CN104370359B - A kind of method of O3 contacted oxidation pond and advanced treatment refinery water thereof - Google Patents
A kind of method of O3 contacted oxidation pond and advanced treatment refinery water thereof Download PDFInfo
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- CN104370359B CN104370359B CN201410643070.9A CN201410643070A CN104370359B CN 104370359 B CN104370359 B CN 104370359B CN 201410643070 A CN201410643070 A CN 201410643070A CN 104370359 B CN104370359 B CN 104370359B
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 102
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 69
- 230000003647 oxidation Effects 0.000 title claims abstract description 68
- 238000000034 method Methods 0.000 title claims abstract description 61
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims abstract description 47
- 230000008569 process Effects 0.000 claims description 34
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 26
- 230000001590 oxidative effect Effects 0.000 claims description 23
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 18
- 239000004576 sand Substances 0.000 claims description 18
- 238000005273 aeration Methods 0.000 claims description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 11
- 239000001301 oxygen Substances 0.000 claims description 11
- 229910052760 oxygen Inorganic materials 0.000 claims description 11
- 239000003054 catalyst Substances 0.000 claims description 10
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 9
- 238000007667 floating Methods 0.000 claims description 9
- 239000006004 Quartz sand Substances 0.000 claims description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 7
- 239000000945 filler Substances 0.000 claims description 7
- 239000010936 titanium Substances 0.000 claims description 7
- 229910052719 titanium Inorganic materials 0.000 claims description 7
- 230000003197 catalytic effect Effects 0.000 claims description 6
- 238000006213 oxygenation reaction Methods 0.000 claims description 6
- 238000009287 sand filtration Methods 0.000 claims description 6
- 239000011800 void material Substances 0.000 claims description 6
- 238000002203 pretreatment Methods 0.000 claims description 5
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 3
- 239000002351 wastewater Substances 0.000 abstract description 19
- 230000000694 effects Effects 0.000 abstract description 10
- 238000001914 filtration Methods 0.000 abstract description 10
- -1 small molecules aliphatic hydrocarbon Chemical class 0.000 abstract description 9
- 230000015556 catabolic process Effects 0.000 abstract description 7
- 238000006731 degradation reaction Methods 0.000 abstract description 7
- 241000894006 Bacteria Species 0.000 abstract description 4
- 238000001179 sorption measurement Methods 0.000 abstract description 3
- 150000001491 aromatic compounds Chemical class 0.000 abstract description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- 239000007789 gas Substances 0.000 description 9
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 6
- 239000003921 oil Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000011001 backwashing Methods 0.000 description 3
- 235000019260 propionic acid Nutrition 0.000 description 3
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 3
- 238000007670 refining Methods 0.000 description 3
- 239000010802 sludge Substances 0.000 description 3
- 230000009471 action Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000010779 crude oil Substances 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 2
- 239000013067 intermediate product Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 241000772415 Neovison vison Species 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000012644 addition polymerization Methods 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000005188 flotation Methods 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000003134 recirculating effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 239000000725 suspension Substances 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
- 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
- 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
- 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
- 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
- C02F2103/36—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds
- C02F2103/365—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds from petrochemical industry (e.g. refineries)
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2301/00—General aspects of water treatment
- C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/02—Aerobic processes
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
The invention discloses a kind of method of O3 contacted oxidation pond and advanced treatment refinery water thereof.Be ozone be small molecules aliphatic hydrocarbon by Degradation of Aromatic Compounds under the katalysis of catalyzer, then by the biological degradation of BAF, the COD content in waste water reduced; Unique adsorption filtration effect of BAF simultaneously effectively can reduce SS, forms stable effluent quality.Three cell structures of O3 contacted oxidation pond of the present invention uniqueness greatly improve the mixed effect of ozone and waste water, enhance the oxygenizement of ozone to pollutent; Arranging of water outlet dividing plate on the one hand avoids the short stream of water outlet, also prevent oxidation water outlet on the other hand and carries ozone and enter biochemical unit, have a negative impact, improve the operating performance of whole technique, in turn save running cost simultaneously biochemical bacterium.
Description
Technical field
The invention belongs to water-treatment technology field, relate to a kind of method of O3 contacted oxidation pond and advanced treatment refinery water thereof.
Background technology
Refinery water mainly refers to the waste water produced in the production process such as refining of the straight run distillation of crude oil, the cracking of mink cell focus and distillation and some cut.Because the crude oil origin of refining is different with the program of refining, pollutant component in refinery water is complicated, grease, phenols, sulfide, ammonia nitrogen, aromatics etc. are also had except general pollutent, its chemical oxygen demand (COD) (COD) content is higher, the aromatics of bio-refractory is many, processes more complicated.
Current, along with the contradiction between China's rapid economic development and environment protection, impel country and local discharge refinery water to have higher requirement.According to incompletely statistics, many provinces and cities such as Beijing, Jiangsu, Shandong, Hebei and Liaoning have all promulgated strict refinery water emission standard and have formally implemented.From Con trolling index, the outer standard of drainage of refinery water of these provinces and cities all requires that COD control indexes is at below 60mg/L.And the process of refinery water at present mainly adopts oil removal, flotation, biochemistry to be main " old three covers " technique, its mesophytization unit many employings traditional activated sludge process or A/O, oxidation ditch and SBR technique etc.Waste water after " old three covers " art breading is commonly referred to as secondary biochemical effluent, and its COD content, substantially at about 100mg/L, is difficult to reach below 60mg/L.Its reason is that existing treatment process and technology are difficult to biochemical degradation due to the mainly aromatic series compounds of the pollutent in secondary biochemical effluent, therefore, needs the corresponding refinery water advanced treatment process of exploitation badly.
" research of the refinery water treatment process of efficient economy " (is permitted shake, water technology, 2013, Vol.39NO.2,133-135 page) in disclose the method for " equalizing tank+oil trap+secondary air-floatation pond series connection+SBR " Refinery Wastewater, this method is the treatment process of " old three covers " improved.In secondary biochemical effluent after above-mentioned art breading, aromatics major part is not removed, and therefore water outlet COD is generally between 100-120mg/L.
" refinery water is back to recirculating cooling water system further treatment technique " (oil-gas field environment protection; Wang Feiyang etc.; 2013, Vol.23,43-47 page) in disclose the technique of " secondary biochemical effluent+ozone oxidation+charcoal absorption+lime soften for sewage+equalizing tank+filtration+process after water outlet ".In this technique, ozone oxidation equipment used is the single synthetic glass post of a Φ 190mm × 950mm, though the waste water COD clearance after this art breading reaches 96%, but this technique does not add filtration or air-floating apparatus between secondary biochemical effluent and ozone oxidation, cause the SS entering ozone oxidation section higher, again because ozone oxidation is not pointed, suspended particulate (SS) will have precedence over hardly degraded organic substance and ozone reaction in water, thus reduce the efficiency of ozone oxidation hardly degraded organic substance, the biodegradability of waste water is not also improved, the follow-up removal effect of biochemical unit to COD is very poor.
The method of refinery water employing BAF (BAF)-ozone oxidation-BAF for high saliferous is refer in CN102690016A, water outlet COD can be down to below 60mg/L by this method, but shortcoming is two-stage aerated biological filter coupling, the treatment effect of one-level biological filter to difficult degradation COD is not obvious, and head loss is large, investment and running cost high.
Summary of the invention
The object of this invention is to provide a kind of method of advanced treatment refinery water, the method has stronger removal effect to the aromatics in secondary biochemical effluent, can ensure that water outlet COD index is stabilized in below 60mg/L.
Another object of the present invention is to provide a kind of O3 contacted oxidation pond.
Technical solution of the present invention is: a kind of O3 contacted oxidation pond, comprises oxidation pond body, one-level dividing plate, secondary dividing plate, water outlet dividing plate, water-in, water outlet and aeration titanium dish, described one-level dividing plate and secondary dividing plate are vertically set on bottom and the top of oxidation pond body respectively, and successively oxidation pond body is divided into intake chamber, oxidizing chamber and attenuation chamber three rooms, between intake chamber with oxidizing chamber, top is communicated with, between oxidizing chamber and attenuation chamber, bottom is communicated with, water-in is arranged on the sidewall at 100mm place bottom intake chamber, water outlet is arranged on apart from the sidewall at 100mm place, attenuation chamber top, water outlet divider upright is arranged on apart from the sidewall at 400mm place, attenuation chamber top, and with secondary dividing plate at a distance of 50mm, aeration titanium dish is arranged on bottom oxidizing chamber, wherein, one-level dividing plate is apart from oxidation pond bodies top 300mm, secondary dividing plate is apart from oxidation pond body bottom portion 50mm, and the volumetric ratio of intake chamber, oxidizing chamber and attenuation chamber is 1:2:1.
Described oxidizing chamber and attenuation chamber top are also provided with tail gas air outlet, and described tail gas air outlet connects ozone exhaust gas treating device.
A method for advanced treatment refinery water is ozone is small molecules aliphatic hydrocarbon by Degradation of Aromatic Compounds under the katalysis of catalyzer, is then reduced by the COD content in waste water by the biological degradation of BAF; Unique adsorption filtration effect of BAF simultaneously effectively can reduce SS, forms stable effluent quality.The method comprises the following steps:
(1) carry out sand filtration pre-treatment to the refinery water after secondary biochemical treatment, sand filter is built with quartz sand filter media, and sand filter water outlet SS is no more than 30mg/L, and process water outlet enters step (2);
(2) ozone catalytic catalytic oxidation process: add floating stuffing in the oxidizing chamber in O3 contacted oxidation pond, and catalyst sulfuric acid ferrous iron is added in intake chamber, process water outlet enters from water-in, flowing is folded to along one-level dividing plate and secondary dividing plate, water outlet finally by attenuation chamber flows out, and after oxidation, water outlet enters step (3);
(3) BAF process: BAF (BAF) adopts intermittent aeration oxygenation, maintains dissolved oxygen 2mg/L.
Quartz sand filter media particle diameter in step (1) is followed successively by Φ 0.5 ~ 1.0mm, Φ 1.0 ~ 2.0mm and Φ 2.0 ~ 4.0mm from top to bottom along sand filter short transverse.
In step (2), in process water outlet, ozone dosage is 20-45mg/L; In waste water, the dosage of catalyst sulfuric acid ferrous iron is 1-3mg/L; Floating stuffing is the three-dimensional ball filler of poly-third ethene, and diameter is Φ 80mm, and specific surface area is 800m
2/ m
3, dosage is 5/m
3; Hydraulic detention time is 25-60min.
In step (3), BAF void tower hydraulic detention time is 80-140min.
the present invention compared with prior art, has following outstanding advantage and effect:
(1) three cell structures of O3 contacted oxidation pond uniqueness greatly improve the mixed effect of ozone and waste water, enhance the oxygenizement of ozone to pollutent; Arranging of water outlet dividing plate on the one hand avoids the short stream of water outlet, also prevent oxidation water outlet on the other hand and carries ozone and enter biochemical unit, have a negative impact, improve the operating performance of whole technique, in turn save running cost simultaneously biochemical bacterium.
(2) under catalyst action, the productive rate of the main component hydroxyl free radical in ozone oxidation reaction is greatly improved, and oxidation water outlet biodegradability increases greatly, removes COD serve keying action to integrated artistic.
(3) before sand filtration is placed on ozone oxidation pond, avoid the unnecessary consumption of the SS in secondary biochemical effluent to ozone, improve the removal efficiency of COD, the running cost of reduction.
(4) the interval oxygenation of BAF, the water outlet SS avoiding biological over oxidation increases problem, again reduces energy consumption, simultaneously BAF filler self with filtering function, avoid again adding settler, decrease cost of investment.
Accompanying drawing explanation
Fig. 1 is the structural representation in O3 contacted oxidation pond of the present invention.
Fig. 2 is refinery water advanced treatment process schematic flow sheet of the present invention.
In Fig. 1,1-aeration titanium dish; 2-water-in; 3-one-level dividing plate; 5-water outlet; 6-water outlet dividing plate; 7-secondary dividing plate; 8-intake chamber; 9-oxidizing chamber; 10-attenuation chamber.
Embodiment
Further illustrate the present invention below in conjunction with embodiment, embodiment is for a better understanding of the present invention, but is not construed as limiting the present invention.
As shown in Figure 1, O3 contacted oxidation pond of the present invention comprises oxidation pond body, one-level dividing plate 3, secondary dividing plate 7, water outlet dividing plate 6, water-in 2, water outlet 5 and aeration titanium dish 1, described one-level dividing plate 3 and secondary dividing plate 7 are vertically set on bottom and the top of oxidation pond body respectively, and successively oxidation pond body is divided into intake chamber 8, oxidizing chamber 9 and attenuation chamber 10 3 rooms, between intake chamber 8 with oxidizing chamber 9, top is communicated with, between oxidizing chamber 9 and attenuation chamber 10, bottom is communicated with, water-in 2 is arranged on the sidewall at 100mm place bottom intake chamber 8, water outlet 5 is arranged on apart from the sidewall at 100mm place, attenuation chamber 10 top, water outlet dividing plate 6 is vertically set on apart from the sidewall at 400mm place, attenuation chamber 10 top, and with secondary dividing plate 7 at a distance of 50mm, aeration titanium dish 1 is arranged on bottom oxidizing chamber 8, wherein, the top of one-level dividing plate 3 is apart from oxidation pond bodies top 300mm, the bottom of secondary dividing plate 7 is apart from oxidation pond body bottom portion 50mm, the volumetric ratio of intake chamber 8, oxidizing chamber 9 and attenuation chamber 10 is 1:2:1, and water outlet dividing plate 6 can not only be avoided the short stream of water outlet can also prevent water outlet from carrying ozone and enter subsequent biochemical unit, in order to avoid produce sterilization functions to the bacterium of subsequent biochemical unit.Oxidizing chamber 8 and attenuation chamber 10 top are also provided with tail gas air outlet separately, and to make the part ozone tail gas effusion of reaction after product oxygen and reaction remnants, ensure oxidation pond internal gas pressure balance, this tail gas air outlet is connected with ozone exhaust gas treating device.
The method of advanced treatment refinery water of the present invention comprises the following steps:
(1) sand filtration pre-treatment is carried out to the refinery water after secondary biochemical treatment, sand filter is built with quartz sand filter media, sand filter water outlet SS is no more than 30mg/L, process water outlet enters step (2), wherein, quartz sand filter media particle diameter is followed successively by Φ 0.5 ~ 1.0mm, Φ 1.0 ~ 2.0mm and Φ 2.0 ~ 4.0mm from top to bottom along sand filter short transverse;
(2) ozone catalytic catalytic oxidation process: add floating stuffing in the oxidizing chamber 9 in O3 contacted oxidation pond, and catalyst sulfuric acid ferrous iron is added in intake chamber 8, process water outlet enters from water-in 2, flowing (namely process water outlet to enter from water-in 2 flow through intake chamber 8 and oxidizing chamber 9) is folded to along one-level dividing plate 3 and secondary dividing plate 7, water outlet 5 finally by attenuation chamber 10 flows out, after oxidation, water outlet enters step (3), and wherein, in process water outlet, ozone dosage is 20-45mg/L; In waste water, the dosage of catalyst sulfuric acid ferrous iron is 1-3mg/L; Floating stuffing is the three-dimensional ball filler of poly-third ethene, and diameter is Φ 80mm, and specific surface area is 800m
2/ m
3, dosage is 5/m
3; Hydraulic detention time is 25-60min;
(3) BAF process: BAF (BAF) adopts intermittent aeration oxygenation, maintain dissolved oxygen 2mg/L, void tower hydraulic detention time is 80-140min.
Embodiment 1:
As Fig. 2, certain refinery 300m
3the water outlet after the conventional processing of sand setting → adjustment → oil removal → mono-secondary floatation → activated sludge process → second pond of/h refinery water, this water outlet is the refinery water after secondary biochemical treatment, is commonly referred to as secondary biochemical effluent, and water-quality guideline is COD120mg/L, BOD
520mg/L, ss suspended solid 150mg/L.
Carry out filtration treatment with sand filter to above-mentioned secondary biochemical effluent, the useful volume of sand filter is 204m
3, add the quartz sand filter media (commercially available) of Φ 0.5 ~ 1.0mm, Φ 1.0 ~ 2.0mm and Φ 2.0 ~ 4.0mm in filter tank from top to bottom successively, hydraulic detention time is 40min, average rate of filtering 7.5m/h.SS in secondary biochemical effluent can be removed more than 80% by quartz sand filtration, ensure that waste water SS is no more than 30mg/L in ozone oxidation pond, in order to avoid non-selective due to ozone oxidation, a lot of ozone of arene compound consumption SS being had precedence over dissolve in water.Water outlet SS in the present embodiment after sand filtration is 28mg/L, COD is 104mg/L, BOD
5for 15mg/L, BOD
5/ COD is 0.14, and the biodegradability of waste water is not high.
Sand filter water outlet enters O3 contacted oxidation pond, catalyst sulfuric acid is added ferrous in the intake chamber 8 of oxidation pond, dosage is 1mg/L, ferrous sulfate can improve the productive rate that ozone decomposed is hydroxyl free radical, hydroxyl free radical standard potential is 2.80V, the phenyl ring of arene compound can be opened, be oxidized to the aliphatic hydrocarbon compounds such as micromolecular propionic acid, acetic acid, thus by biochemical degradation by bacteria; The useful volume in O3 contacted oxidation pond is 124.5m
3, be divided into intake chamber 8, oxidizing chamber 9 and attenuation chamber 10 3 Room with one-level dividing plate 3 and secondary dividing plate 7 in oxidation pond, the volume ratio of three Room is 1:2:1; The three-dimensional ball filler (commercially available) of addition polymerization third ethene in oxidizing chamber 8, diameter is Φ 80mm, and specific surface area is 800m
2/ m
3, dosage is 312, after adding ball filler, and specific surface area huge in ball filler can be relied on to provide sufficient space for ozone and waste water reaction; The water outlet dividing plate 6 that attenuation chamber 10 sidewall is arranged can not be too near apart from water outlet 5, otherwise water outlet can be caused not smooth, the head loss in whole ozone oxidation pond is too high, can not apart from too far away, otherwise the effect preventing the short stream of water outlet and hinder ozone to flow out with waste water cannot be played, through experimental study find, apart from water outlet 5 apart from for 300mm(distance 400mm place, attenuation chamber 10 top) time be optimum distance.Ozone oxidation tank waterpower residence time 25min, ozone dosage 20mg/L in the present embodiment.After ozone oxidation, water outlet COD is 154mg/L, BOD
5for 47mg/L, BOD
5/ COD is 0.31, and the biodegradability of waste water is greatly improved.
After ozone oxidation, water outlet enters BAF, and the existing biodegradable effect of BAF, has the functions such as Filtration Adsorption again, thus it to have possessed volume little, take up an area few, processing efficiency is high, stable effluent quality, economize second pond, simplification of flowsheet and operation, the advantages such as construction investment is less.Adopt the spherical biomass filtrate of commercially available Φ 3 ~ 5mm in the present embodiment in BAF filter tank, filter used is band cap strainer head, length 405mm; The useful volume of BAF is 400m
3, void tower hydraulic detention time is 80min; Aeration fan is controlled by the dissolved oxygen probe in pond, when dissolved oxygen concentration in pond is lower than 2mg/L, Aeration fan starts, when dissolved oxygen concentration reaches 2mg/L, blower fan cuts out, and by this intermittent oxygen supply mode, can avoid biological over oxidation, in water outlet, white suspension thing increases, and water outlet SS is exceeded standard; BAF is filter clogging after 48 hours, carries out back flushing with BAF water outlet to it.
Water outlet COD after BAF process is 35mg/L, SS is 2mg/L, BOD
5for 8mg/L, reach the requirement that COD is less than 60mg/L.
embodiment 2:
Certain refinery refinery water water yield is 650m
3/ h, adopt adjustment-oil removal-cavitation air flotation-air-dissolving air-float-Wastewater Treated by Activated Sludge Process, the water outlet COD after process is 106mg/L, BOD
5for 19mg/L, SS are 120mg/L.Each step method adopting our bright content part to address successively, carries out filtration pre-treatment with sand filter, and sand filter hydraulic detention time is 30min, and the backwashing time cycle is 48 hours, and the SS after process is 22mg/L.Sand filter water outlet enters in O3 contacted oxidation pond, under the katalysis of catalyzer, Recalcitrant chemicals is produced the intermediate product such as acetic acid, propionic acid by the hydroxyl free radical that ozone decomposed produces, the dosage of catalyst sulfuric acid ferrous iron is 3mg/L, O3 contacted oxidation adds floating stuffing in pond, increases gas-to-liquid contact surface-area; Ozone dosage is 45mg/L, and effective duration of contact of ozone and waste water is 60min, the water outlet BOD behind O3 contacted oxidation pond
5/ COD is 0.34; Water outlet after ozone oxidation enters BAF, and the void tower residence time in BAF is 140min, and adopt intermittent aeration oxygenation, in pond, dissolved oxygen concentration is the backwashing period of 2mg/L, BAF is 48 hours.
After BAF process, water outlet COD is 35mg/L, BOD
5for 9mg/L, SS are 3mg/L.
embodiment 3
Certain refinery refinery water water yield is 400m
3/ h, adopt sand setting → adjustment → oil removal → mono-secondary floatation → oxidation ditch → second pond conventional processing, the secondary effluent COD after process is 98mg/L, BOD
5for 14mg/L, SS are 137mg/L.Each step method adopting our bright content part to address successively, carries out filtration pre-treatment with sand filter, and sand filter hydraulic detention time is 45min, and the SS after process is 30mg/L.Sand filter water outlet enters in O3 contacted oxidation pond, under the katalysis of catalyzer, Recalcitrant chemicals is produced the intermediate product such as acetic acid, propionic acid by the hydroxyl free radical that ozone decomposed produces, the dosage of catalyst sulfuric acid ferrous iron is 2mg/L, O3 contacted oxidation adds floating stuffing in pond, increases gas-to-liquid contact surface-area; Ozone dosage is 45mg/L, and effective duration of contact of ozone and waste water is 40min, the water outlet BOD behind O3 contacted oxidation pond
5/ COD is 0.39; Water outlet after ozone oxidation enters BAF, and the void tower residence time in BAF is 120min, and adopt intermittent aeration oxygenation, in pond, dissolved oxygen concentration is the backwashing period of 2mg/L, BAF is 48 hours.
After BAF process, Process for Effluent COD is 45mg/L, BOD
5for 7mg/L, SS are 5mg/L.
Claims (4)
1. a method for advanced treatment refinery water, is characterized in that, comprises the following steps:
Step 1, carry out sand filtration pre-treatment to the refinery water after secondary biochemical treatment, sand filter is built with quartz sand filter media, and sand filter water outlet SS is no more than 30mg/L, and process water outlet enters step 2;
Step 2, ozone catalytic catalytic oxidation process: add floating stuffing in the oxidizing chamber (9) in O3 contacted oxidation pond, and catalyst sulfuric acid ferrous iron is added in intake chamber (8), process water outlet enters from water-in (2), flowing is folded to along one-level dividing plate (3) and secondary dividing plate (7), water outlet (5) finally by attenuation chamber (10) flows out, after oxidation, water outlet enters step 3, wherein, O3 contacted oxidation pond comprises oxidation pond body, one-level dividing plate (3), secondary dividing plate (7), water outlet dividing plate (6), water-in (2), water outlet (5) and aeration titanium dish (1), described one-level dividing plate (3) and secondary dividing plate (7) are vertically set on bottom and the top of oxidation pond body respectively, and successively oxidation pond body is divided into intake chamber (8), oxidizing chamber (9) and attenuation chamber (10) three rooms, between intake chamber (8) with oxidizing chamber (9), top is communicated with, between oxidizing chamber (9) and attenuation chamber (10), bottom is communicated with, water-in (2) is arranged on apart from the sidewall at 100mm place, intake chamber (8) bottom, water outlet (5) is arranged on apart from the sidewall at 100mm place, attenuation chamber (10) top, water outlet dividing plate (6) is vertically set on apart from the sidewall at 400mm place, attenuation chamber (10) top, and with secondary dividing plate (7) at a distance of 50mm, aeration titanium dish (1) is arranged on oxidizing chamber (9) bottom, wherein, one-level dividing plate (3) is apart from oxidation pond bodies top 300mm, secondary dividing plate (7) is apart from oxidation pond body bottom portion 50mm, and the volumetric ratio of intake chamber (8), oxidizing chamber (9) and attenuation chamber (10) is 1:2:1,
Step 3, BAF process: BAF adopts intermittent aeration oxygenation, maintain dissolved oxygen 2mg/L.
2. the method for advanced treatment refinery water as claimed in claim 1, it is characterized in that, the quartz sand filter media particle diameter in step 1 is followed successively by Φ 0.5 ~ 1.0mm, Φ 1.0 ~ 2.0mm and Φ 2.0 ~ 4.0mm from top to bottom along sand filter short transverse.
3. the method for advanced treatment refinery water as claimed in claim 1, it is characterized in that, processing ozone dosage in water outlet in step 2 is 20-45mg/L; The dosage of catalyst sulfuric acid ferrous iron is 1-3mg/L; Floating stuffing is the three-dimensional ball filler of poly-third ethene, and diameter is Φ 80mm, and specific surface area is 800m
2/ m
3, dosage is 5/m
3; Hydraulic detention time is 25-60min.
4. the method for advanced treatment refinery water as claimed in claim 1, it is characterized in that, in step 3, the void tower hydraulic detention time of BAF is 80-140min.
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| CN102145966A (en) * | 2011-04-21 | 2011-08-10 | 化工部长沙设计研究院 | Method for carrying out advanced treatment on oily wastewater |
| CN103896451A (en) * | 2014-03-07 | 2014-07-02 | 佛山市新泰隆环保设备制造有限公司 | Deep papermaking wastewater treatment device and method |
| CN203781901U (en) * | 2014-04-18 | 2014-08-20 | 世纪华扬环境工程有限公司 | Ozone catalytic oxidation device |
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| CN103896451A (en) * | 2014-03-07 | 2014-07-02 | 佛山市新泰隆环保设备制造有限公司 | Deep papermaking wastewater treatment device and method |
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