2.中国轻工业水污染控制工程技术研究中心,西安 710021
1.School of Environmental Science and Engineering, Shaanxi University of Science and Technology, Xi′an 710021, China
2.China Light Industry Water Pollution Control Engineering Center, Xi′an 710021, China
油田压裂返排液中含有高浓度有机物、盐类物质和悬浮物等污染物,如不妥善处置直接外排会对环境产生严重危害。以配制的胍胶压裂返排液为研究对象,采用厌氧颗粒污泥对其进行处理,以COD、TOC去除率及甲烷产量为考察指标,研究了压裂返排液的厌氧生物降解特性。结果表明,压裂返排液经168 h厌氧处理后,COD和TOC由处理前的1 735.2 mg?L
,去除率分别为84.0%和86.4%,每克COD能产生688.2 mL的甲烷。采用红外光谱、紫外可见光谱以及三维荧光光谱对压裂返排液厌氧处理过程中有机物的组分及光谱特性进行了分析,发现厌氧生物处理可显著去除压裂返排液中芳香族化合物和类腐殖酸等物质。凝胶渗透色谱分析结果表明,压裂返排液中分子质量小于200 Da的有机物在厌氧处理过程中被优先去除。此外,将厌氧工艺出水进行好氧生物处理,COD去除率仅为22.2%,说明厌氧处理后的压裂返排液可生物降解性较差,需要采用高级氧化等方法进行深度处理。
Oilfield fracturing flowback fluid contains pollutants such as high concentrations of organic matter, salinity, and suspended solids. If oilfield fracturing flowback fluid is not disposed properly, direct discharge would cause severe harm to the environment. In this study, anaerobic granular sludge was employed to treat the prepared guar gum fracturing flowback fluid, and its anaerobic biodegradation characteristics was explored with COD and TOC removal rates and methane production as the indicators. The results demonstrated that after 168 h treatment, COD and TOC decreased from 1 735.2 mg?L
after anaerobic treatment with the corresponding removal rates of 84.0% and 86.4%, respectively. Meanwhile, the evolution of dissolved organic matter (DOM) in oilfield fracturing flowback fluid during the anaerobic biological treatment was investigated. The DOM was sampled at different treatment stages and characterized through Fourier transform infrared (FTIR) spectroscopy, fluorescence excitation-emission matrix (EEM), and UV-Vis. The results revealed that organic pollutants such as aromatic compounds and humic substances could be significantly removed by anaerobic biological treatment. Gel permeation chromatography (GPC) indicated that the organic matter with molecular weight (MW) less than 0.2 kDa was first removed during the anaerobic treatment. In addition, aerobic biological treatment was used to treat the effluent from anaerobic treatment unit and the COD removal efficiency was only 22.2%, indicating that the fracturing flowback after anaerobic treatment had low biodegradability and the advanced oxidation method would be needed for deep treatment.
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不同初始浓度下压裂返排液厌氧处理过程中累计甲烷产量的变化
Cumulative methane production changes during anaerobic treatment of fracturing wastewater at different initial concentrations
厌氧处理过程中COD、TOC的去除及甲烷产量
COD and TOC removal and methane production
FTIR analysis of anaerobic treated fracturing flowback fluid
UV-Vis spectra analysis of anaerobic treated fracturing flowback fluid
EEM fluorescence spectra analysis of anaerobic treated fracturing flowback fluid
Molecular weight changes during anaerobic treatment of fracturing flowback fluid
COD changes during anaerobic treatment of fracturing wastewater at different initial concentrations
[1] | ZHANG Z. Combined treatment of hydroxypropyl guar gum in oilfield fracturing wastewater by coagulation and the UV/H2O2/ferrioxalate complexes process[J]. Water Science and Technology, 2018, 77(3): 565-575. doi: 10.2166/wst.2017.552 |
[2] | ESTRADA J M, BHAMIDIMARRI R. A review of the issues and treatment options for wastewater from shale gas extraction by hydraulic fracturing[J]. Fuel, 2016, 182(15): 292-303. |
[3] | 李乐楠. 油田压裂返排液处理技术研究综述[J]. 石化技术, 2018, 25(1): 193. |
[4] | 黄靓, 李慧强, 杨平, 等. 页岩气压裂返排液的组成及处理技术[J]. 环境科学与技术, 2016, 39(S2): 172-177. |
[5] | 王志强, 王新艳, 郝华伟. 混凝预处理油田压裂返排液试验研究[J]. 广东化工, 2014, 41(8): 47-49. doi: 10.3969/j.issn.1007-1865.2014.08.024 |
[6] | 高玺莹, 王宝辉, 彭宏飞, 等. 标准Fenton试剂处理压裂余液的实验研究[J]. 水资源与水工程学报, 2010, 21(2): 139-141. |
[7] | 冀忠伦, 周立辉, 赵敏, 等. 臭氧催化氧化处理压裂废液的实验研究[J]. 环境工程, 2011, 29(S1): 117-119. |
[8] | RILEY S M, OLIVEIRA J, REGNERY J, et al. Hybrid membrane bio-systems for sustainable treatment of oil and gas produced water and fracturing flowback water[J]. Separation and Purification Technology, 2016, 171: 297-311. doi: 10.1016/j.seppur.2016.07.008 |
[9] | 陈翱翔. 好氧颗粒污泥SBR处理页岩气开采水力压裂返排废水的研究[D]. 重庆: 重庆大学, 2017. |
[10] | YANG J, LIANG H, LIU Y H, et al. Treatment of oilfield fracturing wastewater by a sequential combination of flocculation, Fenton oxidation and SBR process[J]. Environmental Technology, 2014, 35(21/22/23/24): 2878. |
[11] | 王海蒙. 预处理+生物法处理压裂废水的实验研究[D]. 西安: 西安建筑科技大学, 2013. |
[12] | KEKACS D, DROLLETTE B D, BROOKER M, et al. Aerobic biodegradation of organic compounds in hydraulic fracturing fluids[J]. Biodegradation, 2015, 26(4): 271-287. doi: 10.1007/s10532-015-9733-6 |
[13] | RITTMANN B E, MCCARTY P L. Environmental Biotechnology: Principles and Applications[M]. McGraw-Hill Education, 2001. |
[14] | SU D, CONG L, WANG J, et al. Treatment of oil-field produced water by combined process of anaerobic baffled reactor (ABR)-biological aerated filter (BAF): A pilot study[J]. International Journal of Environment and Pollution, 2009, 38(1/2): 69-80. doi: 10.1504/IJEP.2009.026644 |
[15] | LI G, GUO S, LI F. Treatment of oilfield produced water by anaerobic process coupled with micro-electrolysis[J]. Journal of Environmental Sciences, 2010, 22(12): 1875-1882. doi: 10.1016/S1001-0742(09)60333-8 |
[16] | ZHANG X, CHEN A, ZHANG D, et al. The treatment of flowback water in a sequencing batch reactor with aerobic granular sludge: Performance and microbial community structure[J]. Chemosphere, 2018, 211: 1065-1072. doi: 10.1016/j.chemosphere.2018.08.022 |
[17] | 钟显, 赵立志, 杨旭, 等. 生化处理压裂返排液的试验研究[J]. 石油与天然气化工, 2006(1): 70-72. doi: 10.3969/j.issn.1007-3426.2006.01.022 |
[18] | PENG S, HE X, PAN H. 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: 206-216. doi: 10.1016/j.jes.2018.04.006 |
[19] | WANG K, LI W, GONG X, et al. Spectral study of dissolved organic matter in biosolid during the composting process using inorganic bulking agent: UV-vis, GPC, FTIR and EEM[J]. International Biodeterioration & Biodegradation, 2013, 85: 617-623. |
[20] | 孙秀玥, 唐珠, 杨新萍. 活性污泥胞外多聚物提取方法的比较[J]. 环境科学, 2018, 39(7): 3306-3313. |
[21] | 樊月. 油田压裂废水的微波/化学氧化联合处理方法研究[D]. 西安: 西安石油大学, 2016. |
[22] | 周圆, 李怀波, 郑凯凯, 等. 新型组合工艺处理印染废水中试效能及微生物菌群分析[J]. 环境工程学报, 2020, 14(11): 126-137. |
[23] | FERRER I, THURMAN E M. Chemical constituents and analytical approaches for hydraulic fracturing waters[J]. Trends in Environmental Analytical Chemistry, 2015, 5: 18-25. doi: 10.1016/j.teac.2015.01.003 |
[24] | LESTER Y, YACOB T, MORRISSEY I, et al. Can we treat hydraulic fracturing flowback with a conventional biological process? The case of Guar Gum[J]. Environmental Science & Technology Letters, 2013, 1(1): 133-136. |
[25] | 单莉莉. CSTR-EGSB-SBR与电化学氧化联合处理纤维素乙醇废水的效能与机制[D]. 哈尔滨: 哈尔滨工业大学, 2017. |
[26] | 郭广军, 周利英, 何建平, 等. 瓜尔胶及其衍生物的过硫酸铵氧化降解研究[J]. 化学研究与应用, 2010, 22(12): 1546-1550. doi: 10.3969/j.issn.1004-1656.2010.12.013 |
[27] | 韩洪晶, 杨元林, 王宝辉. 绿色氧化剂K2FeO4对瓜尔胶的降解实验研究[J]. 硅酸盐通报, 2018, 37(6): 2057-2061. |
[28] | 李才华, 姜枫, 邹秋爽, 等. 臭氧-过硫酸盐工艺深度处理垃圾焚烧渗沥液[J]. 环境工程学报, 2017, 11(4): 2233-2240. doi: 10.12030/j.cjee.201602003 |
[29] | FU H. Treatment of oilfield fracturing wastewater[J]. Petroleum Science and Technology, 2017, 35(17): 1743-1749. doi: 10.1080/10916466.2017.1363777 |
[30] | WANG Y, WU X, YI J, et al. Pretreatment of printing and dyeing wastewater by Fe/C micro-electrolysis combined with H2O2 process[J]. Water Science and Technology, 2018, 2017(3): 707-717. doi: 10.2166/wst.2018.244 |
[31] | 刘璐. 典型煤化工废水中特征污染物的迁移转化及废水毒性削减研究[D]. 北京: 中国科学院大学, 2017. |
[32] | YAN H, NIAN Y, ZHOU Y, et al. A detailed dissolved organic matter characterization of starch processing wastewater treated by a sedimentation and biological hybrid system[J]. Microchemical Journal, 2017, 130: 295-300. doi: 10.1016/j.microc.2016.10.001 |
[33] | WESTERHOFF P, PINNEY M. Dissolved organic carbon transformations during laboratory-scale groundwater recharge using lagoon-treated wastewater[J]. Waste Management, 2000, 20(1): 75-83. doi: 10.1016/S0956-053X(99)00277-9 |
[34] | 李达. 水解酸化-UASB工艺处理煤制气废水的研究[D]. 哈尔滨: 哈尔滨工业大学, 2018. |
[35] | 卜琳. 垃圾渗滤液溶解性有机物在生化-物化处理中的降解规律[D]. 哈尔滨: 哈尔滨工业大学, 2011. |
[36] | CHEN W, WESTERHOFF P, LEENHEER J A, et al. Fluorescence excitation-emission matrix regional integration to quantify spectra for dissolved organic matter[J]. Environmental Science & Technology, 2003, 37(24): 5701-5710. |
[37] | 张一欣, 崔欣欣, 刘淑琴, 等. 三维电极耦合臭氧技术处理油田压裂返排液[J]. 中国环境科学, 2020, 40(5): 417-422. |
[38] | 李志华, 余科, 唐姚辉, 等. 污水厂活性污泥荧光物质的温度敏感性[J]. 环境工程学报, 2017, 11(6): 3399-3404. doi: 10.12030/j.cjee.201603128 |
[39] | 周明罗, 陈海焱, 谌书, 等. 移动床生物膜技术处理校园污水过程中DOM的光谱特征[J]. 光谱学与光谱分析, 2019, 39(7): 2160-2165. |
[40] | LI W, XU Z, WU Q, et al. Characterization of fluorescent-dissolved organic matter and identification of specific fluorophores in textile effluents[J]. Environmental Science and Pollution Research, 2015, 22(6): 4183-4189. doi: 10.1007/s11356-014-3201-4 |
[41] | 金鹏康, 贺栋, 刘岚, 等. 压裂废水粘度对二氧化锰臭氧催化氧化处理特性的影响[J]. 环境工程学报, 2013, 7(10): 3719-3724. |