CN101863589A - Method for advanced treatment of wastewater by using combination of catalytic ozonation and internal circulation biological filter - Google Patents
Method for advanced treatment of wastewater by using combination of catalytic ozonation and internal circulation biological filter Download PDFInfo
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- CN101863589A CN101863589A CN 201010200264 CN201010200264A CN101863589A CN 101863589 A CN101863589 A CN 101863589A CN 201010200264 CN201010200264 CN 201010200264 CN 201010200264 A CN201010200264 A CN 201010200264A CN 101863589 A CN101863589 A CN 101863589A
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- 238000000034 method Methods 0.000 title claims abstract description 24
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 18
- 238000006385 ozonation reaction Methods 0.000 title claims abstract description 15
- 239000002351 wastewater Substances 0.000 title abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 44
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims abstract description 29
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 28
- 230000006641 stabilisation Effects 0.000 claims abstract description 8
- 238000011105 stabilization Methods 0.000 claims abstract description 8
- 238000001914 filtration Methods 0.000 claims abstract description 7
- 239000010865 sewage Substances 0.000 claims description 28
- 230000003647 oxidation Effects 0.000 claims description 25
- 239000000126 substance Substances 0.000 abstract description 14
- 239000003054 catalyst Substances 0.000 abstract description 4
- 239000002184 metal Substances 0.000 abstract description 4
- 230000004913 activation Effects 0.000 abstract description 3
- 229920002521 macromolecule Polymers 0.000 abstract description 2
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 abstract 1
- 238000007670 refining Methods 0.000 abstract 1
- 239000003403 water pollutant Substances 0.000 abstract 1
- -1 hydroxyl radical free radical Chemical class 0.000 description 9
- 230000015556 catabolic process Effects 0.000 description 5
- 238000006731 degradation reaction Methods 0.000 description 5
- 230000001590 oxidative effect Effects 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 3
- 235000011089 carbon dioxide Nutrition 0.000 description 3
- JYYOBHFYCIDXHH-UHFFFAOYSA-N carbonic acid;hydrate Chemical compound O.OC(O)=O JYYOBHFYCIDXHH-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000011010 flushing procedure Methods 0.000 description 3
- 230000005484 gravity Effects 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000002957 persistent organic pollutant Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 150000003384 small molecules Chemical class 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000003631 expected effect Effects 0.000 description 2
- 230000002070 germicidal effect Effects 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 206010058490 Hyperoxia Diseases 0.000 description 1
- 238000011001 backwashing Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 230000031018 biological processes and functions Effects 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003657 drainage water Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000000222 hyperoxic effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 239000013586 microbial product Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 235000016709 nutrition Nutrition 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 1
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Abstract
The invention discloses a method for the advanced treatment of wastewater. The method comprises the following steps of: 1) filtering off-standard wastewater, delivering the wastewater into a catalytic ozonation tower, and simultaneously adding ozone for contact oxidization reaction; 2) delivering the effluent of the catalytic ozonation tower into an oxidization buffer stabilization basin for stabilization; 3) and after the stabilization, delivering the effluent into a BAF basin for treatment, and delivering discharged water into a clean water basin. The method reduces the addition amount of the ozone, improves the utilization efficiency of the ozone, converts the ozone into hydroxyl radicals by using a metal catalyst, and reduces the activation energy of hydroxyl radical oxidation reaction to promote hardly biodegradable macromolecule organic substances in the wastewater to be oxidized into easily biodegradable micromolecule substances, so that the biochemical limit to refining the wastewater is broken through and the biodegradability of the wastewater is increased; and the water quality of the effluent can meet the provincial standard of Jiangsu province, namely Chemical Industry Main Water Pollutant Discharge Standard, completely by further treatment in the BAF basin.
Description
Technical field
The present invention relates to the combination of a kind of using ozone catalyzed oxidation and internal circulation biological filter and carry out the method for advanced treatment of wastewater.
Background technology
At present, most of easily degraded type organic is handled for a long time by biochemical in the refinery sewage, and removal substantially is degraded.And difficult degradation type organics such as nitrogen heterocyclic ring class and polycyclic aromatic hydrocarbons are not the oxidation of biological institute basically, and solubility microbial product (SMP) biodegradation rate that produces in the process of biochemical treatment simultaneously is very slow.Therefore, directly with biological process refinery water being carried out advanced treatment obviously falls flat, at present domestic comparatively advanced method is to adopt ozone oxidation and biological aerated filter technical finesse lower concentration hardly degraded organic substance, but exist the ozone dosage too big, utilization ratio is low, speed of response is slow, energy consumption is high to be reached problems such as organic selectivity are strong, prior art comes aspects such as sewage quality modification raising biodegradability are not played expected effect by ozone oxidation simultaneously, ozone oxidation is not brought into play expected effect, the macromolecular substance of difficult degradation is not oxidized to the small-molecule substance of easy degraded, do not have effectively to improve the biodegradability of poor nutritional substance in the biochemical section sewage of back, cause the generate subsequent metallization processes can not bring into play the biological degradation function of its expection.
Summary of the invention
Advanced treatment method for sewage water provided by the present invention comprises the steps:
1) enters the catalytic ozonation tower behind the below standard sewage water filtration, and in described catalytic ozonation tower, add ozone simultaneously, carry out catalytic oxidation;
2) make the water outlet of catalytic ozonation tower enter in the oxidation buffer stabilization pond stable;
3) after stable, enter inner circulating aerating biological filtering tank again and handle, the water of discharge enters clean water basin.
Wherein, in the step 1) dosage of ozone described in every liter of sewage less than 15mg; The dosage of ozone is relevant with the organic content in the waste water, and the suitableeest dosage is 8-12mg.
Step 2) catalyzer in the tower of catalytic ozonation described in exists with the form of fixed bed, and described catalyzer specifically can be the agent of metal ion loading type ozone catalytic, and the model of producing as ring Environmental Protection Technology Co., Ltd of Suzhou section is the Cu/TiO of KH-SC-XT
2/ Al
2O
3Catalyzer.
The present invention adopts metal catalyst that ozone is converted into hydroxyl radical free radical, reduce the activation energy of hydroxyl radical free radical oxidizing reaction simultaneously, make the larger molecular organics of difficult degradation in the sewage be more prone to be oxidized into the small-molecule substance of readily biodegradable, even directly be degraded to carbonic acid gas and water, improve biodegradability.
Owing to still also have certain density ozone and hydroxyl radical free radical (OH) in the water outlet of ozone oxidation tower, have strong oxidation and germicidal action, can not directly enter inner circulating aerating biological filtering tank (BAF pond), need to stablize residual ozone and hydroxyl radical free radical (OH) to be decomposed fully in 0.5-4 hour.
Method of the present invention enters water collecting basin with below standard sewage earlier, entering more medium filter through the pump lifting filters, remove suspended substance in the water, purpose is to reduce the oxidation load that enters the catalyzed oxidation tower, improve the service efficiency of ozone, reduce obstruction simultaneously, the normal operation and the effluent quality of assurance device to oxidizing tower.The water outlet of strainer enters the catalyzed oxidation tower of metal catalyst, throw in certain density ozonized air simultaneously, under the effect of metal catalyst, the ozone of hyperoxia voltinism is transformed into hydroxyl radical free radical, and (hydroxyl radical free radical is a kind of strong oxidizer, the organism speed of response is fast in it and the sewage, and low to organic selectivity.), also reduced the activation energy of hydroxyl radical free radical oxidizing reaction simultaneously, with macromolecular pollutant oxidation, chain rupture, be transformed into the small molecules that is easy to biochemistry, even directly be degraded to carbonic acid gas and water, broken through the biochemical limit of refinery sewage, improve the biodegradability of sewage, reduce the colourity of sewage.The oxidizing tower water outlet is from flowing into the oxidation buffer stabilization pond, owing to still also have certain density ozone and hydroxyl radical free radical (OH) in the water outlet of ozone oxidation tower, have strong oxidation and germicidal action, can not directly enter biochemical system internal recycle BAF pond, back, need to stablize residual ozone and hydroxyl radical free radical (OH) to be decomposed fully in 0.5-4 hour, guarantee that it is not to microorganisms toxic action in the biological filter.Through the sewage after the modification of catalyzed oxidation tower, gravity flow enters internal recycle BAF pond and carries out biochemical treatment, utilize internal recycle BAF pond to carry out organic pollutant in the biochemical degradation sewage, microorganism oxidizes away organic pollutant in internal recycle BAF pond, organic carbon is converted into inorganic carbon, guarantees the stably reaching standard of follow-up water outlet.Internal recycle BAF draining gravity flow enters clean water basin, and overflows mouth of a river discharge by clean water basin.Clean water basin also provide backwash water for the back flushing of facilities such as internal recycle BAF pond, strainer and catalyzed oxidation tower simultaneously, all the muddy water mixed solution of back flushing discharge enters the mud-water separation pond, supernatant liquor enters original system oily(waste)water pond, and sedimentary mud uses muddy water to be pumped to three mud water knockouts.Remove pollutents such as COD, ammonia nitrogen, petroleum-type, suspended substance by catalytic ozonation and internal circulation biological filter combination process,, improved removal efficient, reduced processing cost than other technology.
After adopting above technical scheme, the present invention has following beneficial effect:
1) water quality of refinery sewage is carried out degree of depth modification, even directly be degraded to carbonic acid gas and water, broken through the biochemical limit of refinery sewage, increased its biodegradability, carried out further biochemical treatment by the internal recycle biological aerated filter again and remove organic pollutant (the COD clearance can reach 40%) remaining in the sewage.
2) stable, the ozone dosage O of present method
3＜15mg/L, working cost low (the newly-increased processing cost of sewage per ton is about 0.5 yuan), operational management is simple, floor space is little, initial cost is few.Effluent quality after the processing is as clear as crystal, suspended substance≤10mg/L, COD＜60mg/L, oleaginousness＜5mg/L, ammonia nitrogen＜15mg/L reaches Jiangsu Province's provincial standard fully--" the main pollution discharge standard of chemical industry ", and effluent quality has reached petroleum chemical enterprise's reuse water standard after handling, reduce organic quantity discharged, produced social benefit energetically, realized the harmonious development of man and nature.
3) present method is not added other chemical agents, does not produce secondary pollution.
Description of drawings
Fig. 1 is a process flow diagram of the present invention.
Embodiment
Following embodiment is convenient to understand better the present invention, but does not limit the present invention.Experimental technique among the following embodiment if no special instructions, is ordinary method.Used test materials among the following embodiment if no special instructions, is to buy from routine biochemistry reagent shop and obtains.
Embodiment 1, employing catalytic ozonation and internal circulation biological filter combination are handled refinery sewage
Adopt technical process shown in Figure 1 that this refinery sewage is handled.
A). below standard refinery sewage (water quality analysis sees Table 1) is promoted through pump, enter strainer and filter;
B). (catalyzer in the catalytic ozonation tower is: Cu/TiO to enter the catalytic ozonation tower through the water after filtering
2/ Al
2O
3, model: KH-SC-XT, manufacturer:, and carry out contact oxidation, reaction 0.5h Suzhou section ring Environmental Protection Technology Co., Ltd) with the ozone that adds simultaneously; The dosage of ozone is a 8-12mg/L sewage;
C). the oxidizing tower water outlet enters the oxidation buffer stabilization pond and stablizes 0.5-4h;
D). after stable, enter internal recycle BAF pond again and handle;
E). the draining gravity flow enters clean water basin, and overflows mouth of a river discharge by clean water basin, and the water quality analysis of this drainage water sees Table 1.
F). backwashing pump provides backwash water for the back flushing of internal recycle BAF pond, strainer and catalyzed oxidation tower.
Table 1, water quality analysis before and after treatment
As shown in Table 1, effluent quality after method of the present invention is handled is as clear as crystal, COD＜60mg/L, reach Jiangsu Province's provincial standard fully--" the main pollution discharge standard of chemical industry ", and effluent quality has reached petroleum chemical enterprise's reuse water standard after handling, and has reduced organic quantity discharged.
Claims (6)
1. an advanced treatment method for sewage water comprises the steps:
1) enters the catalytic ozonation tower behind the below standard sewage water filtration, and in described catalytic ozonation tower, add ozone simultaneously, carry out catalytic oxidation;
2) make the water outlet of catalytic ozonation tower enter in the oxidation buffer stabilization pond stable;
3) after stable, enter inner circulating aerating biological filtering tank again and handle, the water of discharge enters clean water basin.
2. method according to claim 1 is characterized in that: the dosage of ozone is less than 15mg described in every liter of sewage of step 1).
3. method according to claim 1 and 2 is characterized in that: the dosage of ozone is 8-12mg described in every liter of sewage of step 1).
4. according to arbitrary described method among the claim 1-3, it is characterized in that: the catalyzer described in the step 1) in the described catalytic ozonation tower exists with the form of fixed bed.
5. according to arbitrary described method among the claim 1-4, it is characterized in that: step 2) in described oxidation buffer stabilization pond the stable time be 0.5-4 hour.
6. according to arbitrary described method among the claim 1-5, it is characterized in that: sewage described in the step 1) is refinery sewage.
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| CN2010102002643A CN101863589B (en) | 2010-06-09 | 2010-06-09 | Method for advanced treatment of wastewater by using combination of catalytic ozonation and internal circulation biological filter |
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|---|---|---|---|
| CN2010102002643A CN101863589B (en) | 2010-06-09 | 2010-06-09 | Method for advanced treatment of wastewater by using combination of catalytic ozonation and internal circulation biological filter |
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| CN101863589B CN101863589B (en) | 2012-04-18 |
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| CN103304096A (en) * | 2013-06-13 | 2013-09-18 | 中国海洋石油总公司 | Method for performing ozone catalysis-coupled biological nitrification treatment on acrylonitrile wastewater |
| CN103979735A (en) * | 2014-05-21 | 2014-08-13 | 青岛中通臭氧科技有限公司 | Process and device for treating refractory industrial wastewater |
| CN104193114A (en) * | 2014-09-18 | 2014-12-10 | 广东溢达纺织有限公司 | Sewage treatment method and sewage treatment system |
| CN104609533A (en) * | 2015-01-27 | 2015-05-13 | 北京中科圣泰环境科技有限公司 | Control system and method for degradation-resistant organic wastewater ozone heterogeneous catalysis oxidation treatment process |
| CN104671391A (en) * | 2015-01-27 | 2015-06-03 | 北京中科圣泰环境科技有限公司 | Ozone heterogeneous catalysis oxidization treatment device and technology for hardly degradable organic wastewater |
| CN104787924A (en) * | 2015-03-13 | 2015-07-22 | 苏州科环环保科技有限公司 | Caprolactam sewage advanced treatment method using ozone catalytic oxidation |
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