CN101863589B - 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 PDF

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Publication number
CN101863589B
CN101863589B CN2010102002643A CN201010200264A CN101863589B CN 101863589 B CN101863589 B CN 101863589B CN 2010102002643 A CN2010102002643 A CN 2010102002643A CN 201010200264 A CN201010200264 A CN 201010200264A CN 101863589 B CN101863589 B CN 101863589B
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China
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wastewater
ozone
water
catalytic ozonation
basin
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CN2010102002643A
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Chinese (zh)
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CN101863589A (en
Inventor
王亚明
唐新亮
张金钧
陈建军
雷勇
宋小林
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中国海洋石油总公司
中海沥青(泰州)有限责任公司
苏州科环环保科技有限公司
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Priority to CN2010102002643A priority Critical patent/CN101863589B/en
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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 IndustryMain Water Pollutant Discharge Standard, completely by further treatment in the BAF basin.

Description

The method of advanced treatment of wastewater is carried out in a kind of using ozone catalyzed oxidation and internal circulation biological filter combination
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 degraded type organic that is prone to is handled through biochemical for a long time in the refinery sewage, and removal basically 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; The ozone dosage is too big, utilization ratio is low, speed of response is slow, energy consumption is high reaches problems such as organic selectivity are strong but exist; Prior art comes aspects such as sewage quality modification raising biodegradability are not played expected effect through ozone oxidation simultaneously, and ozone oxidation is not brought into play expected effect, and the macromolecular substance with difficult degradation is not oxidized to the small-molecule substance that is prone to 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) gets into the catalytic ozonation tower behind the below standard sewage water filtration, and in said catalytic ozonation tower, add ozone simultaneously, carry out catalytic oxidation;
2) make the water outlet of catalytic ozonation tower get in the oxidation buffer stabilization pond stable;
3) after stable, get into inner circulating aerating biological filtering tank again and handle, the water of discharge gets into 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 righttest dosage is 8-12mg.
Step 2) catalyzer in the tower of catalytic ozonation described in exists with the form of fixed bed, and said catalyzer specifically can be the agent of metals ion loading type ozone catalytic, and the model of producing like 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 get into inner circulating aerating biological filtering tank (BAF pond), need to stablize could residual ozone and hydroxyl radical free radical (OH) be decomposed fully in 0.5-4 hour.
Method of the present invention gets into water collecting basin with below standard sewage earlier; Promoting the entering more medium filter through pump filters; Remove suspended substance in the water, purpose is to reduce the oxidation load that gets into the catalyzed oxidation tower, improves 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 gets into 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, and 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 get into biochemical system internal recycle BAF pond, back, need to stablize could residual ozone and hydroxyl radical free radical (OH) 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; Carry out biochemical treatment from flowing into internal recycle BAF pond; Utilize internal recycle BAF pond to carry out the organic pollutant in the biochemical degradation sewage; Internal recycle BAF pond mikrobe oxidizes away organic pollutant, and organic carbon is converted into inorganic carbon, guarantees the stably reaching standard of follow-up water outlet.Internal recycle BAF draining flows into clean water basin certainly, and discharges through clean water basin overflow water outlet.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 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 through 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 through 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 like no specified otherwise, is ordinary method.Used test materials among the following embodiment like no specified otherwise, 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 (table 1 is seen in water) is promoted through pump, get into strainer and filter;
B). (catalyzer in the catalytic ozonation tower is: Cu/TiO to get into 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 gets into the oxidation buffer stabilization pond and stablizes 0.5-4h;
D). after stable, get into internal recycle BAF pond again and handle;
E). draining flows into clean water basin certainly, and discharges through clean water basin overflow water outlet, and table 1 is seen in the water of this drainage water.
F). backwashing pump is that the back flushing of internal recycle BAF pond, strainer and catalyzed oxidation tower provides backwash water.
Table 1, handle before and handle after water
Can know by 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 also effluent quality has reached petroleum chemical enterprise's reuse water standard after handling, and has reduced organic quantity discharged.

Claims (1)

1. a refinery advanced treatment method for sewage water comprises the steps:
1) below standard sewage adopts more medium filter to filter back entering catalytic ozonation tower, and in said catalytic ozonation tower, adds ozone simultaneously, carries out catalytic oxidation; Wherein, the catalyzer in the said catalytic ozonation tower exists with the form of fixed bed; The dosage of ozone is 8-12mg described in every liter of sewage;
2) water outlet of catalytic ozonation tower being got in the oxidation buffer stabilization pond stablized 0.5-4 hour;
3) after stable, get into inner circulating aerating biological filtering tank again and handle, the water of discharge gets into clean water basin.
CN2010102002643A 2010-06-09 2010-06-09 Method for advanced treatment of wastewater by using combination of catalytic ozonation and internal circulation biological filter CN101863589B (en)

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CN104609533B (en) * 2015-01-27 2017-07-28 王丽英 A kind of control system and method for organic wastewater with difficult degradation thereby ozone heterogeneous catalytic oxidation handling process
CN104671391B (en) * 2015-01-27 2017-01-25 王丽英 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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CN106517515A (en) * 2016-10-21 2017-03-22 中海油天津化工研究设计院有限公司 Deep treatment system and method for ozone combined biological filters
CN110540336A (en) * 2018-05-29 2019-12-06 中国石油化工股份有限公司 treatment method and application of ammoximation wastewater
CN109320013A (en) * 2018-10-31 2019-02-12 首创爱华(天津)市政环境工程有限公司 A kind of advanced treatment method for sewage water

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CN101323493A (en) * 2008-07-24 2008-12-17 华南理工大学 Waste water treatment apparatus based on ozone oxidation and aerating biological filter
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Address after: 100010 Chaoyangmen North Street, Dongcheng District, Dongcheng District, Beijing

Co-patentee after: Zhonghai asphalt (Taizhou) Co., Ltd.

Patentee after: China Offshore Oil Group Co., Ltd.

Co-patentee after: Zhonghai asphalt (Taizhou) Co., Ltd.

Address before: 100010 Chaoyangmen North Street, Dongcheng District, Dongcheng District, Beijing

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Patentee after: China Offshore Oil Group Co., Ltd.

Co-patentee after: Zhonghai Asphalt (Taizhou) Co., Ltd.

Address before: 100010 Beijing, Chaoyangmen, North Street, No. 25, No.

Co-patentee before: Zhonghai asphalt (Taizhou) Co., Ltd.

Patentee before: China Offshore Oil Group Co., Ltd.

Co-patentee before: Zhonghai asphalt (Taizhou) Co., Ltd.