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CN103274514A - Process method for performing advanced treatment on petrochemical wastewater through catalytic ozonation - Google Patents

Process method for performing advanced treatment on petrochemical wastewater through catalytic ozonation Download PDF

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Publication number
CN103274514A
CN103274514A CN2013102000603A CN201310200060A CN103274514A CN 103274514 A CN103274514 A CN 103274514A CN 2013102000603 A CN2013102000603 A CN 2013102000603A CN 201310200060 A CN201310200060 A CN 201310200060A CN 103274514 A CN103274514 A CN 103274514A
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China
Prior art keywords
tower
catalyzed oxidation
oxidation tower
ozone
preoxidation
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CN103274514B (en
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陆彩霞
郑书忠
陈爱民
钱光磊
张艳芳
陈军
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Tianjin Zhengda Science & Technology Co ltd
CNOOC Energy Technology and Services Ltd
CNOOC Tianjin Chemical Research and Design Institute Co Ltd
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China National Offshore Oil Corp CNOOC
CNOOC Energy Technology and Services Ltd
CNOOC Tianjin Chemical Research and Design Institute Co Ltd
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Abstract

The invention discloses a process method for performing advanced treatment on petrochemical wastewater through catalytic ozonation. The method is characterized by comprising the following steps of: allowing petrochemical wastewater to sequentially flow through a pre-oxidation tower, a catalytic oxidation tower I and a catalytic oxidation tower II, and respectively filling high-porosity inert filler, activated aluminum oxide-based catalyst and granular active carbon in three towers, wherein the pre-oxidation tower operates under pressure. The ozone is prepared by an oxygen-enriched source or oxygen source ozone generator, and tail gas in the tower is collected and treated in a unified mode.

Description

A kind of processing method of catalytic ozonation advanced treatment petrochemical wastewater
Technical field
The present invention relates to technology for treating industrial waste water, particularly a kind of processing method of catalytic ozonation advanced treatment petrochemical wastewater.
Background technology
Petrochemical wastewater contains a large amount of hardly degraded organic substances and hazardous and noxious substances usually, thereby influences traditional biochemical process treatment effect.Along with the raising of Environmental Protection in China standard-required and the demand of sewage recycling, the advanced treatment of wastewater technology of development of new becomes inexorable trend.
Ozone is a kind of stronger oxygenant, macromole hardly degraded organic substance in the waste water at first can be changed into small-molecule substance by modes such as chain rupture, open loops, thereby further mineralising is that carbonic acid gas and water are realized organic removal fully again.In addition, ozone produces oxygen after decomposing, and can not cause secondary pollution.Therefore, ozonation technology has a wide range of applications in field of waste water treatment.But also there are some problems in ozonation technology, has limited its large-scale application in field of waste water treatment, mainly shows following three aspects: the one, and ozone utilization rate is low, and dosage is big, causes processing cost to increase greatly; The 2nd, ozone has selectivity to organic oxidation, causes partial organic substances to remove; The 3rd, ozone oxidation is not thorough, usually the macromole hardly degraded organic substance is converted into small-molecule substance and can't removes fully, need combine with biochemical technology and finish the thorough removal of pollutent jointly, thereby increase cost of investment and operational management difficulty.
Summary of the invention
The purpose of this invention is to provide a kind of is the petrochemical wastewater advanced treatment process method of technological core with band pressure preoxidation and catalyzed oxidation.
The present invention is a kind of processing method of catalytic ozonation advanced treatment petrochemical wastewater, it is characterized in that:
1) the catalytic ozonation advanced treatment system is composed in series by preoxidation tower, catalyzed oxidation tower I, catalyzed oxidation tower II, waste water three towers of flowing through from bottom to top successively; Ozone is produced by ozonizer, and the tower inner exhaust gas is drawn laggard ozone breaker by cat head and handled the back discharging; According to the waste water quality water volume condition, increase the number of preoxidation tower, catalyzed oxidation tower I and catalyzed oxidation tower II serial or parallel connection;
2) described preoxidation tower band is pressed operation, and the tower internal gas pressure maintains 0.02 ~ 0.05Mpa; Described catalyzed oxidation tower I and the operation of catalyzed oxidation tower II normal pressure;
3) described preoxidation tower is equipped with the high porosity inert filler, is selected to be Pall ring, Raschig ring, cascade ring or rectangular saddle ring; Described catalyzed oxidation tower I and catalyzed oxidation tower II are equipped with activated alumina Quito phase catalyst and grain active carbon respectively;
4) waste water residence time ratio in described preoxidation tower, catalyzed oxidation tower I and catalyzed oxidation tower II is 1: 1.5 ~ 3: 1, and time length is decided according to concrete water quality situation;
5) the ozone dosage ratio of described preoxidation tower and catalyzed oxidation tower I is 1 ~ 2: 1, and the ozone ratio of adding of catalyzed oxidation tower I and catalyzed oxidation tower II is 1 ~ 3: 1; The concrete waste water quality of how many bases of dosage is determined;
6) the used source of the gas of described ozonizer is oxygen rich source or source of oxygen, and the ozone concn that provides is 50 ~ 150 mg/L.
Compared with prior art, the present invention has following characteristics:
1) the preoxidation tower is equipped with the high porosity inert filler, has increased the rate of mass transfer of ozone and waste water; Keep certain gaseous tension in the tower, increased the concentration of ordinary dissolution of ozone in water, its function mainly contains: 1. remove the ozone an oxidisable substance, reduce the subsequent catalyst load; 2. destroy some colloids and macromolecular substance structure in the water, prevent that such material from wrapping up, polluting catalyzer and cause catalyst failure and harden in catalytic tower; 3. for catalyzed oxidation tower I provides solvability ozone, ozone utilization rate and catalyzed oxidation efficient have been improved.
2) in the catalyzed oxidation tower I be that the heterogeneous catalyst inducing ozone of carrier decomposes and produces than ozone activity all kinds of free radical higher and almost non-selectivity with the activated alumina, thereby degraded is removed in the water and is difficult to by the various organism of ozone direct oxidation.
3) function of catalyzed oxidation tower II mainly be further oxidation removal preoxidation tower and the oxidation of catalyzed oxidation tower I internal cause not thoroughly and the small organic molecule that produces.This unit takes full advantage of gac to the strong absorption property of small organic molecule and ozone, in the local high density substrate reaction district that forms of activated carbon capillary, under the activated carbon catalysis effect, strengthen the removal effect of small organic molecule, thereby realize the thorough removal of hardly degraded organic substance in the water.
4) the present invention is by organically combining preoxidation tower, catalyzed oxidation tower I and catalyzed oxidation tower II, catalytic ozonation efficient and ozone utilization rate have not only been improved, and be conducive to prolong catalyzer work-ing life, prevent poisoning of catalyst, inactivation, thereby realized the organic effect of the collaborative removal of this device, improved effluent quality, provided cost savings.
Description of drawings
Accompanying drawing 1 is the process flow diagram of a kind of catalytic ozonation advanced treatment of the present invention petrochemical wastewater.
Wherein 1 is the preoxidation tower, and 2 is catalyzed oxidation tower I, and 3 is catalyzed oxidation tower II, and 4 is the high porosity inert filler, and 5 is activated alumina Quito phase catalyst, and 6 is grain active carbon, and 7 is ozonizer, and 8 is relief valve, and 9 is tensimeter.
Embodiment
Embodiment 1
Heilungkiang refinery company day is handled wastewater flow rate 2400m3/d, adopts secondary biochemical technology to handle at present.For realizing the comprehensive recycling of sewage, intend existing technology is carried out upgrading, increase advanced treatment unit on original secondary biochemical treatment technology basis.Adopt catalytic ozonation processing method of the present invention (shown in the accompanying drawing 1) that advanced treatment is carried out in the secondary biochemical water outlet, the scale of having carried out is the on-the-spot pilot plant test of 15m3/d.The hydraulic detention time of manufacturer's secondary biochemical water outlet in preoxidation tower 1, catalyzed oxidation tower I 2 and catalyzed oxidation tower II 3 is respectively 0.5h, 1h and 0.5h, and the ozone dosage is respectively 30 ~ 45mg/L, 30 ~ 45mg/L and 10 ~ 15 mg/L.Preoxidation tower 2 tower bands are pressed operation, and pressure-controlling is at 0.02 ~ 0.05Mpa.Ozone is produced by oxygen rich source ozonizer 7, and ozone concn is 80 ~ 105 mg/L.
Advanced treatment apparatus water inlet COD is 89 ~ 142mg/L, average out to 114 mg/L, after processing method of the present invention is handled, water outlet COD is 26 ~ 58 mg/L, average out to 49 mg/L, clearance has on average reached 57%, has reached the primary standard of country's " integrated wastewater discharge standard " in (GB8976-1996), satisfies manufacturer to the requirement of reusing sewage.
Embodiment 2
Guangdong petro-chemical corporation day is handled waste water 1200m3, adopts secondary biochemical technology to handle at present, has the problem of the difficult qualified discharge of waste water.Adopt catalytic ozonation processing method of the present invention (shown in Figure 1) that it has been carried out on-the-spot lab scale research.The hydraulic detention time of manufacturer's secondary biochemical water outlet in preoxidation tower 1, catalyzed oxidation tower I 2 and catalyzed oxidation tower II 3 is respectively 0.5h, 1.5h and 0.5h, and the ozone dosage is respectively 60 ~ 80mg/L, 40 ~ 60mg/L and 30 ~ 40 mg/L.Preoxidation tower 2 tower bands are pressed operation, and pressure-controlling is at 0.02 ~ 0.05Mpa.Ozone is produced by oxygen rich source ozonizer 7, and ozone concn is 100 ~ 150 mg/L.
Advanced treatment apparatus water inlet COD is 128 ~ 325 mg/L, average out to 234 mg/L, and after processing method of the present invention was handled, water outlet COD was 78-116 mg/L, average out to 97 mg/L, clearance has on average reached 59%.
Embodiment 3
Tianjin petro-chemical corporation day is handled waste water 1800m3, adopts secondary biochemical technology to handle at present, has waste water situation not up to standard once in a while, intends increasing catalytic ozonation advanced treatment process (shown in Figure 1), and it is carried out on-the-spot lab scale research.The hydraulic detention time of manufacturer's secondary biochemical water outlet in preoxidation tower 1, catalyzed oxidation tower I 2 and catalyzed oxidation tower II 3 is respectively 10min, 15min and 10min, and the ozone dosage is respectively 10 ~ 15mg/L, 10 ~ 15mg/L and 5 ~ 10 mg/L.Preoxidation tower 2 tower bands are pressed operation, and pressure-controlling is at 0.02 ~ 0.05Mpa.Ozone is produced by oxygen rich source ozonizer 7, and ozone concn is 50 ~ 80 mg/L.
Advanced treatment apparatus water inlet COD is 78 ~ 135 mg/L, average out to 107 mg/L, and after processing method of the present invention was handled, water outlet COD was 69 ~ 114 mg/L, average out to 86 mg/L.

Claims (1)

1. the processing method of a catalytic ozonation advanced treatment petrochemical wastewater is characterized in that:
1) the catalytic ozonation advanced treatment system is composed in series by preoxidation tower, catalyzed oxidation tower I, catalyzed oxidation tower II, waste water three towers of flowing through from bottom to top successively; Ozone is produced by ozonizer, and the tower inner exhaust gas is drawn laggard ozone breaker by cat head and handled the back discharging; According to the waste water quality water volume condition, increase the number of preoxidation tower, catalyzed oxidation tower I and catalyzed oxidation tower II serial or parallel connection;
2) described preoxidation tower band is pressed operation, and the tower internal gas pressure maintains 0.02 ~ 0.05Mpa; Described catalyzed oxidation tower I and the operation of catalyzed oxidation tower II normal pressure;
3) described preoxidation tower is equipped with the high porosity inert filler, is selected to be Pall ring, Raschig ring, cascade ring or rectangular saddle ring; Described catalyzed oxidation tower I and catalyzed oxidation tower II are equipped with activated alumina Quito phase catalyst and grain active carbon respectively;
4) waste water residence time ratio in described preoxidation tower, catalyzed oxidation tower I and catalyzed oxidation tower II is 1: 1.5 ~ 3: 1, and time length is decided according to concrete water quality situation;
5) the ozone dosage ratio of described preoxidation tower and catalyzed oxidation tower I is 1 ~ 2: 1, and the ozone ratio of adding of catalyzed oxidation tower I and catalyzed oxidation tower II is 1 ~ 3: 1; The concrete waste water quality of how many bases of dosage is determined;
6) the used source of the gas of described ozonizer is oxygen rich source or source of oxygen, and the ozone concn that provides is 50 ~ 150 mg/L.
CN201310200060.3A 2013-05-27 2013-05-27 Process method for performing advanced treatment on petrochemical wastewater through catalytic ozonation Active CN103274514B (en)

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Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103936235A (en) * 2014-04-29 2014-07-23 武汉市润之达石化设备有限公司 Sewage treatment equipment of continuous ozone reaction tower
CN105692866A (en) * 2014-11-27 2016-06-22 中国海洋石油总公司 Packing method of catalyst for processing high-acid heavy crude oil processing wastewater
CN105692864A (en) * 2014-11-27 2016-06-22 中国海洋石油总公司 Method for processing wastewater
CN106348422A (en) * 2016-10-13 2017-01-25 中海油天津化工研究设计院有限公司 Multistage catalytic ozonation treating device for degradation-resistant organic wastewater
CN106865736A (en) * 2015-12-11 2017-06-20 中国石油天然气股份有限公司 Industrial wastewater treatment method and device
CN107311359A (en) * 2016-06-12 2017-11-03 中国石油化工股份有限公司 Product oil storage field oil-polluted water deep treatment method
CN108117148A (en) * 2016-11-29 2018-06-05 中国石油天然气股份有限公司 Device and method for treating salt-containing sewage
CN108217912A (en) * 2016-12-21 2018-06-29 中国石油天然气股份有限公司 Treatment method for refining high-concentration brine
CN108516634A (en) * 2018-05-15 2018-09-11 济南云水腾跃环保科技有限公司 A kind of catalytic ozonation processing method of alkalinity organic wastewater containing stink
CN108906073A (en) * 2018-07-18 2018-11-30 南京大学盐城环保技术与工程研究院 A kind of catalyst, decoloration device and its discoloration method for industrial wastewater decoloration
CN110937760A (en) * 2019-12-20 2020-03-31 中海油天津化工研究设计院有限公司 Baffling type ozone pre-oxidation combined biological filter advanced treatment method
CN113429010A (en) * 2021-05-28 2021-09-24 郑州大学综合设计研究院有限公司 Ozone and active carbon advanced treatment waste water's device in coordination
CN116239211A (en) * 2023-05-11 2023-06-09 天津群峰环保科技有限公司 Photovoltaic wastewater treatment system and treatment method

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JP4195499B2 (en) * 2005-10-11 2008-12-10 有限会社K2R Photocatalytic reaction water generator
CN102432125A (en) * 2011-11-11 2012-05-02 华南理工大学 Device for treating pulping wastewater by catalytic ozone and treatment method thereof
CN102491563A (en) * 2011-12-22 2012-06-13 哈尔滨工业大学 Three-stage catalysis ozone oxidation water purifying device
CN102923913A (en) * 2012-11-09 2013-02-13 中国海洋石油总公司 Combined treatment method of oil-refining wastewater containing naphthenic acid

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Publication number Priority date Publication date Assignee Title
JP4195499B2 (en) * 2005-10-11 2008-12-10 有限会社K2R Photocatalytic reaction water generator
CN101269892A (en) * 2008-05-04 2008-09-24 哈尔滨工业大学 Method for removing subaqueous organic matter with catalysis ozone oxidization
CN102432125A (en) * 2011-11-11 2012-05-02 华南理工大学 Device for treating pulping wastewater by catalytic ozone and treatment method thereof
CN102491563A (en) * 2011-12-22 2012-06-13 哈尔滨工业大学 Three-stage catalysis ozone oxidation water purifying device
CN102923913A (en) * 2012-11-09 2013-02-13 中国海洋石油总公司 Combined treatment method of oil-refining wastewater containing naphthenic acid

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103936235A (en) * 2014-04-29 2014-07-23 武汉市润之达石化设备有限公司 Sewage treatment equipment of continuous ozone reaction tower
CN105692866B (en) * 2014-11-27 2018-07-13 中国海洋石油集团有限公司 A kind of packing method of the catalyst of processing high-acid heavy crude oil processing waste water
CN105692866A (en) * 2014-11-27 2016-06-22 中国海洋石油总公司 Packing method of catalyst for processing high-acid heavy crude oil processing wastewater
CN105692864A (en) * 2014-11-27 2016-06-22 中国海洋石油总公司 Method for processing wastewater
CN105692864B (en) * 2014-11-27 2018-09-07 中国海洋石油集团有限公司 A method of processing waste water
CN106865736A (en) * 2015-12-11 2017-06-20 中国石油天然气股份有限公司 Industrial wastewater treatment method and device
CN107311359A (en) * 2016-06-12 2017-11-03 中国石油化工股份有限公司 Product oil storage field oil-polluted water deep treatment method
CN106348422A (en) * 2016-10-13 2017-01-25 中海油天津化工研究设计院有限公司 Multistage catalytic ozonation treating device for degradation-resistant organic wastewater
CN108117148A (en) * 2016-11-29 2018-06-05 中国石油天然气股份有限公司 Device and method for treating salt-containing sewage
CN108217912A (en) * 2016-12-21 2018-06-29 中国石油天然气股份有限公司 Treatment method for refining high-concentration brine
CN108516634A (en) * 2018-05-15 2018-09-11 济南云水腾跃环保科技有限公司 A kind of catalytic ozonation processing method of alkalinity organic wastewater containing stink
CN108906073A (en) * 2018-07-18 2018-11-30 南京大学盐城环保技术与工程研究院 A kind of catalyst, decoloration device and its discoloration method for industrial wastewater decoloration
CN108906073B (en) * 2018-07-18 2020-11-03 南京大学盐城环保技术与工程研究院 Catalyst for industrial wastewater decolorization, decolorization device and decolorization method thereof
CN110937760A (en) * 2019-12-20 2020-03-31 中海油天津化工研究设计院有限公司 Baffling type ozone pre-oxidation combined biological filter advanced treatment method
CN113429010A (en) * 2021-05-28 2021-09-24 郑州大学综合设计研究院有限公司 Ozone and active carbon advanced treatment waste water's device in coordination
CN113429010B (en) * 2021-05-28 2023-08-22 郑州大学综合设计研究院有限公司 Device and method for advanced wastewater treatment by cooperation of ozone and activated carbon
CN116239211A (en) * 2023-05-11 2023-06-09 天津群峰环保科技有限公司 Photovoltaic wastewater treatment system and treatment method

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