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 PDFInfo
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- 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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- tower
- catalyzed oxidation
- oxidation tower
- ozone
- preoxidation
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- 239000002351 wastewater Substances 0.000 title claims abstract description 27
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 16
- 238000006385 ozonation reaction Methods 0.000 title claims abstract description 15
- 238000000034 method Methods 0.000 title abstract description 9
- 230000003647 oxidation Effects 0.000 claims abstract description 51
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 51
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims abstract description 36
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 10
- 239000001301 oxygen Substances 0.000 claims abstract description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000003054 catalyst Substances 0.000 claims abstract description 7
- 239000007789 gas Substances 0.000 claims abstract description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000000945 filler Substances 0.000 claims abstract description 5
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 238000003672 processing method Methods 0.000 claims description 9
- 241000282326 Felis catus Species 0.000 claims description 2
- 238000007599 discharging Methods 0.000 claims description 2
- 238000005516 engineering process Methods 0.000 description 11
- 239000000126 substance Substances 0.000 description 11
- 230000000694 effects Effects 0.000 description 5
- 230000001965 increasing effect Effects 0.000 description 3
- 239000010865 sewage Substances 0.000 description 3
- 238000004064 recycling Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 150000003384 small molecules Chemical class 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000003851 biochemical process Effects 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- JYYOBHFYCIDXHH-UHFFFAOYSA-N carbonic acid;hydrate Chemical compound O.OC(O)=O JYYOBHFYCIDXHH-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000001473 noxious effect Effects 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000003245 working effect Effects 0.000 description 1
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- Treatment Of Water By Oxidation Or Reduction (AREA)
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
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.
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| CN201310200060.3A CN103274514B (en) | 2013-05-27 | 2013-05-27 | Process method for performing advanced treatment on petrochemical wastewater through catalytic ozonation |
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| CN103274514A true CN103274514A (en) | 2013-09-04 |
| CN103274514B CN103274514B (en) | 2014-06-04 |
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Cited By (13)
| 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 |
| CN105692864A (en) * | 2014-11-27 | 2016-06-22 | 中国海洋石油总公司 | Method for processing wastewater |
| 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 |
| 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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Cited By (17)
| 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 |
| CN105692864A (en) * | 2014-11-27 | 2016-06-22 | 中国海洋石油总公司 | Method for processing wastewater |
| 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 |
| 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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Address after: 100010 Beijing, Chaoyangmen, North Street, No. 25, No. Patentee after: CHINA NATIONAL OFFSHORE OIL Corp. Patentee after: CNOOC TIANJIN CHEMICAL RESEARCH & DESIGN INSTITUTE Co.,Ltd. Patentee after: CNOOC ENERGY TECHNOLOGY & SERVICES Ltd. Address before: 100010 Beijing, Chaoyangmen, North Street, No. 25, No. Patentee before: CHINA NATIONAL OFFSHORE OIL Corp. Patentee before: CNOOC TIANJIN CHEMICAL RESEARCH & DESIGN INSTITUTE Patentee before: CNOOC ENERGY TECHNOLOGY & SERVICES Ltd. |
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Effective date of registration: 20161010 Address after: No. three road 300131 Tianjin city Hongqiao District dingzigu No. 85 Patentee after: CNOOC TIANJIN CHEMICAL RESEARCH & DESIGN INSTITUTE Co.,Ltd. Patentee after: CNOOC ENERGY TECHNOLOGY & SERVICES Ltd. Address before: 100010 Beijing, Chaoyangmen, North Street, No. 25, No. Patentee before: CHINA NATIONAL OFFSHORE OIL Corp. Patentee before: CNOOC TIANJIN CHEMICAL RESEARCH & DESIGN INSTITUTE Co.,Ltd. Patentee before: CNOOC ENERGY TECHNOLOGY & SERVICES Ltd. |
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Effective date of registration: 20180214 Address after: No. three road 300131 Tianjin city Hongqiao District dingzigu No. 85 Co-patentee after: CNOOC ENERGY TECHNOLOGY & SERVICES Ltd. Patentee after: CNOOC TIANJIN CHEMICAL RESEARCH & DESIGN INSTITUTE Co.,Ltd. Co-patentee after: TIANJIN HAIHUA ENVIRONMENTAL ENGINEERING CO.,LTD. Address before: No. three road 300131 Tianjin city Hongqiao District dingzigu No. 85 Co-patentee before: CNOOC ENERGY TECHNOLOGY & SERVICES Ltd. Patentee before: CNOOC TIANJIN CHEMICAL RESEARCH & DESIGN INSTITUTE Co.,Ltd. |
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Effective date of registration: 20230308 Address after: 300131 No. three, No. 85, Tianjin Road, Hongqiao District, China Patentee after: CNOOC TIANJIN CHEMICAL RESEARCH & DESIGN INSTITUTE Co.,Ltd. Patentee after: CNOOC ENERGY TECHNOLOGY & SERVICES Ltd. Patentee after: TIANJIN ZHENGDA SCIENCE & TECHNOLOGY CO.,LTD. Address before: 300131 No. three, No. 85, Tianjin Road, Hongqiao District, China Patentee before: CNOOC TIANJIN CHEMICAL RESEARCH & DESIGN INSTITUTE Co.,Ltd. Patentee before: CNOOC ENERGY TECHNOLOGY & SERVICES Ltd. Patentee before: TIANJIN HAIHUA ENVIRONMENTAL ENGINEERING CO.,LTD. |
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