铁刨花催化臭氧氧化深度处理制药废水
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摘要
研究采用铁刨花催化臭氧氧化深度处理抗生素制药废水。结果表明,在原水pH为7.28、体积2.1 L、臭氧气体进气体积流量为30 L/h、O_3的质量浓度为10.8 mg/L、催化剂使用量为20 g/L、总处理时长为300 min的条件下,铁刨花催化O_3氧化工艺出水COD、SCOD分别由135、128 mg/L减少至48、44 mg/L,DOC的质量浓度由37 mg/L减少至14 mg/L。除TN外,铁刨花催化臭氧氧化工艺的出水水质满足GB 21903-2008排放要求。出水B/C从0.015提升至0.17,可生化性提高。原水中有机物的主要组成部分为溶解性微生物产物(SMP),其中腐殖酸的含量最高,反应后蛋白质、多糖和腐殖酸的去除率分别为100%、48%和87%。在O_3/ZVI出水中未检出蛋白质、多糖及分子量较大的腐殖酸物质。
The advanced treatment of antibiotic pharmaceutical wastewater by iron shavings catalytic ozonation was studied. The results showed that, the COD and SCOD in effluent was reduced from 135 and 128 mg/L to 48 and 44 mg/L, respectively, and the mass concentration of DOC was reduced from37 mg/L to 14 mg/L by iron shavings catalytic ozonation process, when p H of raw water, the volume of test water, the ozone gas intake volume flow rate,the mass concentration of O_3, the catalyst dosage and the total reaction time was 7.28, 2.1 L, 30 L/h, 10.8 mg/L, 20 g/L, and 300 min respectively. In addition to TN, the effluent quality of the iron shavings catalytic ozonation process met the emission requirements of GB 21903-2008. The B/C increased from 0.015 to 0.17, which indicated the biodegradability of the effluent was increased. The main component of organic matter in raw water was SMP, in which the content of humic acid was the highest, and the removal rates of protein, polysaccharide and humic acid after reaction were 100%, 48% and 87%,respectively. No protein, polysaccharide or humic acid substance with a large molecular weight was detected in the O_3/ZVI effluent.
The advanced treatment of antibiotic pharmaceutical wastewater by iron shavings catalytic ozonation was studied. The results showed that, the COD and SCOD in effluent was reduced from 135 and 128 mg/L to 48 and 44 mg/L, respectively, and the mass concentration of DOC was reduced from37 mg/L to 14 mg/L by iron shavings catalytic ozonation process, when p H of raw water, the volume of test water, the ozone gas intake volume flow rate,the mass concentration of O_3, the catalyst dosage and the total reaction time was 7.28, 2.1 L, 30 L/h, 10.8 mg/L, 20 g/L, and 300 min respectively. In addition to TN, the effluent quality of the iron shavings catalytic ozonation process met the emission requirements of GB 21903-2008. The B/C increased from 0.015 to 0.17, which indicated the biodegradability of the effluent was increased. The main component of organic matter in raw water was SMP, in which the content of humic acid was the highest, and the removal rates of protein, polysaccharide and humic acid after reaction were 100%, 48% and 87%,respectively. No protein, polysaccharide or humic acid substance with a large molecular weight was detected in the O_3/ZVI effluent.
引文
[1]发酵类制药工业水污染物排放标准:GB 21903-2008[S].
[2]国家环保总局办公厅.关于征求《制药工业水污染物排放标准发酵类》(征求意见稿)等两项国家环境保护标准意见的函[EB/OL].(2007-10-19)[2018-07-23].http://www.zhb.gov.cn/gkml/zj/bgth/200910/t20091022_174393.htm.
[3]宋鑫,任立人,吴丹,等.制药废水深度处理技术的研究现状及进展[J].广州化工,2012,40(12):29-31.
[4]涂勇,张耀辉,徐军,等.臭氧对化工园区废水厂二级出水的选择性氧化[J].环境工程学报,2015,9(11):5295-5300.
[5] CHEN W, LI X, PAN Z, et al. Effective mineralization of Diclofenac by catalytic ozonation using Fe-MCM-41 catalyst[J].Chemical Engineering Journal,2016,304:594-601.
[6] YUAN M H, CHANG C Y, SHIE J L, et al. Destruction of naphthalene via ozone-catalytic oxidation process over Pt/Al2O3catalyst[J].Journal of Hazardous Materials,2010,175(1/3):809-815.
[7] ZHANG J, WU Y, LIU L, et al. Rapid removal of p-chloronitrobenzene from aqueous solution by a combination of ozone with zero-valent zinc[J].Separation&Purification Technology,2015,151:318-323.
[8] WANG K, LIN C, WEI M, et al. Effects of dissolved oxygen on dye removal by zero-valent iron[J].Journal of Hazardous Materials,2010,182(1/3):886-895.
[9]吴瑾.铁刨花催化臭氧氧化印染废水生化出水中的有机物及其途径研究[D].上海:复旦大学,2016.
[10] SHON H K, VIGNESWARAN S, SNYDER S A. Effluent organic matter(EfOM)in wastewater:constituents, effects, and treatment[J].Critical reviews in environmental science and technology,2006,36(4):327-374.
[11]国家环境保护总局《水和废水监测分析方法》编委会.水和废水监测分析方法[M].4版.北京:中国环境科学出版社,2002.
[12] FR覫LUND B, PALMGREN R, KEDING K, et al. Extraction of extracellular polymers from activated sludge using a cation exchange resin[J].Water Research 1996,30,(8):1749-1758.
[13] Water quality-Determination of the inhibitory effect of water samples on the light emission of Vibrio fischeri(Luminescent bacteria test)-Part 3:Method using freeze-dried bacteria:ISO 11348-3[S].
[14] YAN M, KORSHIN G, WANG D, et al. Characterization of dissolved organic matter using high-performance liquid chromatography(HPLC)-size exclusion chromatography(SEC)with a multiple wavelength absorbance detector[J].Chemosphere,2012,87(8):879-885.
[15]傅平青,吴丰昌,刘丛强.洱海沉积物间隙水中溶解有机质的地球化学特性[J].水科学进展,2005,16(3):338-344.
[16] QUIROZ C A, BARRERA-D魱AZ C, ROA-MORALES G, et al.Wastewater ozonation catalyzed by iron[J].Industrial&Engineering Chemistry Research,2011,50(5):2488-2494.
[17] L覫GAGER T, HOLCMAN J, SEHESTED K, et al. Oxidation of ferrous ions by ozone in acidic solutions[J].Inorganic Chemistry,1992,31(17):3523-3529.
[18] BARKER D J, STUCKEY D C. A review of soluble microbial products(SMP)in wastewater treatment systems[J].Water Research,1999,33(14):3063-3082.
[19] AQUINO S F, STUCKEY D C. Soluble microbial products formation in anaerobic chemostats in the presence of toxic compounds[J].Water Research,2004,38(2):255-266.
[20] QIAN F, SUN X, LIU Y. Removal characteristics of organics in biotreated textile wastewater reclamation by a stepwise coagulation and intermediate GAC/O3oxidation process[J].Chemical Engineering Journal,2013,214(4):112-118.
[21]储旭.磁吸附强化混凝深度处理制药废水生化尾水研究[D].南京:南京大学,2016.
[22] WU J, MA L, CHEN Y, et al. Catalytic ozonation of organic pollutants from bio-treated dyeing and finishing wastewater using recycled waste iron shavings as a catalyst:Removal and pathways[J].Water Research,2016,92:140-148.
[2]国家环保总局办公厅.关于征求《制药工业水污染物排放标准发酵类》(征求意见稿)等两项国家环境保护标准意见的函[EB/OL].(2007-10-19)[2018-07-23].http://www.zhb.gov.cn/gkml/zj/bgth/200910/t20091022_174393.htm.
[3]宋鑫,任立人,吴丹,等.制药废水深度处理技术的研究现状及进展[J].广州化工,2012,40(12):29-31.
[4]涂勇,张耀辉,徐军,等.臭氧对化工园区废水厂二级出水的选择性氧化[J].环境工程学报,2015,9(11):5295-5300.
[5] CHEN W, LI X, PAN Z, et al. Effective mineralization of Diclofenac by catalytic ozonation using Fe-MCM-41 catalyst[J].Chemical Engineering Journal,2016,304:594-601.
[6] YUAN M H, CHANG C Y, SHIE J L, et al. Destruction of naphthalene via ozone-catalytic oxidation process over Pt/Al2O3catalyst[J].Journal of Hazardous Materials,2010,175(1/3):809-815.
[7] ZHANG J, WU Y, LIU L, et al. Rapid removal of p-chloronitrobenzene from aqueous solution by a combination of ozone with zero-valent zinc[J].Separation&Purification Technology,2015,151:318-323.
[8] WANG K, LIN C, WEI M, et al. Effects of dissolved oxygen on dye removal by zero-valent iron[J].Journal of Hazardous Materials,2010,182(1/3):886-895.
[9]吴瑾.铁刨花催化臭氧氧化印染废水生化出水中的有机物及其途径研究[D].上海:复旦大学,2016.
[10] SHON H K, VIGNESWARAN S, SNYDER S A. Effluent organic matter(EfOM)in wastewater:constituents, effects, and treatment[J].Critical reviews in environmental science and technology,2006,36(4):327-374.
[11]国家环境保护总局《水和废水监测分析方法》编委会.水和废水监测分析方法[M].4版.北京:中国环境科学出版社,2002.
[12] FR覫LUND B, PALMGREN R, KEDING K, et al. Extraction of extracellular polymers from activated sludge using a cation exchange resin[J].Water Research 1996,30,(8):1749-1758.
[13] Water quality-Determination of the inhibitory effect of water samples on the light emission of Vibrio fischeri(Luminescent bacteria test)-Part 3:Method using freeze-dried bacteria:ISO 11348-3[S].
[14] YAN M, KORSHIN G, WANG D, et al. Characterization of dissolved organic matter using high-performance liquid chromatography(HPLC)-size exclusion chromatography(SEC)with a multiple wavelength absorbance detector[J].Chemosphere,2012,87(8):879-885.
[15]傅平青,吴丰昌,刘丛强.洱海沉积物间隙水中溶解有机质的地球化学特性[J].水科学进展,2005,16(3):338-344.
[16] QUIROZ C A, BARRERA-D魱AZ C, ROA-MORALES G, et al.Wastewater ozonation catalyzed by iron[J].Industrial&Engineering Chemistry Research,2011,50(5):2488-2494.
[17] L覫GAGER T, HOLCMAN J, SEHESTED K, et al. Oxidation of ferrous ions by ozone in acidic solutions[J].Inorganic Chemistry,1992,31(17):3523-3529.
[18] BARKER D J, STUCKEY D C. A review of soluble microbial products(SMP)in wastewater treatment systems[J].Water Research,1999,33(14):3063-3082.
[19] AQUINO S F, STUCKEY D C. Soluble microbial products formation in anaerobic chemostats in the presence of toxic compounds[J].Water Research,2004,38(2):255-266.
[20] QIAN F, SUN X, LIU Y. Removal characteristics of organics in biotreated textile wastewater reclamation by a stepwise coagulation and intermediate GAC/O3oxidation process[J].Chemical Engineering Journal,2013,214(4):112-118.
[21]储旭.磁吸附强化混凝深度处理制药废水生化尾水研究[D].南京:南京大学,2016.
[22] WU J, MA L, CHEN Y, et al. Catalytic ozonation of organic pollutants from bio-treated dyeing and finishing wastewater using recycled waste iron shavings as a catalyst:Removal and pathways[J].Water Research,2016,92:140-148.
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