A/O-混凝-BDD组合工艺处理垃圾渗滤液的研究:Ⅱ. 有机物去除机理

doi:10.13209/j.0479-8023.2017.045

摘要/Abstract

摘要：

在A/O-混凝-BDD组合工艺系统最优运行条件下, 采用紫外扫描、分子荧光、GC-MS、红外光谱等多种方法从不同角度深入分析A/O-混凝-BDD组合工艺的各段工艺进出水有机物组成和结构特性的变化, 剖析不同工艺去除有机物的机理。结果表明, A/O工艺对脂肪族有机物支链和类色氨酸容易去除, 对类富里酸有较好的去除, 而对类腐殖酸较难去除; 水力停留时间(HRT)从4.0 d增加至10.7 d时, 增强了系统对类色氨酸和类富里酸的去除; 回流比从3.0增加至3.5时, 增强了系统对类色氨酸的去除, 但对类富里酸的去除效果变差。混凝过程主要去除脂肪族和蛋白质类有机物以及类腐殖酸, 对类富里酸去除效果较差, 出水中仍残留部分芳香性物质。BDD对渗滤液中残留的各种难降解有机物均能够有效降解。

关键词: 垃圾渗滤液, 组合工艺, 有机物, 光谱, GC-MS

Abstract:

Landfill leachate was treated by A/O-coagulation-BDD combined processes, and the organic matters during treatment processes were characterized by UV spectra, fluorescence excitation-emission matrix, GC-MS, and Fourier transform infrared spectra under optimum operating conditions. Aliphatic organic matters, tryptophan-like matters, and some fulvic acid-like organic matters can be easily removed by A/O treatment while humic acid-like organic matters can not. The removal efficiencies of ryptophan-like matters and fulvic acid-like organic matters were better as HRT increasing from 4.0 d to 10.7 d. As sludge recirculation ratio increasing from 3.0 to 3.5, the removal efficiency of ryptophan-like matters was better while the removal efficiency of fulvic acid-like organic matters was worse. Coagulation mainly removed aliphatic organic matters, proteins, and some humic acid-like organic matters, but can’t easily remove fulvic acid-like organic matters, and there were still some aroma organic matter in the effluent. BDD treatment can effectively remove kinds of refractory organic matters.

Key words: landfill leachate, group technology, organic matter, spectrum, GC-MS

单迎春, 王琮禾, 魏婧淼, 孙海美, 孙卫玲. A/O-混凝-BDD组合工艺处理垃圾渗滤液的研究:Ⅱ. 有机物去除机理[J]. 北京大学学报自然科学版, 2017, 53(3): 507-517.

Yingchun SHAN, Conghe WANG, Jingmiao WEI, Haimei SUN, Weiling SUN. Treatment of Landfill Leachate Using A/O-Coagulation-BDD:Ⅱ. Removal Mechanism of the Organic Matters[J]. Acta Scientiarum Naturalium Universitatis Pekinensis, 2017, 53(3): 507-517.

图/表 11

图1 各工艺出水SUVA254值

Fig. 1 SUVA254 value of landfill leachate out of each treatment

图2 不同HRT(a)和回流比(b)下各工艺出水SUVA254值

Fig. 2 SUVA254 value of landfill leachate out of each treatment at different HRT (a) and sludge recirculation ratios (b)

图3 组合工艺各阶段出水EEM分析

Fig. 3 EEM analysis of landfill leachate out of each treatment

图4 组合工艺各阶段出水F/DOC值

Fig. 4 F/DOC value of landfill leachate out of each treatment

图5 不同HRT下各阶段出水标准化峰强度

Fig. 5 F/DOC value of effluent from each treatment at different HRT

图6 不同回流比下各阶段出水的标准化峰强度

Fig. 6 Standardized peak strength of effluents from each treatment under different sludge recirculation ratios

图7 工艺各阶段出水IA/IC值

Fig. 7 IA/IC value of effluent from each treatment

图8 不同HRT和回流比下各阶段出水IA/IC值（R: 进水; A: 缺氧出水; O: 好氧出水）

Fig. 8 IA/IC value of leachate effluent from each treatment at different HRT and sludge recirculation ratios

图9 组合工艺各阶段出水有机污染物的红外分析图

Fig. 9 FTIR spectra of landfill leachate effluents after each treatment

表1 组合工艺进出水中的有机物定性分析

Table 1 Qualitative analysis of organic compounds from effluent of each treatment

序号	出峰时间/min	响应值	有机物	匹配度/%
1	8.103	110678	丁酸	64
2	14.632	178999	戊酸	83
3	22.486	385157	己酸	72
4	25.269	151829	庚酸	64
5	27.638	123858	环己烷羧酸	78
6	30.114	92762	苯甲酸	83
7	34.866	117828	苯乙酸	83
8	40.341	26969	苯丙酸	94
9	65.198	49858	嘧啶	97
10	73.288	80685	十六烷酸	98
11	81.907	37335	4,4′-{1-异亚丙基苯酚}聚合物	98
12	91.282	134829	苯氧基-2,2′-亚甲基[6-(1,1-二甲基乙基)]-4-甲基	97
13	96.257	29826	1,2-苯二羧酸单脂	91

图10 组合工艺各阶段出水有机污染物的GC-MS分析

Fig. 10 GC-MS analysis of leachate effluent from each treatment

参考文献 43

[1]	关莉. 一体式超滤膜生物反应器对城市生活垃圾渗滤液有机物的去除[D]. 长春: 吉林大学, 2003: 8-9
[2]	杜晓文. 水解酸化—缺氧—膜生物反应器复合工艺处理垃圾渗滤液的试验研究[D]. 北京: 华北电力大学能源动力与机工程学院, 2013: 2-4
[3]	李莉. 生活垃圾填埋场渗滤液物化和生化预处理及组合处理工艺研究[D]. 重庆: 重庆大学城市建设与环境工程学院, 2010: 1-6
[4]	Weishaar J L, Aiken G R, Bergamaschi B A, et al.Evaluation of specific ultraviolet absorbance as an indicator of the chemical composition and reactivity of dissolved organic carbon. Environmental Science & Technology, 2003, 37(20): 4702-4708
[5]	Boyer T H, Singer P C.Stoichiometry of removal of natural organic matter by ion exchange. Environmen-tal Science & Technology, 2007, 42(2): 608-613
[6]	Patel-Sorrentino N, Mounier S, Benaim J Y.Excitation-emission fluorescence matrix to study pH influence on organic matter fluorescence in the Amazon basin rivers. Water Research, 2002, 36(10): 2571-2581
[7]	Chen W, Westerhoff P, Leenheer J A, et al.Fluorescence excitation-emission matrix regional integration to quantify spectra for dissolved organic matter. Environmental Science & Technology, 2003, 37(24): 5701-5710
[8]	吉芳英, 谢志刚, 黄鹤, 等. 垃圾渗滤液处理工艺中有机污染物的三维荧光光谱. 环境工程学报, 2009, 3(10): 1783-1788
[9]	杨志, 汪蘋, 张月琴, 等. GC-MS 法对垃圾渗滤液生物处理前后微量有机物的研究. 环境污染与防治, 2005, 27(3): 218-221
[10]	叶秀雅, 周少奇, 郑可. 运用GC-MS 技术分析垃圾渗滤液有机污染物的去除特性. 化工进展, 2011, 30(6): 1374-1378
[11]	Sierra M M D, Giovanela M, Parlanti E, et al. Fluorescence fingerprint of fulvic and humic acids from varied origins as viewed by single-scan and excitation/emission matrix techniques. Chemosphere, 2005, 58(6): 715-733
[12]	Guo Xujing, Yuan Donghai, Li Qiang, et al.Spec-troscopic techniques for quantitative characterization of Cu (II) and Hg (II) complexation by dissolved organic matter from lake sediment in arid and semi-arid region. Ecotoxicology and Environmental Safety, 2012, 85: 144-150
[13]	赵庆良, 卜琳, 夏小青. 垃圾渗滤液厌氧降解中溶解性有机物的光谱特性. 天津大学学报(自然科学版), 2012, 45(1): 13-19
[14]	何小松, 于静, 席北斗, 等. 填埋垃圾渗滤液中水溶性有机物去除规律研究. 光谱学与光谱分析, 2012, 32(9): 2528-2533
[15]	石岩, 王启山, 岳琳. 三维电极-电 Fenton 法去除垃圾渗滤液中有机物. 北京化工大学学报(自然科学版), 2008, 35(6): 84-89
[16]	卜琳, 赵庆良. SBR处理垃圾渗滤液中溶解性有机物降解特性. 水工业市场, 2011(8): 29-33
[17]	武文会, 刘智萍, 方芳, 等. SBR-混凝处理渗滤液过程中有机物的变化特征. 环境工程学报, 2015, 9(3): 1124-1130
[18]	单迎春, 王庆玮, 潘伟一, 等. A/O-混凝-BDD组合工艺处理垃圾渗滤液研究: I. 参数优化. 北京大学学报(自然科学版), 2017, 53(3): 491-500
[19]	Saadi I, Borisover M, Armon R, et al.Monitoring of effluent DOM biodegradation using fluorescence, UV and DOC measurements. Chemosphere, 2006, 63(3): 530-539
[20]	Kalbitz K, Schmerwitz J, Schwesig D, et al.Biodegradation of soil-derived dissolved organic matter as related to its properties. Geoderma, 2003, 113(3): 273-291
[21]	Marschner B, Kalbitz K.Controls of bioavailability and biodegradability of dissolved organic matter in soils. Geoderma, 2003, 113(3): 211-235
[22]	Chin Y P, Aiken G,O’Loughlin E. Molecular weight, polydispersity, and spectroscopic properties of aquatic humic substances. Environmental Science & Techno-logy, 1994, 28(11): 1853-1858
[23]	Edzwald J K.Coagulation in drinking water treat-ment: particles, organics and coagulants. Water Science and Technology, 1993, 27(11): 21-35
[24]	Westerhoff P, Pinney M.Dissolved organic carbon transformations during laboratory-scale groundwater recharge using lagoon-treated wastewater. Waste Management, 2000, 20(1): 75-83
[25]	Archer A D, Singer P C.An evaluation of the relationship between SUVA and NOM coagulation using the ICR database. Journal — American Water Works Association, 2006, 98(7): 110-123
[26]	Coble P G.Characterization of marine and terrestrial DOM in seawater using excitation-emission matrix spectroscopy. Marine Chemistry, 1996, 51(4): 325-346
[27]	Shao Zhenghao, He Pinjing, Zhang Dongqing, et al.Characterization of water-extractable organic matter during the biostabilization of municipal solid waste. Journal of Hazardous Materials, 2009, 164(2): 1191-1197
[28]	Provenzano M R, D’Orazio V, Jerzykiewicz M, et al. Fluorescence behaviour of Zn and Ni complexes of humic acids from different sources. Chemosphere, 2004, 55(6): 885-892
[29]	Sun Weiling, Ni Jinren, Xu Nan, et al,Fluorescence of sediment humic substance and its effect on the sorption of selected endocrine disruptors. Chemos-phere, 2007, 66(4): 700-707
[30]	He Xiaosong, Xi Beidou, Wei Zimin, et al.Physicochemical and spectroscopic characteristics of dissolved organic matter extracted from municipal solid waste (MSW) and their influence on the landfill biological stability. Bioresource Technology, 2011, 102(3): 2322-2327
[31]	Baker A, Curry M.Fluorescence of leachates from three contrasting landfills. Water Research, 2004, 38(10): 2605-2613
[32]	Kang K H, Shin H S, Park H.Characterization of humic substances present in landfill leachates with different landfill ages and its implications. Water Research, 2002, 36(16): 4023-4032
[33]	Park S, Choi K S, Joe K S, et al.Variations of landfill leachate’s properties in conjunction with the treatment process. Environmental Technology, 2001, 22(6): 639-645
[34]	Bu Lin, Wang Kun, Zhao Qingliang, et al.Characterization of dissolved organic matter during landfill leachate treatment by sequencing batch reactor, aeration corrosive cell-Fenton, and granular activated carbon in series. Journal of Hazardous Materials, 2010, 179(1): 1096-1105
[35]	d’Abzac P, Bordas F, van Hullebusch E, et al. Effects of extraction procedures on metal binding properties of extracellular polymeric substances (EPS) from anaerobic granular sludges. Colloids and Surfaces B: Biointerfaces, 2010, 80(2): 161-168
[36]	Leenheer J A, Rostad C E, Gates P M, et al.Molecular resolution and fragmentation of fulvic acid by electrospray ionization/multistage tandem mass spectrometry. Analytical Chemistry, 2001, 73(7): 1461-1471
[37]	Marley N A, Gaffney J S, Orlandini K A.Charac-terization of aquatic humic and fulvic materials by cylindrical internal reflectance infrared spectroscopy // Humic and fulvic acids: isolation, Structure, and Environmental Role. Washington DC, 1996: 96-107
[38]	贾陈忠, 刘松, 张彩香, 等. 光催化氧化降解垃圾渗滤液中溶解性有机物. 环境工程学报, 2013, 7(2): 451-456
[39]	Simjouw J P, Minor E C, Mopper K.Isolation and characterization of estuarine dissolved organic matter: comparison of ultrafiltration and C18 solid-phase extraction techniques. Marine Chemistry, 2005, 96(3): 219-235
[40]	Droussi Z, D’Orazio V, Hafidi M, et al. Elemental and spectroscopic characterization of humic-acid-like compounds during composting of olive mill by-products. Journal of Hazardous Materials, 2009, 163(2): 1289-1297
[41]	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: 109-111
[42]	Cabeza A, Urtiaga A M, Ortiz I.Electrochemical treatment of landfill leachates using a boron-doped diamond anode. Industrial & Engineering Chemistry Research, 2007, 46(5): 1439-1446
[43]	Raghu S, Lee C W, Chellammal S, et al.Evaluation of electrochemical oxidation techniques for degradation of dye effluents — a comparative approach. Journal of Hazardous Materials, 2009, 171(1): 748-754