in catalytic ozonation reactor, molecular sieve catalyst is loaded in reactor；
And/or when catalytic ozonation, ozone dosage be 30~350mg/L, preferably 100~250mg/L, more preferably
100~200mg/L；
And/or when catalytic ozonation, the reaction time is 0.5~2h；
And/or when MBR reaction, carried out in MBR reaction tank, doughnut MBR film is loaded in pond；
And/or when MBR reaction, gas-water ratio is (5~15) in pond in MBR reaction tank: 1；
And/or when MBR reaction, MBR membrane aperture is 0.02~0.05 μm；
And/or when MBR reaction, film average flux is 12~20L/m2*h；
And/or MBR water outlet COD be 50~70mg/L, 30~50 times of coloration；
And/or when activated carbon adsorption, filtering velocity is 5~10m/h；
And/or when resin adsorption, resin is non-polar macroporous resin；
And/or the specific surface area of the resin is 700~1000m2/ g, average pore size are 8~15nm；
And/or when resin adsorption, 2~10BV/h of filtering velocity；
And/or when resin adsorption, the cycle of operation of resin is 100~150h.
5. waste water reuse treatment method according to claim 1, it is characterised in that: to the resulting eluent of resin regeneration into
Row Fenton oxidation, water outlet returns to wastewater biochemical system and is handled after oxidation.
6. waste water reuse treatment method according to claim 5, it is characterised in that: when Fenton oxidation reacts, reaction solution pH
Value control is 3~4；
And/or when Fenton oxidation reaction, hydrogen peroxide is added, hydrogen peroxide and influent COD mass ratio are (0.5~8): 1, dioxygen
Water quality concentration is 27.5%, it is preferable that hydrogen peroxide is 4:1 with influent COD mass ratio；
And/or when Fenton oxidation reaction, ferrous sulfate is added, the ratio between hydrogen peroxide and the amount of ferrous sulfate substance are (1~5): 1.
7. waste water reuse treatment method according to claim 1, it is characterised in that: when reverse osmosis, using dish tubular type reverse osmosis
Permeable membrane；
And/or when reverse osmosis, operating pressure is 0.5~5Mpa, preferably 4Mpa；
And/or the clean water rate of recovery of reverse osmosis membrane is 70~75% (v/v)；
And/or the membrane flux of reverse osmosis membrane is 13~30LMH；
And/or the cycle of operation of reverse osmosis membrane is 6~7 months.
8. waste water reuse treatment method according to claim 1, it is characterised in that: reverse osmosis resulting dope enters positive seep
Thoroughly；
And/or the clean water rate of recovery of forward osmosis membrane is 50% (v/v)~75% (v/v)；
And/or the membrane flux of forward osmosis membrane is 25~30LMH；
And/or when positive infiltration, intakes and draw after liquid mix, then through forward osmosis membrane；
And/or the liquid that draws is selected from ammonium carbonate solution；
And/or it just permeates resulting dope and enters evaporation and crystallization system.
9. waste water reuse treatment method according to claim 1, it is characterised in that: to the resulting eluent of resin regeneration into
Row Fenton oxidation, water outlet returns to wastewater biochemical system and is handled after oxidation.
10. a kind of waste water recycling treatment system, it is characterised in that: including sequentially connected flocculation tank, filtration system, ozone
Catalytic oxidation system, MBR reaction tank, activated carbon adsorption system, resin adsorption system, counter-infiltration system；
The flocculation tank is used to carry out flocculation sedimentation to waste water；
The filtration system is for being filtered processing to the water outlet of the flocculation tank；
The catalytic ozonation system is used for the water outlet to the filtration system and carries out catalytic ozonation processing；
The MBR reaction tank is used to carry out the water outlet of the catalytic ozonation system aeration membrane biological reaction processing；
The activated carbon adsorption system is used for the water outlet to the MBR reaction tank and carries out adsorption treatment；
The resin adsorption system is used for the water outlet to the activated carbon adsorption system and carries out resin adsorption processing；
The counter-infiltration system is used for the water outlet to the resin adsorption system and carries out reverse osmosis treatment.
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