CN102923913A - Combined treatment method of oil-refining wastewater containing naphthenic acid - Google Patents
Combined treatment method of oil-refining wastewater containing naphthenic acid Download PDFInfo
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Abstract
The invention relates to a combined treatment method of oil-refining wastewater containing naphthenic acid. The combined treatment method of the oil-refining wastewater containing naphthenic acid is characterized in that a pre-treatment technology is added at the front end of an 'anoxic/oxic' ('A/O') step of an oil removing + A/O process, and an advanced treatment process is added at the back end of the 'A/O' step. Air-floatation oil removing effluent enters a modified biological aerated filter to be pre-treated, a filler is subjected to modification treatment, and the combined treatment method adopts upstream continuous operation. Hydraulic loading is controlled in a range of 1.0-3.0 m<3>/m<2>-h, the temperature is controlled in a range of 25-35 DEG C, the reflux ratio is controlled to be 100-150%, the gas-water ratio is controlled to be 3:1-5:1, and an automatic back washing period is controlled to be 48-72 hours. The effluent of the modified biological aerated filter is subjected to treatment of an 'A/O' biochemical system, enters an intermediate reaction tank and then enters a pre-mixing tower in parallel. The effluent of the pre-mixing tower enters a catalytic oxidation tower to quickly oxidize difficultly-biodegradable organic matter in sewage and reduce chemical oxygen demand (COD) of the sewage, and finally treated effluent enters a clean water pond.
Description
Technical field
The present invention relates to the Treatment of Industrial Water technical field, be a kind of combination treatment method that contains the naphthenic acid oil refining sewerage.
Background technology
At present, China part refinery process for processing heavy crude, its sewage quality complicated component, mainly contain the Persistent organic pollutants such as naphthenic acid and higher soluble solid and (be generally 3000～5000mg/L), after traditional " oil removing+A/O " method processing, CODcr is 200mg/L, BOD
5For 5mg/L(B/C only is 0.025, belong to utmost point waste water difficult for biological degradation), this is higher than country-level A emission standard far away.For discharging or the reuse requirement of satisfying increasingly stringent, the methods such as some enterprises' employing charcoal absorptions are carried out advanced treatment to it, although the water outlet after processing can reach emission standard, but gac is very easily saturated, and pollutent just shifts and do not removed, and has produced the solid pollutant of secondary pollution when changing gac, and change frequent, running cost is high, for solving this distinct issues, contains naphthenic acid oil refining sewerage treatment process in the urgent need to the development process effect stability.
A kind of combination treatment method that contains the naphthenic acid oil refining sewerage of the present invention increases the modification BAF as pretreatment technology at original tradition " oil removing+A/O " treatment process " A/O " front end, improve the biodegradability of sewage, increase simultaneously the catalytic ozonation system in " A/O " rear end as advanced treatment process, further reduce water outlet CODcr, make it reach discharging or reuse requirement, concrete technology is seen summary of the invention.
Summary of the invention
The present invention is a kind of combination treatment method that contains the naphthenic acid oil refining sewerage.Technique is provided with modification BAF and catalytic ozonation system, increase the modification BAF as pretreatment technology at tradition " oil removing+A/O " technique " A/O " front end, increase the catalytic ozonation system in " A/O " rear end as advanced treatment process.
The present invention is a kind of combination treatment method that contains the naphthenic acid oil refining sewerage, it is characterized in that:
" A/O " front end in tradition " oil removing+A/O " technique increases the modification BAF as pretreatment technology, increases the catalytic ozonation system in " A/O " rear end as advanced treatment process, and former water CODcr is 2500～3200mg/L, and its process is as follows:
1. modification BAF is provided with aeration and promotes reactor, modified filler and backwashing system; Aeration promotes reactor and adopts the upflowing operation, and hydraulic load is controlled at 1.0～3.0m
3/ m
2H, temperature is controlled at 25～35 ℃, and control of reflux ratio is 100～150%, and gas-water ratio is controlled at 3:1～5:1, and the automatic backwash periodic Control is at 48～72h; Simultaneously filler is carried out modification, the properties-correcting agent of selecting is sulfuric acid or hydrochloric acid, and the filler of employing is a kind of of haydite, zeolite, volcanics, flyash or aluminum oxide; To strengthen its biological adsorption degradation capability, in the inner anaerobic environment that forms of filler, make the difficult degradation larger molecular organics be transformed into easy degradation of small molecular organism, improve the biodegradability of sewage, at the outside aerobic environment that forms of filler, realize the removal of most COD cr, the sewage B/C after processing through the modification BAF brings up to 0.3, A/O from 0.15; Art breading water outlet CODcr is reduced to 100～120mg/L from 160～200mg/L;
2. the catalytic ozonation system is provided with two-stage catalyst oxidation reactor, recycling tail gas and decomposer and ozone generation system; Catalyst oxidation reactor comprises premixing tower and catalyzed oxidation tower, select modified aluminas, flyash or granulated active carbon as support of the catalyst in the catalyzed oxidation tower, strengthen the organic effect of its adsorption and enrichment, and one or more reactive metal elements of the copper of load 2.0～5.0%, iron, nickel, manganese; Utilize operation scheme in parallel, sewage enters premixing tower and catalyzed oxidation tower successively, the single-stage premixing tower reaction times is 30～60min, the single-stage ozone dosage is 25～35mg/L, the single-stage catalyzed oxidation tower reaction times is 15～20min, under the effect of ozone and catalyzer, removal is difficult to biodegradable CODcr, and processing water outlet CODcr is 48～50mg/L; Recycling tail gas and decomposer are that the premixing tower emission is reclaimed, and utilize remaining ozone that former water is carried out preaeration, further improve ozone utilization rate, simultaneously final emission are carried out disaggregating treatment, reach emission request.
According to combination treatment method of the present invention, it is characterized in that: the properties-correcting agent of selecting 1. is sulfuric acid or hydrochloric acid, and the filler of employing is haydite, zeolite, flyash.
According to combination treatment method of the present invention; it is characterized in that: premixing tower adopts the method for classification air feed 2.; improve ozone utilization rate; select modified aluminas, flyash or granulated active carbon as support of the catalyst in the catalyzed oxidation tower; strengthen the organic effect of its adsorption and enrichment; and one or more reactive metal elements of the copper of load 3.0～4.0%, iron, nickel, rapid organism in the oxidation sewage under its katalysis.
Description of drawings
Accompanying drawing 1 is a kind of process flow diagram that contains the combination treatment method of naphthenic acid oil refining sewerage of the present invention:
Wherein 1 is the modification BAF, and 2 is the A/O biochemical system, and 3 is the intermediate reaction pond, and 4 is premixing tower, and 5 is the catalyzed oxidation tower, and 6 is ozone generation system, and 7 is clean water basin, and 8 is the tail gas destructor, and 9 is sewage pump.
Embodiment
By reference to the accompanying drawings 1, the present invention is further elaborated by embodiment, below described embodiment be not determinate, can not limit protection scope of the present invention with this.
The oil removal by air bubbling water outlet promotes reactor through the aeration that sewage pump enters the modification BAF, sewage is mixed and dissolved oxygen fully, then enter uniformly packing layer and carry out microbial reaction, water outlet is back to Reactor inlet according to certain reflux ratio, the reactor water outlet enters " A/O " biochemical system, through its biodegradation process, water outlet enters the intermediate reaction pond, then enter premixing tower through the lift pump parallel connection from the top, introduce ozone with the time-division two-stage, sewage fully mixes with ozone in premixing tower, and the premixing tower water outlet relies on static pressure to enter the catalyzed oxidation tower from the bottom, pass through faster catalytic bed, under the effect of active element, rapidly be difficult to biodegradable organism in the oxidation sewage, reduce the CODcr of sewage, final processing water outlet enters clean water basin, reaches discharging standards or reuse requirement.Reclaim and react remaining ozone tail gas in the premixing tower to the intermediate reaction pond, the sewage that enters the catalytic ozonation system is done preaeration, improve the utilization ratio of ozone, and final emission is carried out disaggregating treatment, make it reach emission request.
Embodiment one:
By above-mentioned flow process certain refinery is carried out sewage disposal, reaction conditions is as follows: the modification BAF adopts the upper reaches succession running, and filler is selected through sulfuric acid modified volcanics, and hydraulic load is 2.0m
3/ m
2H, medial temperature is 30 ℃, and reflux ratio is 120%, and gas-water ratio is 4:1, and the automatic backwash cycle is 48h.Select modified aluminas as the carrier of catalyzer, load has the active metal oxide of 3.0% bronze medal and 2.0% manganese, and the single-stage premixing tower reaction times is 30min, and the single-stage ozone dosage is 30mg/L, and the single-stage catalyzed oxidation tower reaction times is 20min, the results are shown in Table 1:
Table 1 is processed effluent quality
Embodiment two:
By above-mentioned flow process certain refinery is carried out sewage disposal, reaction conditions is as follows: the modification BAF adopts the upper reaches succession running, and filler is selected through sulfuric acid modified flyash, and hydraulic load is 3.0m
3/ m
2H, medial temperature is 25 ℃, and reflux ratio is 100%, and gas-water ratio is 3:1, and the automatic backwash cycle is 72h.Select granulated active carbon as the carrier of catalyzer, load has the active metal oxide of 4.0% iron and 2.5% nickel, and the single-stage premixing tower reaction times is 45min, and the single-stage ozone dosage is 25mg/L, and the single-stage catalyzed oxidation tower reaction times is 15min, the results are shown in Table 2:
Table 2 is processed effluent quality
Embodiment three:
By above-mentioned flow process certain refinery is carried out sewage disposal, reaction conditions is as follows: the modification BAF adopts the upper reaches succession running, and filler is selected the zeolite through hydrochloric Acid Modification, and hydraulic load is 1.0m
3/ m
2H, medial temperature is 35 ℃, and reflux ratio is 150%, and gas-water ratio is 5:1, and the automatic backwash cycle is 60h.Select flyash as the carrier of catalyzer, load has the active metal oxide of 2.0% bronze medal, 3.0% iron and 5.0% manganese, and the single-stage premixing tower reaction times is 60min, and the single-stage ozone dosage is 35mg/L, the single-stage catalyzed oxidation tower reaction times is 20min, the results are shown in Table 3:
Table 3 is processed effluent quality
Claims (3)
1. combination treatment method that contains the naphthenic acid oil refining sewerage is characterized in that:
" A/O " front end in tradition " oil removing+A/O " technique increases the modification BAF as pretreatment technology, increases the catalytic ozonation system in " A/O " rear end as advanced treatment process, and former water CODcr is 2500～3200mg/L, and its process is as follows:
1. modification BAF is provided with aeration and promotes reactor, modified filler and backwashing system; Aeration promotes reactor and adopts the upflowing operation, and hydraulic load is controlled at 1.0～3.0m
3/ m
2H, temperature is controlled at 25～35 ℃, and control of reflux ratio is 100～150%, and gas-water ratio is controlled at 3:1～5:1, and the automatic backwash periodic Control is at 48～72h.Simultaneously filler is carried out modification, the properties-correcting agent of selecting is sulfuric acid or hydrochloric acid, and the filler of employing is a kind of of haydite, zeolite, volcanics, flyash or aluminum oxide; To strengthen its biological adsorption degradation capability, in the inner anaerobic environment that forms of filler, make the difficult degradation larger molecular organics be transformed into easy degradation of small molecular organism, improve the biodegradability of sewage, at the outside aerobic environment that forms of filler, realize the removal of most COD cr, the sewage B/C after processing through the modification BAF brings up to 0.3, A/O from 0.15; Art breading water outlet CODcr is reduced to 100～120mg/L from 160～200mg/L;
2. the catalytic ozonation system is provided with two-stage catalyst oxidation reactor, recycling tail gas and decomposer and ozone generation system; Catalyst oxidation reactor comprises premixing tower and catalyzed oxidation tower, select modified aluminas, flyash or granulated active carbon as support of the catalyst in the catalyzed oxidation tower, strengthen the organic effect of its adsorption and enrichment, and one or more reactive metal elements of the copper of load 2.0～5.0%, iron, nickel, manganese; Utilize operation scheme in parallel, sewage enters premixing tower and catalyzed oxidation tower successively, the single-stage premixing tower reaction times is 30～60min, the single-stage ozone dosage is 25～35mg/L, the single-stage catalyzed oxidation tower reaction times is 15～20min, under the effect of ozone and catalyzer, removal is difficult to biodegradable CODcr, and processing water outlet CODcr is 48～50mg/L; Recycling tail gas and decomposer are that the premixing tower emission is reclaimed, and utilize remaining ozone that former water is carried out preaeration, further improve ozone utilization rate, simultaneously final emission are carried out disaggregating treatment, reach emission request.
2. combination treatment method according to claim 1, it is characterized in that: the properties-correcting agent of selecting 1. is sulfuric acid or hydrochloric acid, the filler of employing is haydite, zeolite, flyash.
3. combination treatment method according to claim 1; it is characterized in that: premixing tower adopts the method for classification air feed 2.; improve ozone utilization rate; select modified aluminas, flyash or granulated active carbon as support of the catalyst in the catalyzed oxidation tower; strengthen the organic effect of its adsorption and enrichment; and one or more reactive metal elements of the copper of load 3.0～4.0%, iron, nickel, rapid organism in the oxidation sewage under its katalysis.
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Cited By (13)
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| CN103274514A (en) * | 2013-05-27 | 2013-09-04 | 中国海洋石油总公司 | Process method for performing advanced treatment on petrochemical wastewater through catalytic ozonation |
| 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 |
| CN103864265A (en) * | 2014-03-20 | 2014-06-18 | 中国海洋石油总公司 | Combined treatment method of phenol-containing coal gas wastewater |
| CN105254135A (en) * | 2015-11-17 | 2016-01-20 | 中蓝连海设计研究院 | Coal-to-liquid production wastewater treatment method |
| CN105502808A (en) * | 2015-12-07 | 2016-04-20 | 江苏博大环保股份有限公司 | System for treating oil field effluent by combining double A/O biochemistry with advanced oxidation |
| CN105692865A (en) * | 2014-11-27 | 2016-06-22 | 中国海洋石油总公司 | Method 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 |
| 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 |
| CN106256787A (en) * | 2015-06-18 | 2016-12-28 | 中国石油化工股份有限公司 | A kind of refinery sewage O3 catalytic oxidation processing method |
| CN106277414A (en) * | 2015-05-18 | 2017-01-04 | 中国石油化工股份有限公司 | A kind of oil-polluted water eliminates the method for foam |
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| CN103274514A (en) * | 2013-05-27 | 2013-09-04 | 中国海洋石油总公司 | Process method for performing advanced treatment on petrochemical wastewater through catalytic ozonation |
| 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 |
| CN103864265A (en) * | 2014-03-20 | 2014-06-18 | 中国海洋石油总公司 | Combined treatment method of phenol-containing coal gas wastewater |
| CN103864265B (en) * | 2014-03-20 | 2015-07-08 | 中国海洋石油总公司 | Combined treatment method of phenol-containing coal gas 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 |
| CN105692865B (en) * | 2014-11-27 | 2018-09-07 | 中国海洋石油集团有限公司 | A method of processing high-acid heavy crude oil processing waste water |
| CN105692865A (en) * | 2014-11-27 | 2016-06-22 | 中国海洋石油总公司 | Method 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 |
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| CN106277414B (en) * | 2015-05-18 | 2018-08-14 | 中国石油化工股份有限公司 | A kind of method that oily wastewater eliminates foam |
| CN106256787A (en) * | 2015-06-18 | 2016-12-28 | 中国石油化工股份有限公司 | A kind of refinery sewage O3 catalytic oxidation processing method |
| CN106256787B (en) * | 2015-06-18 | 2019-05-31 | 中国石油化工股份有限公司 | A kind of refinery sewage O3 catalytic oxidation processing method |
| CN105254135B (en) * | 2015-11-17 | 2017-12-12 | 中蓝连海设计研究院 | Coal liquifaction production wastewater treatment method |
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| CN105502808A (en) * | 2015-12-07 | 2016-04-20 | 江苏博大环保股份有限公司 | System for treating oil field effluent by combining double A/O biochemistry with advanced oxidation |
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Effective date of registration: 20180305 Address after: 100010 Beijing, Chaoyangmen, North Street, No. 25, No. Co-patentee after: CNOOC TIANJIN CHEMICAL RESEARCH & DESIGN INSTITUTE CO., LTD. Patentee after: China National Offshore Oil Corporation Co-patentee after: CNOOC Huizhou Petrochemical Co., Ltd. Address before: 100010 Beijing, Chaoyangmen, North Street, No. 25, No. Co-patentee before: CNOOC Tianjin Chemical Research & Design Institute Patentee before: China National Offshore Oil Corporation Co-patentee before: Huizhou Refinery Branch, CNOOC Oil & Petrochemicals Co., Ltd. |