CN105601038B - The advanced treatment method for sewage water of ozone reflux secondary oxidation after a kind of - Google Patents
The advanced treatment method for sewage water of ozone reflux secondary oxidation after a kind of Download PDFInfo
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- CN105601038B CN105601038B CN201511020280.3A CN201511020280A CN105601038B CN 105601038 B CN105601038 B CN 105601038B CN 201511020280 A CN201511020280 A CN 201511020280A CN 105601038 B CN105601038 B CN 105601038B
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/20—Treatment of water, waste water, or sewage by degassing, i.e. liberation of dissolved gases
-
- 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
- C02F2101/32—Hydrocarbons, e.g. oil
- C02F2101/327—Polyaromatic Hydrocarbons [PAH's]
-
- 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
Abstract
The invention discloses a kind of advanced treatment method for sewage water of rear ozone reflux secondary oxidation.It is characterized in that ozone flows back after increasing on the basis of traditional ozone and biofilter group technology, by rationally designing reflux ratio, the removal efficiency for further promoting difficult biochemical sewage COD, effectively solves the problems, such as that level-one ozone and biofilter group technology COD removal efficiency are limited.This method includes the following steps：1) sewage after two stage treatment enters preceding ozone oxidation pond, adds ozone and improves Biodegradability of Wastewater；2) water outlet of ozone oxidation pond enters BAF progress biochemical treatments before, and discharge water enters clear water reserviors；3) part sewage lifting enters rear ozone oxidation pond in clear water reserviors, again by ozone oxidation open loop chain rupture；4) ozone oxidation pond effluent recycling is discharged to BAF and preceding ozone oxidation pond and carries out biochemical treatment together afterwards.The method of the present invention takes full advantage of the selectivity of ozone oxidation, has broken the biochemical limit of difficult biochemical sewage.
Description
Technical field
The present invention relates to a kind of advanced treatment method for sewage water of rear ozone reflux secondary oxidation.
Background technology
Degradable organic pollution in refinery sewage can largely be removed by two stage treatment, but be difficult to remove double bond,
The hardly degraded organic substances such as phenyl ring, multiring aromatic hydrocarbon, secondary effluent COD concentration is still higher, and B/C, than low, biodegradability is poor.With
China's sewage drainage standard is continuously improved, currently, the domestic following two methods of generally use are difficult to degrade as advanced treating removal
Organic matter.
The first, ozone oxidation and biological aerated filter group technology.It is dense that the technique can further decrease COD in sewage
Degree, but since ozone oxidation has selectivity so that raising sewage B/C is more limited than ability, and the technique totality removal rate is caused to have
It limits (the COD removal rates that COD removal rates are only capable of realization 55% under 45%~50%, optimal situation under normal conditions).Work as water
When COD excessive concentrations, it is difficult to ensure that stable water outlet is up to standard, usually also need to increase the subsequent techniques such as activated carbon filter.Meanwhile the work
The ozone utilization rate of skill is low.
Second, catalytic ozonation and biological aerated filter group technology.The technique effectively increases the utilization of ozone
Rate improves the selectivity of ozone oxidation, and COD removal efficiency is high, but ozone acts synergistically with two kinds of biofilter technique category, and one
Taste improves the COD removal rates of ozone oxidation, and biological aerated filter biofilm can be caused difficult, reduce the total removal rate etc. of integrated artistic
Problem.In addition, since the technique increases catalyst, backwash and replacement need to be carried out, equipment is more, operation sequence is complicated,
Investment and operating cost are high, while the technique generates solid waste, it is also necessary to carry out fixed-end forces.
Invention content
A kind of advanced treatment method for sewage water of rear ozone reflux secondary oxidation provided by the present invention, includes the following steps：
1) sewage after two stage treatment enters preceding ozone oxidation pond (B), ozone generator (A) production by water inlet pipe (1)
Raw ozone adds pipeline (2) by ozone and is added to ozone oxidation pond, and oxidation reaction is carried out in preceding ozone oxidation pond (B),
Water COD concentration is reduced, while improving Biodegradability of Wastewater, converting part larger molecular organics difficult to degrade to small molecule easily drops
Solve organic matter；
2) ozone oxidation pond (B) water outlet enters BAF distributing channels through channel before, then enters the ponds BAF through BAF water inlet pipes (3)
(C) biochemical treatment is carried out, COD is further removed, the ponds BAF (C) water outlet is sent into clear water reserviors (D) by BAF outlet pipes (4)；
3) part of contaminated water ozone oxidation pond (E) after reflux pump (5) is lifted into clear water reserviors (D), will be in preceding ozone oxygen
Changing in pond does not have the macromolecular hardly degraded organic substance of complete oxidation further to aoxidize, and another part sewage passes through total outlet pipe (6)
Standard discharge；
4) ozone oxidation pond (E) effluent recycling is discharged to the ponds BAF (C) and preceding ozone oxidation pond (B) and carries out biochemistry together afterwards
Processing.
It, can be by adjusting ozone dosage, ozone after raising when COD removal rates require high when water COD concentration height
COD removal rates make the COD removal rates of entire technique accordingly improve.Meanwhile this deep treatment method can realize flexible and efficient fortune
Row, when project initial stage water COD concentration is relatively low, can shut down rear ozone oxidation pond (E) and reflux pump (5), while adjusting ozone
The ozone yield of generator (A), save ozone dosage, when COD come water concentration it is high when, plug and play.
Wherein, when water COD concentration is relatively stablized, technique requires to maintain always stable COD removal rates, or to whole COD
Removal rate require it is relatively low when, step 3), 4) in can omit after ozone oxidation pond (E), by part of contaminated water in clear water reserviors (D) through reflux
Pump (5), which is directly promoted, is back to preceding ozone oxidation pond (B).
Wherein, ozone oxidation pond (B) best ozone contact time is 45~60min before step 1).Control ozone dosage
COD of sewage concentration is set to decline 35%, BOD concentration at this time is higher, and Biodegradability of Wastewater is best.If time of contact is too short, COD is dense
Degree declines unobvious；Time of contact is long, and BOD concentration is relatively low, and biodegradability is relatively poor, while wasting ozone.Preceding ozone oxygen
It is 2-3kgO to change pond most preferably to add ozone amount3/kgCOD.The COD concentration removal rates in the ponds step 2) BAF (C) can reach 27~
35%.By controlling above two steps, it can be achieved that the best COD removal rates of entire technique in design.
Wherein, step 3) reflux ratio can be determined according to Inlet and outlet water COD concentration.By the COD removal rates of rear ozone oxidation pond (E)
At 35%, reflux ratio takes 25%, 50%, 75%, 100% respectively, and the COD highest removal rates of entire technique are respectively for control
61%, 63%, 64%, 64.8%.By the control of the COD removal rates of rear ozone oxidation pond (E) at 50%, reflux ratio equally takes
25%, 50%, 75%, 100%, the COD highest removal rates of entire technique are respectively 61%, 64.5%, 67.2%, 69.3%.
Reflux ratio is bigger, and the COD removal rates of rear ozone are higher, and the COD removal rates of integrated artistic are higher.Ozone efficiency is higher afterwards, whole
The COD removal rates of technique are higher.
Wherein, step 3), 4) in can omit after ozone oxidation pond (E), by part of contaminated water in clear water reserviors (D) through reflux pump
(5) ozone oxidation pond (B) before being back to directly is promoted.When reflux ratio takes 25%, 50%, 75%, 100% respectively, entire technique
COD highest removal rates be respectively 61%, 63%, 64%, ozone oxidation pond and by COD removal rate controls after 64.8%, with increase
The effect made at 35% is identical.
The present invention has B/C low according to refinery sewage after biochemical treatment, biodegradability, and the highly concentrated features of COD, carries
A kind of efficient deep treatment method for reducing COD concentration has been supplied to be effectively utilized ozone by ozone reflux technique after increase
The selectivity of oxidation has broken through the biochemical limit of refinery sewage, realizes high COD removal rates.
This method runs efficient stable, can flexible operating, construction and operating cost is low, operational management is simple, without secondary dirt
It contaminates, without fixed-end forces.
Description of the drawings
Fig. 1, Fig. 2 are the process flow diagram of the present invention.
A, ozone generator；B, preceding ozone oxidation pond；C, the ponds BAF；D, clear water reserviors；E, rear ozone oxidation pond；1, water inlet pipe；
2, ozone adds pipeline；3, BAF water inlet pipes；4, BAF outlet pipes；5, reflux pump；6, total outlet pipe.
Specific implementation mode
In conjunction with the attached drawing in the embodiment of the present invention, the processing method in the embodiment of the present invention is clearly and completely retouched
It states.The described embodiments are merely a part of the embodiments of the present invention, rather than whole embodiments.Based on the implementation in the present invention
Example, the every other embodiment that those of ordinary skill in the art are obtained shall fall within the protection scope of the present invention.
Referring to Fig.1, ozone oxidation pond before refinery secondary clarifier effluent initially enters stops 45~60min, ozone generator warp
Ozone distribution system is added to preceding ozone oxidation pond, and ozone dosage is with COD removal rates 35%, 2kgO3/ kgCOD is calculated.Preceding
In ozone oxidation pond, ozone gas is divided into countless tiny bubbles, realizes that ozone carries out the mistake of mass transfer from gas phase to liquid phase
Dirty water part larger molecular organics difficult to degrade are oxidized to small molecule labile organic compound by journey, improve Biodegradability of Wastewater, remaining
Ozone destroys system decomposition through tail gas.Zoneofoxidation water outlet enters degassing district through water channel, stops 30~45min, avoids residual ozone
Subsequent film biosystem is damaged.
Preceding ozone oxidation pond water outlet enters the ponds BAF distribution well through water channel, then is assigned in the ponds BAF through BAF water inlet pipes, passes through
Biochemical method further removes COD.The water outlet of the ponds BAF is sent to clear water reserviors through outlet pipe, and part of contaminated water is through reflux pump in clear water reserviors
It is lifted into rear ozone oxidation pond, rear ozone oxidation pond dwell time of sewage is 45~60min, and ozone generator is distributed through ozone
System is added to preceding ozone oxidation pond, and ozone dosage is with COD removal rates 35%, 2kgO3/ kgCOD is calculated or with COD removal rate
50%, 2.5kgO3/ kgCOD, ozone is by the macromolecular hardly degraded organic substance for not having complete oxidation in preceding ozone oxidation pond into one
Step oxidation, secondary raising Biodegradability of Wastewater, rear ozone oxidation pond effluent recycling to the ponds BAF are discharged together with preceding ozone oxidation pond
Carry out biochemical treatment.Clear water reserviors another part sewage passes through total outlet pipe standard discharge.
The present invention is described in further detail with reference to embodiment.
Embodiment 1
Pilot scale raw water water sample is certain Petrochemical Enterprises sewage farm secondary clarifier effluent, water quality and quantity such as following table：
Raw water initially enters preceding ozone oxidation pond B, stops 45min, and the ozone that ozone generator A is generated is thrown by ozone
Pipeline 2 is added to add to preceding ozone oxidation pond B, ozone dosage 2kgO3/ kgCOD, ozone oxidation COD removal rates are before controlling
35%.Preceding ozone oxidation pond B water outlets enter the filtering velocity control of the ponds the BAF pond C, BAF in 4m/h by channel, and C water outlets in the ponds BAF enter clear
Pond D, clear water reserviors part water ozone oxidation pond E, reflux ratio after the promotion of reflux pump 5 is arrived take 25%, 50%, 75% respectively,
100%, 45min is stopped, rear ozone dosage is 2kgO3/ kgCOD, ozone oxidation COD removal rates are 35% after control.It is smelly afterwards
The E water outlets of oxygen oxidation pond are sent the ponds BAF C back to and are further processed.
Entire process spent water COD removal rates such as following table：
It is 35% when front and back ozone COD removal rates are controlled by ozone dosage, reflux ratio takes 25%, 50% respectively,
75%, when 100%, the COD highest removal rates of entire technique are respectively 61%, 63%, 64%, 64.8%.Overall removal rate is bright
It is aobvious to be higher than the 55%COD maximum material removal rates without rear ozone reflux technique, and reflux ratio is higher, and COD removal rates are higher.
Embodiment 2
Ensure that other conditions are constant in embodiment 1, rear ozone dosage is 2.5kgO3/ kgCOD, ozone oxidation after control
COD removal rates are 50%.
Entire process spent water COD removal rates such as following table：
When reflux ratio takes 25% respectively, when 50%, 75%, 100%, the COD highest removal rates of entire technique are respectively
61%, 64.5%, 67.2%, 69.3%.
When the COD removal rates of rear ozone oxidation improve, total COD removal rates of integrated artistic significantly improve.Same reflux
Than higher, COD removal rates are higher.
Embodiment 3
Ensure that other conditions are constant in embodiment 1, ozone oxidation pond E after cancellation, clear water reserviors part of contaminated water is passed straight back to
Preceding ozone oxidation pond B.
Entire process spent water COD removal rates such as following table：
When reflux ratio takes 25% respectively, when 50%, 75%, 100%, the COD highest removal rates of entire technique are respectively
61%, 63%, 64%, 64.8%.
When total ozone dosage is identical, only increase reflux and when without rear ozone oxidation pond with 1 effect having the same of embodiment
Fruit.
Claims (4)
1. the advanced treatment method for sewage water of ozone reflux secondary oxidation after a kind of, which is characterized in that in the refining after two stage treatment
When change COD of sewage concentration is high, it the described method comprises the following steps：
1) the refinery sewage after two stage treatment enters preceding ozone oxidation pond (B), ozone generator (A) production by water inlet pipe (1)
Raw ozone adds pipeline (2) by ozone and is added to ozone oxidation pond, and oxidation reaction is carried out in preceding ozone oxidation pond (B),
Water COD concentration is reduced, while improving Biodegradability of Wastewater, converting part larger molecular organics difficult to degrade to small molecule easily drops
Solve organic matter；Wherein, preceding ozone oxidation pond (B) COD removal rates control is 35%；
2) ozone oxidation pond (B) water outlet enters BAF distributing channels after channel enters 30~45min of degassing district stop through channel before,
The ponds BAF (C) being entered through BAF water inlet pipes (3) again and carrying out biochemical treatment, further remove COD, the ponds BAF (C) water outlet is gone out by BAF
Water pipe (4) is sent into clear water reserviors (D)；
3) part of contaminated water ozone oxidation pond (E) after pump (5) is lifted into clear water reserviors (D), will not have in preceding ozone oxidation pond
There is the macromolecular hardly degraded organic substance of complete oxidation further to aoxidize, another part sewage passes through total outlet pipe (6) standard discharge；
4) ozone oxidation pond (E) effluent recycling is discharged to the ponds BAF (C) and preceding ozone oxidation pond (B) and carries out biochemical treatment together afterwards.
2. according to the method described in claim 1, wherein, stablizing in the COD concentration of the refinery sewage after two stage treatment, technique
When requiring to maintain stable COD removal rates always, or requiring low to whole COD removal rates, the method further includes：
1) the refinery sewage after two stage treatment enters preceding ozone oxidation pond (B), ozone generator (A) production by water inlet pipe (1)
Raw ozone adds pipeline (2) by ozone and is added to ozone oxidation pond, and oxidation reaction is carried out in preceding ozone oxidation pond (B),
Water COD concentration is reduced, while improving Biodegradability of Wastewater, converting part larger molecular organics difficult to degrade to small molecule easily drops
Solve organic matter；
2) ozone oxidation pond (B) water outlet enters BAF distributing channels after channel enters 30~45min of degassing district stop through channel before,
The ponds BAF (C) being entered through BAF water inlet pipes (3) again and carrying out biochemical treatment, further remove COD, the ponds BAF (C) water outlet is gone out by BAF
Water pipe (4) is sent into clear water reserviors (D)；
3) part of contaminated water is directly promoted through pump (5) and is back to preceding ozone oxidation pond (B) in clear water reserviors (D), and another part sewage is logical
Cross total outlet pipe (6) standard discharge.
3. according to the method described in claim 1, wherein, step 3) reflux ratio is determined according to Inlet and outlet water COD concentration；Reflux ratio is got over
Height, integrated artistic COD removal rates are higher；Wherein, the COD removal rates in front and back ozone oxidation pond are controlled in step 3)
35%, reflux ratio reaches 100%.
4. method according to claim 1 or 3, wherein in step 3), by the COD removal rates of rear ozone oxidation pond (E)
It is increased to 50%, reflux ratio reaches 100%.
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Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106007193A (en) * | 2016-06-29 | 2016-10-12 | 北京桑德环境工程有限公司 | Advanced treatment system and method of gasification wastewater of Lurgi gasifier |
| CN107226582A (en) * | 2016-08-18 | 2017-10-03 | 李磊 | A kind of sewage-treatment plant and method |
| CN111747600A (en) * | 2019-03-26 | 2020-10-09 | 中蓝连海设计研究院有限公司 | Ozone oxidation-biochemical coupling water treatment method |
| CN110937765A (en) * | 2019-12-30 | 2020-03-31 | 中海油天津化工研究设计院有限公司 | Method for deeply treating refractory organic wastewater by sectional ozone combined BFA |
| CN112174430B (en) * | 2020-09-25 | 2023-05-26 | 中蓝连海设计研究院有限公司 | Advanced sewage treatment method and device by ozone oxidation-biochemical coupling |
| CN112125478A (en) * | 2020-09-25 | 2020-12-25 | 中蓝连海设计研究院有限公司 | Biochemical treatment-ozone oxidation coupled sewage treatment method and application thereof |
| CN112125476A (en) * | 2020-09-25 | 2020-12-25 | 中蓝连海设计研究院有限公司 | Two-stage ozone oxidation-biological contact coupling sewage advanced treatment method and device |
| CN112125475B (en) * | 2020-09-25 | 2023-05-23 | 中蓝连海设计研究院有限公司 | Ozone oxidation-biological film coupling sewage treatment method |
| CN115583716A (en) * | 2022-05-07 | 2023-01-10 | 北京首创生态环保集团股份有限公司 | Serial ozone catalytic oxidation sewage treatment system and method |
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| EP2307323B1 (en) * | 2008-02-15 | 2012-05-23 | C.S.A. S.r.l. | Plant and process for the purification of wastewaters |
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Address after: Room 1107, Block D, Jiahua Building, No. 9 Shangdi Third Street, Haidian District, Beijing, 100085 Patentee after: Beijing Hanqi Environmental Technology Co.,Ltd. Address before: Room 1107, Block D, Jiahua Building, No. 9 Shangdi Third Street, Haidian District, Beijing, 100085 Patentee before: BEIJING HANQI ENVIRONMENT TECHNOLOGY CO.,LTD. |