低温水热耦合亚铁离子活化过硫酸盐提高剩余污泥的脱水性能

doi:10.16085/j.issn.1000-6613.2022-1837

摘要/Abstract

摘要：

含水率高的剩余污泥给污泥的无害化处理和资源化利用带来了挑战。本文采用低温水热耦合Fe²⁺活化过硫酸盐提高剩余污泥的脱水性能。结果表明，在80℃、Fe²⁺/S₂O₈^2-的摩尔比为1.25的条件下，加入0.75mmol/g DS的Fe²⁺和0.6mmol/g DS的S₂O₈^2-，污泥的毛细吸水时间（CST）由397.4s±7.9s下降到18.9s±0.4s。研究发现在低温水热耦合Fe²⁺活化过硫酸盐提高污泥脱水性能的过程中，污泥的粒径先减小后增大，胞外聚合物（EPS）被降解和絮体结构遭到破坏。在热和Fe²⁺的共同作用下加速了过硫酸盐的分解，生成的硫酸根自由基（SO₄^•-）和羟基自由基（^•OH）降解了EPS，促进结合水转化为自由水，有利于污泥的固液分离。这些研究可为低温水热耦合Fe²⁺活化过硫酸盐对污泥进行脱水处理提供了理论基础。

关键词: 剩余污泥, 脱水能力, 过硫酸盐, 水热, 活化, 高级氧化工艺

Abstract:

Waste activated sludge with high moisture content challenges the harmless treatment and resource utilization of sludge. In this study, low temperature hydrothermal coupling Fe²⁺-activated persulfate was used to improve the dewatering performance of waste activated sludge. The results showed that when 0.75mmol/g DS Fe²⁺ and 0.6mmol/g DS S₂O₈^2- were added at 80℃, the molar ratio of Fe²⁺/S₂O₈^2- was 1.25, capillary suction time (CST) of sludge decreased from 397.4s±7.9s to 18.9s±0.4s. It was found that in the process of activating persulfate with hydrothermal coupling Fe²⁺ at low temperature to enhance the dewatering performance of sludge, the particle size of sludge first decreased and then increased, the extracellular polymer substance (EPS) was degraded, and the floc structure was damaged. The combination of heat and Fe²⁺ accelerated the decomposition of persulfates to generate sulfate radicals (SO₄^•-) and hydroxyl radicals (^•OH) for oxidizing EPS, promoted the conversion of bound water into free water, and facilitated the solid-liquid separation of sludge. These studies provided a theoretical basis for dewatering sludge with low temperature hydrothermal coupling Fe²⁺-activated persulfate.

Key words: waste activated sludge, dewaterability, persulfate, hydrothermal, activation, advanced oxidation process

中图分类号:

X703

孙千千, 刘阵, 李瑞, 张溪, 杨明德, 吴玉龙. 低温水热耦合亚铁离子活化过硫酸盐提高剩余污泥的脱水性能[J]. 化工进展, 2023, 42(2): 595-602.

SUN Qianqian, LIU Zhen, LI Rui, ZHANG Xi, YANG Mingde, WU Yulong. Low temperature hydrothermal coupling of ferrous ion activated persulfate to improve the dewatering performance of waste activated sludge[J]. Chemical Industry and Engineering Progress, 2023, 42(2): 595-602.

图/表 9

图1 在不同温度加入不同量的S2O82-（mmol/g DS）条件下污泥的CST值变化（Fe2+/S2O82-=1.25）

图2 在80℃条件下添加不同量的S2O82-（mmol/ g DS）污泥的粒径变化

表1 污泥的粒径分布

样品	D10/μm	D50/μm	D90/μm
原污泥	18.9	50.6	120
0	16	43.9	103
0.3	12.1	39.2	96.1
0.6	18.3	47.8	115
0.9	21.2	58.2	149

图3 不同处理条件下污泥EPS组分分布

图4 污泥处理前后的XPS分析

图5 污泥处理前后的热重分析

图6 EPR图谱和猝灭实验

图7 污泥处理前后的SEM图像

图8 低温水热耦合Fe2+活化S2O82-提高剩余污泥脱水性能的机理

参考文献 43

1	XIAO Keke, PEI Kangyue, WANG Hui, et al. Citric acid assisted Fenton-like process for enhanced dewaterability of waste activated sludge with in-situ generation of hydrogen peroxide[J]. Water Research, 2018, 140: 232-242.
2	WANG Liping, ZHANG Lei, LI Aimin. Hydrothermal treatment coupled with mechanical expression at increased temperature for excess sludge dewatering: Influence of operating conditions and the process energetics[J]. Water Research, 2014, 65:85-97.
3	SKINNER Samuel J, STUDER Lindsay J, DIXON David R, et al. Quantification of wastewater sludge dewatering[J]. Water Research, 2015, 82: 2-13.
4	SHI Yahui, HUANG Jinhui, ZENG Guangming, et al. Exploiting extracellular polymeric substances (EPS) controlling strategies for performance enhancement of biological wastewater treatments: An overview[J]. Chemosphere, 2017, 180:396-411.
5	HE Dongqin, WANG Longfei, JIANG Hong, et al. A Fenton-like process for the enhanced activated sludge dewatering[J]. Chemical Engineering Journal, 2015, 272:128-134.
6	TANG Yanfei, DAI Xiaohu, DONG Bin, et al. Humification in extracellular polymeric substances (EPS) dominates methane release and EPS reconstruction during the sludge stabilization of high-solid anaerobic digestion[J]. Water Research, 2020, 175: 115686.
7	HE Dongqin, BAO Bo, SUN Mingkai, et al. Enhanced dewatering of activated sludge by acid assisted heat-CaO₂ treatment: Simultaneously removing heavy metals and mitigating antibiotic resistance genes[J]. Journal of Hazardous Materials, 2021, 418: 126248.
8	SHI Xuchuan, ZHU Ling, LI Bing, et al. Surfactant-assisted thermal hydrolysis off waste activated sludge for improved dewaterability, organic release, and volatile fatty acid production[J]. Waste Management, 2021, 124:339-347.
9	XU Zhixiang, SONG Hao, DENG Xiaoqiang, et al. Dewatering of sewage sludge via thermal hydrolysis with ammonia-treated Fenton iron sludge as skeleton material[J]. Journal of Hazardous Materials, 2019, 379: 120810.
10	XIAO Keke, CHEN Yun, JIANG Xie, et al. Variations in physical, chemical and biological properties in relation to sludge dewaterability under Fe(‍Ⅱ‍)-oxone conditioning[J]. Water Research, 2017, 109:13-23.
11	WEI Hua, TANG Yunong, LI Aimin, et al. Insights into the effects of acidification on sewage sludge dewaterability through pH repeated adjustment[J]. Chemosphere, 2019, 227:269-276.
12	XIAO Ke, DENG Jianping, ZENG Li, et al. Enhancement of municipal sludge dewaterability by electrochemical pretreatment[J]. Journal of Environmental Sciences, 2019, 75:98-104.
13	ZHANG Xiaochun, KANG Huashan, ZHANG Qingrui, et al. The porous structure effects of skeleton builders in sustainable sludge dewatering process[J]. Journal of Environmental Management, 2019, 230:14-20.
14	XIAO Keke, SEOW Wan Yi, CHEN Yun, et al. Effects of thermal-Fe (‍Ⅱ‍) activated oxone treatment on sludge dewaterability[J]. Chemical Engineering Journal, 2017, 322:463-471.
15	GUAN Baohong, YU Jie, FU Hailu, GUO Minhui, et al. Improvement of activated sludge dewaterability by mild thermal treatment in CaCl₂ solution[J]. Water Research, 2012, 46(2):425-432.
16	LIU Xuran, XU Quxiang, WANG Dongbo, et al. Enhanced short-chain fatty acids from waste activated sludge by heat-CaO₂advanced thermal hydrolysis pretreatment: Parameter optimization, mechanisms, and implications[J]. ACS Sustainable Chemistry & Engineering, 2019, 7(3):3544-3555.
17	XU Mengyuan, DENG Jing, CAI Anhong, et al. Comparison of UVC and UVC/persulfate processes for tetracycline removal in water[J]. Chemical Engineering Journal, 2020, 384: 123320.
18	LI Yifu, YUAN Xingzhong, WANG Dongbo, et al. Recyclable zero-valent iron activating peroxymonosulfate synchronously combined with thermal treatment enhances sludge dewaterability by altering physicochemical and biological properties[J]. Bioresource Technology, 2018, 262: 294-301.
19	LUO Lu, GE Yongjian, YUAN Shuyu, et al. Enhanced dewaterability of waste activated sludge by a combined use of permanganate and peroxymonosulfate[J]. RSC Advances, 2019, 9(47): 27593-27601.
20	WANG Xiaomeng, WANG Wei, ZHOU Bo, et al. Improving solid-liquid separation performance of anaerobic digestate from food waste by thermally activated persulfate oxidation[J]. Journal of Hazardous Materials, 2020, 398: 122989.
21	RUAN Shuyu, DENG Jing, CAI Anhong, et al. Improving dewaterability of waste activated sludge by thermally-activated persulfate oxidation at mild temperature[J]. Journal of Environmental Management, 2021, 281: 111899.
22	KIM Min Sik, LEE Ki Myeong, KIM Hyung Eun, et al. Disintegration of waste activated sludge by thermally-activated persulfates for enhanced dewaterability[J]. Environmental Science & Technology, 2016, 50(13):7106-7115.
23	LE Chencheng, KUNACHEVA Chinagarn, STUCKEY David C. “Protein” measurement in biological wastewater treatment systems: A critical evaluation[J]. Environmental Science & Technology, 2016, 50(6):3074-3081.
24	RAUNKJAER K, HVITVED-JACOBSEN T, NIELSEN P H. Measurement of pools of protein, carbohydrate and lipid in domestic wastewater[J]. Water Research, 1994, 28(2):251-262.
25	LAURENT J, PIERRA M, CASELLAS M, et al. Fate of cadmium in activated sludge after changing its physico-chemical properties by thermal treatment[J]. Chemosphere, 2009, 77(6):771-777.
26	AUDREY P, JULIEN L, CHRISTOPHE D, et al. Sludge disintegration during heat treatment at low temperature: A better understanding of involved mechanisms with a multiparametric approach[J]. Biochemical Engineering Journal, 2011, 54(3):178-184.
27	ZHANG Siwei, LIANG Jialin, HUANG Jinjia, et al. Analysis of the relationship of extracellular polymeric substances to the dewaterability and rheological properties of sludge treated by acidification and anaerobic mesophilic digestion[J]. Journal of Hazardous Materials, 2019, 369:31-39.
28	SHAO Liming, HE Peipei, YU Guanghui, et al. Effect of proteins, polysaccharides, and particle sizes on sludge dewaterability[J]. Journal of Environmental Sciences, 2009, 21(1):83-88.
29	LIU Rongzhan, YU Xiao, YU Panfen, et al. New insights into the effect of thermal treatment on sludge dewaterability[J]. Science of the Total Environment, 2019, 656:1082-1090.
30	NIU Tianhao, ZHOU Zhen, REN Weichao, et al. Effects of potassium peroxymonosulfate on disintegration of waste sludge and properties of extracellular polymeric substances[J]. International Biodeterioration & Biodegradation, 2016, 106:170-177.
31	ZHEN Guangyin, LU Xueqin, SU Lianghu, et al. Unraveling the catalyzing behaviors of different iron species (Fe²⁺ vs. Fe⁰) in activating persulfate-based oxidation process with implications to waste activated sludge dewaterability[J]. Water Research, 2018, 134:101-114.
32	WU Boran, NI Bingjie, HORVAT Kristine, et al. Occurrence state and molecular structure analysis of extracellular proteins with implications on the dewaterability of waste-activated sludge[J]. Environmental Science & Technology, 2017, 51(16):9235-9243.
33	Maria RUIZ-HERNANDO, CABANILLAS Esther, LABANDA Jordi, et al. Ultrasound, thermal and alkali treatments affect extracellular polymeric substances (EPSs) and improve waste activated sludge dewatering[J]. Process Biochemistry, 2015, 50(3):438-446.
34	WANG Longfei, QIAN Chen, JIANG Jiankai, et al. Response of extracellular polymeric substances to thermal treatment in sludge dewatering process[J]. Environmental Pollution, 2017, 231:1388-1392.
35	LIU Jibao, WEI Yuansong, LI Kun, et al. Microwave-acid pretreatment: A potential process for sludge dewaterability[J]. Water Research, 2016, 90:225-234.
36	TIAN Ke, LIU Wujun, QIAN Tingting, et al. Investigation on the evolution of N-containing organic compounds during pyrolysis of sewage sludge[J]. Environmental Science & Technology, 2014, 48(18):10888-10896.
37	GENG Nannan, WANG Yili, ZHANG Daxin, et al. An electro-peroxone oxidation-Fe(Ⅱ) coagulation sequential conditioning process for the enhanced waste activated shudge dewatering: Bound water release and organics multivariate change[J]. Science of the Total Environment, 2022, 833: 155272.
38	CHEN Dandan, DOU Yuhao, TANG Qin, et al. New insight on the combined effects of hydrothermal treatment and FeSO₄/Ca(ClO)₂ oxidation for sludge dewaterability improvement: From experimental to theoretical investigation[J]. Fuel Processing Technology, 2020, 197: 106196.
39	JIN B, WILEN B M, LANT P. Impacts of morphological, physical and chemical properties of sludge flocs on dewaterability of activated sludge[J]. Chemical Engineering Journal, 2004, 98 (1/2):115-126.
40	CHEN Wei, YANG Haiping, CHEN Yingquan, et al. Transformation of nitrogen and evolution of N-containing species during algae pyrolysis[J]. Environmental Science & Technology, 2017, 51(11): 6570-6579.
41	CHEN Liwei, HU Xiaoxin, YANG Ying, et al. Degradation of atrazine and structurally related s-triazine herbicides in soils by ferrous-activated persulfate: Kinetics, mechanisms and soil-types effects[J]. Chemical Engineering Journal, 2018, 351: 523-531.
42	GUO Junyuan, GAO Qifan, YANG Shuqing, et al. Degradation of pyrene in contaminated water and soil by Fe²⁺-activated persulfate oxidation: Performance, kinetics, and background electrolytes (Cl^-, HCO₃ ^- and humic acid) effects[J]. Process Safety and Environmental Protection, 2021, 146: 686-693.
43	GE Dongdong, DONG Yanting, ZHANG Wenrui, et al. A novel Fe²⁺/persulfate/tannic acid process with strengthened efficacy on enhancing waste activated sludge dewaterability and mechanism insight[J]. Science of the Total Environment, 2020, 733: 139146.

[1]	王晋刚, 张剑波, 唐雪娇, 刘金鹏, 鞠美庭. 机动车尾气脱硝催化剂Cu-SSZ-13的改性研究进展[J]. 化工进展, 2023, 42(9): 4636-4648.
[2]	王雪婷, 顾霞, 徐先宝, 赵磊, 薛罡, 李响. 水热预处理对餐厨垃圾厌氧发酵产戊酸的影响[J]. 化工进展, 2023, 42(9): 4994-5002.
[3]	张耀杰, 张传祥, 孙悦, 曾会会, 贾建波, 蒋振东. 煤基石墨烯量子点在超级电容器中的应用[J]. 化工进展, 2023, 42(8): 4340-4350.
[4]	李艳玲, 卓振, 池亮, 陈曦, 孙堂磊, 刘鹏, 雷廷宙. 氮掺杂生物炭的制备与应用研究进展[J]. 化工进展, 2023, 42(7): 3720-3735.
[5]	龚鹏程, 严群, 陈锦富, 温俊宇, 苏晓洁. 铁酸钴复合碳纳米管活化过硫酸盐降解铬黑T的性能及机理[J]. 化工进展, 2023, 42(7): 3572-3581.
[6]	杨家添, 唐金铭, 梁恣荣, 黎胤宏, 胡华宇, 陈渊. 新型淀粉基高吸水树脂抑尘剂的制备及其应用[J]. 化工进展, 2023, 42(6): 3187-3196.
[7]	王久衡, 荣鼐, 刘开伟, 韩龙, 水滔滔, 吴岩, 穆正勇, 廖徐情, 孟文佳. 水蒸气强化纤维素模板改性钙基吸附剂固碳性能及强度[J]. 化工进展, 2023, 42(6): 3217-3225.
[8]	王雪, 徐期勇, 张超. 木质纤维素类生物质水热炭化机理及水热炭应用进展[J]. 化工进展, 2023, 42(5): 2536-2545.
[9]	李云闯, 谢方明, 席亚男, 万新月, 孙玉虎, 赵永峰, 李根, 刘宏海, 高雄厚, 刘洪涛. 高水热稳定性介孔分子筛的低成本合成研究进展[J]. 化工进展, 2023, 42(4): 1877-1884.
[10]	陈绍勤, 胡玲, 雷天涯, 王蓉, 舒建成, 陈梦君. 机械活化强化锌焙砂中锌的浸出[J]. 化工进展, 2023, 42(3): 1649-1658.
[11]	张晨光, 封硕, 邢玉烨, 沈伯雄, 苏立超. 柴油车用NH₃-SCR铜基分子筛催化剂孤立态Cu²⁺研究进展[J]. 化工进展, 2023, 42(3): 1321-1331.
[12]	陈韶云, 周贤太, 纪红兵. 金属卟啉/碳纳米管仿生催化剂的制备及其在Baeyer-Villiger氧化反应中的催化机理[J]. 化工进展, 2023, 42(3): 1332-1340.
[13]	段一航, 高宁博, 全翠. 水热处理对含油污泥热解特性及动力学影响[J]. 化工进展, 2023, 42(2): 603-613.
[14]	王妍, 秦振平, 刘越, 张文海, 郭红霞. 环糊精原位改性MoS₂管式陶瓷复合膜的制备及性能[J]. 化工进展, 2023, 42(10): 5373-5380.
[15]	刘培慧, 刘宇喆, 李琳, 王少辉, 王同华. 具有多级孔道结构的高比表面多孔炭活化策略及VOCs吸附性能[J]. 化工进展, 2022, 41(S1): 613-621.