Study on the removal of benzenes pollutants from coal chemical wastewater based on ozonation technology
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摘要: 苯、甲苯、乙苯、二甲苯(BTEX)是煤化工废水中的典型有机污染物，通常情况下较难被生物降解，实际生产过程中通常使用化学手段对其进行去除。本研究以臭氧氧化过程中产生的强氧化性自由基为基础，采用臭氧氧化技术对模拟废水中的BTEX进行去除实验。探究了pH值、温度、臭氧投加量以及臭氧投加模式对BTEX降解效果的影响；使用叔丁醇作为羟基自由基抑制剂、自由基歧化酶作为超氧自由基抑制剂，探究臭氧降解BTEX时的反应机理。实验结果表明：当pH值为8、反应温度为30 ℃、臭氧投加量为3.5 g/L、臭氧投加模式为逆流投加时，BTEX的降解效果最佳；羟基自由基和超氧自由基的存在是臭氧有效去除水中BTEX的根本原因。Abstract: Benzene, toluene, ethylbenzene and xylene(BTEX)are typical organic pollutants in coal chemical wastewater, which were difficult to be biodegraded under normal conditions, and were often removed by chemical means in the actual production process. This study based on the strong oxidizing free radicals generated in the process of ozone oxidation, used ozone oxidation technology to remove BTEX in simulated wastewater. The effects of pH value, temperature, ozone dosage and ozone dosing mode on the degradation of BTEX were investigated. The reaction mechanism of degradation by ozone was explored by using tertiary butanol as hydroxyl radical inhibitor and free radical dismutase as superoxide radical inhibitor. The results showed that the degradation effect of BTEX was the best when pH was 8, reaction temperature was 30 ℃, ozone dosage was 3.5 g/L and ozone dosage mode was countercurrent. The existence of superoxide radicals and hydroxyl radicals were the fundamental reason for the effective removal of BTEX from water by ozonization.
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Key words:
- ozonation /
- benzenes /
- radicals /
- inhibitor /
- reaction mechanism
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图 1 臭氧氧化反应系统
1—氧气罐；2—臭氧发生器；3—废水存储装置；4—蠕动泵；5—臭氧氧化反应装置；6—取样点；7—KI尾气回收装置
Figure 1. Ozonation reaction system
图 5 臭氧投加模式对臭氧氧化去除BTEX的影响
Figure 5. Effect of different ozone dosing methods on removal of BTEX by ozonation
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[1] Li X F, Chen W Y, Ma L M, et al. Industrial wastewater advanced treatment via catalytic ozonation with an Fe-based catalyst[J]. Chemosphere, 2018, 195: 336-343. doi: 10.1016/j.chemosphere.2017.12.080 [2] 林冲. 焦化废水外排水中残余组分的环境行为及臭氧氧化过程分析[D]. 广州: 华南理工大学, 2014. [3] 王兵, 周鋆, 任宏洋, 等. MgO催化臭氧氧化降解苯酚机理研究[J]. 环境科学学报, 2016, 36(11): 4009-4016. https://www.cnki.com.cn/Article/CJFDTOTAL-HJXX201611016.htmWang Bing, Zhou Yun, Ren Hongyang, et al. Study on mechanism of MgO catalytic ozonation process for phenol degradation[J]. Acta Scientiae Circumstantiae, 2016, 36(11): 4009-4016. https://www.cnki.com.cn/Article/CJFDTOTAL-HJXX201611016.htm [4] Peng S W, He X W, Pan H W.Spectroscopic study on transformations of dissolved organic matter in coal-to-liquids wastewater under integrated chemical oxidation and biological treatment process[J]. Journal of Environmental Sciences, 2018, 70(8): 206-216. http://www.cnki.com.cn/Article/CJFDTotal-HJKB201808020.htm [5] Peng S W, Zhang W J, He J, et al. Enhancement of Fenton oxidation for removing organic matter from hypersaline solution by accelerating ferric system with hydroxylamine hydrochloride and benzoquinone[J]. Journal of Environmental Sciences, 2016, 41(3): 16-23. http://www.cnki.com.cn/Article/CJFDTotal-HJKB201603003.htm [6] 李翔君. 高级氧化技术处理水中难降解苯系物的研究[D]. 济南: 山东建筑大学, 2018. [7] 张秋勉, 侯宝芹, 倪杭娟. 活性炭对钱塘江萧山江段原水中苯酚和苯系物去除效果[J]. 净水技术, 2015, 34(4): 83-86, 116. https://www.cnki.com.cn/Article/CJFDTOTAL-ZSJS201504017.htmZhang Qiumian, Hou Baoqin, Ni Hangjuan, et al. Efficiency of phenol and benzene series removal in raw water from Xiaoshan section of Qiantangjiang river with activated carbon process[J]. Water Purification Technology, 2015, 34(4): 83-86, 116. https://www.cnki.com.cn/Article/CJFDTOTAL-ZSJS201504017.htm [8] 刁春鹏. 焦化废水处理过程苯系物、苯胺类、重金属污染物的存在及去除特性分析[D]. 广州: 华南理工大学, 2012. [9] 郑瑾, 陈宏坤, 杜显元, 等. 微生物降解苯系污染物的机理及研究进展[J]. 中国资源综合利用, 2020, 38(1): 118-120. https://www.cnki.com.cn/Article/CJFDTOTAL-ZWZS202001035.htmZheng Jin, Chen Hongkun, Du Xianyuan, et al. The mechanism and research progress of microbial degradation of benzene series pollutants[J]. China Resources Comprehensive Utilization, 2020, 38(1): 118-120. https://www.cnki.com.cn/Article/CJFDTOTAL-ZWZS202001035.htm [10] 张方, 王晓丽, 吴功德, 等. 碘改性的含铜复合氧化物催化氧化苯系物[J]. 分子催化, 2019, 33(4): 333-338. https://www.cnki.com.cn/Article/CJFDTOTAL-FZCH201904006.htmZhang Fang, Wang Xiaoli, Wu Gongde, et al. Catalytic oxidation of benzene homologues by lodine modified copper-containing mixed oxides[J]. Journal of Molecular Catalysis, 2019, 33(4): 333-338. https://www.cnki.com.cn/Article/CJFDTOTAL-FZCH201904006.htm [11] 王艳丽, 李利荣, 杨华. 固相微萃取-气相色谱法测定水中痕量苯系物[J]. 理化检验: 化学分册, 2011, 47(10): 1195-1197. https://www.cnki.com.cn/Article/CJFDTOTAL-LHJH201110023.htmWang Yanli, Li Lirong, Yang Hua. GC determination of benzene homologues in water samples with solid phase micro-extraction[J]. PTCA Part B: Chem. Anal, 2011, 47(10): 1195-1197. https://www.cnki.com.cn/Article/CJFDTOTAL-LHJH201110023.htm [12] 田雷. 复合介质PRB去除地下水中氯代烃和苯系物混合污染研究[D]. 北京: 中国地质大学(北京), 2014. [13] 王俊芳, 师彬, 陈建峰, 等. O3/H2O2高级氧化技术在处理难降解有机废水中的应用进展[J]. 化工进展, 2010(6): 1138-1142.Wang Junfang, Shi Bin, Chen Jianfeng, et al. Application of advanved oxidation process with O3/H2O2 for refractory organic wastewater treatment[J]. Chemical Industry and Engineering Process, 2010(6): 1138-1142. [14] 钱建华, 陈明明, 李君华, 等. CuO/Al2O3催化臭氧氧化降解酸性红B的研究[J]. 工业水处理, 2019, 39(9): 67-77, 79. https://www.cnki.com.cn/Article/CJFDTOTAL-GYSC201909017.htmQian Jianhua, Chen Mingming, Li Junhua, et al. Study on degradation of acid red B by CuO/Al2O3 catalytic ozone oxidation[J]. Industrial Water Treatment, 2019, 39(9): 67-77, 79. https://www.cnki.com.cn/Article/CJFDTOTAL-GYSC201909017.htm [15] 彭澍晗, 吴德礼. 催化臭氧氧化深度处理工业废水的研究及应用[J]. 工业水处理, 2019, 39(1): 1-7. https://www.cnki.com.cn/Article/CJFDTOTAL-GYSC201901002.htmPeng Shuhan, Wu Deli. Research on catalytic ozonation and its application to the advanced treatment of industrial wastewater[J]. Industrial Water Treatment, 2019, 39(1): 1-7. https://www.cnki.com.cn/Article/CJFDTOTAL-GYSC201901002.htm [16] 徐红岩, 王俊, 张原洁, 等. 多相催化臭氧氧化技术处理染料废水生化出水[J]. 环境工程学报, 2017, 11(5): 2819-2827. https://www.cnki.com.cn/Article/CJFDTOTAL-HJJZ201705030.htmXu Hongyan, Wang Jun, Zhang Yuanjie, et al. Treatment of biologically-treated effluent of dye wastewater by heterogeneous catalytic ozonation technology[J]. Chinese Journal of Environmental Engineering, 2017, 11(5): 2819-2827. https://www.cnki.com.cn/Article/CJFDTOTAL-HJJZ201705030.htm [17] Yao W K, Rehman S W U, Wang H J, et al. Pilot-scale evaluation of micropollutant abatements by conventional ozonation, UV/O3, and an electro-peroxone process[J]. Water Research, 2018, 138: 106-117. doi: 10.1016/j.watres.2018.03.044 [18] Xu Y, Wu Y, Zhang W, et al. Performance of artificial sweetener sucralose mineralization via UV/O3 process: Kinetics, toxicity and intermediates[J]. Chemical Engineering Journal, 2018, 353: 626-634. doi: 10.1016/j.cej.2018.07.090 [19] 彭思伟, 戴子瑜, 何绪文. 煤制油废水中溶解性有机物(DOM)在生物处理过程中的变化特性[J]. 矿业科学学报, 2018, 3(6): 587-595. http://www.cnki.com.cn/Article/CJFDTotal-KYKX201806010.htmPeng Siwei, Dai Ziyu, He Xuwen. Variation characteristics of dissolved organic matter(DOM)in coal-to-liquids wastewater during biological treatment process[J]. Journal of Mining Science and Technology, 2018, 3(6): 587-595. http://www.cnki.com.cn/Article/CJFDTotal-KYKX201806010.htm [20] 张怡鸣, 张玉秀, 祖德彪, 等. 焦化废水处理技术及其污泥细菌菌群结构功能研究进展[J]. 矿业科学学报, 2020, 5(2): 232-241. doi: 10.19606/j.cnki.jmst.2020.02.012Zhang Yiming, Zhang Yuxiu, Zu Debiao, et al. Coking wastewater treatment technology and its bacterial community structure and function in sludge[J]. Journal of Mining Science and Technology, 2020, 5(2): 232-241. doi: 10.19606/j.cnki.jmst.2020.02.012 -
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