Oxidation characteristics and spectral analysis of leachate reverse osmosis concentrate by catalytic ozonation

doi:10.11949/0438-1157.20210400

Abstract

Abstract:

The removal efficiency of humus is the key to catalytic ozone oxidation to degrade the organic matter in the RO concentrate of landfill leachate. Activated carbon-supported metal cerium catalyst (Ce-AC) catalytic ozone oxidation can effectively improve the removal efficiency of humus. In this paper, the Ce-AC catalyst was characterized by XRD, SEM and EDS. The effects of different catalysts on COD removal and biodegradability of RO concentrate were compared. The degradation mechanism of humus was clarified by analyzing the degradation product spectrum. The results show that cerium oxide is loaded on AC in the form of CeO₂ fluorite crystal. After loading, the specific surface area and pore volume of AC decrease, and the average pore diameter increases. Ce-AC had the best removal effect on COD and UV₂₅₄, which were 44.7% and 67.3%, respectively. The effluent biodegradability was significantly improved, and the B/C ratio was increased from 0.06 to 0.47. UV-Vis spectra showed that the degradation efficiency of aromatic compounds representing humus in the system was obvious. Three-dimensional fluorescence spectroscopy showed that the humic substances in the system were degraded to a large extent. The results of fluorescence region integration showed that the removal efficiency of humic substances reached 66.7%. Fourier transform infrared spectroscopy showed that humic substances were oxidized and decomposed into relatively small molecules of carbohydrates and organic amines, sulfur and alcohols.

Key words: activated carbon, Ce-AC catalyst, ozonation, leachate reverse osmosis concentrate, spectroscopic analyses

摘要：

腐殖质的去除效率是催化臭氧氧化降解垃圾渗滤液RO浓液中有机物的关键，活性炭负载金属铈催化剂（Ce-AC）催化臭氧氧化可有效提高腐殖质的去除效率。本文通过XRD、SEM和EDS等手段对Ce-AC催化剂进行表征，对比不同催化剂催化臭氧氧化对RO浓液COD去除及可生化性的影响，通过降解产物光谱分析明晰腐殖质的降解机制。结果表明，铈氧化物是以CeO₂萤石晶型的形式负载在AC上，负载后的AC比表面积和孔容积减少，平均孔径增加。催化剂Ce-AC对COD和UV₂₅₄的去除效果最好，为44.7%和67.3%，出水可生化性显著提升，B/C比从0.06提升到0.47。紫外-可见光谱表明，体系代表腐殖质的芳香类化合物降解效率明显；三维荧光光谱表明体系中腐殖质类物质被极大程度地降解，荧光区域积分的结果表明腐殖质类物质的去除效率达到了66.7%；傅里叶红外光谱表明腐殖质类物质被氧化分解成了相对小分子的碳水化合物和有机胺、硫和醇等。

关键词: 活性炭, Ce-AC催化剂, 臭氧氧化, 渗滤液RO浓液, 光谱分析

CLC Number:

TQ 032.41

Zhengyi ZHANG,Qian ZHANG,Ziyang LOU,Wei LIU,Yunan ZHU,Chunbo YUAN,Xiao YU,Tiantao ZHAO. Oxidation characteristics and spectral analysis of leachate reverse osmosis concentrate by catalytic ozonation[J]. CIESC Journal, 2021, 72(10): 5362-5371.

张正义,张千,楼紫阳,刘伟,朱宇楠,袁春波,于潇,赵天涛. 催化臭氧氧化处理渗滤液RO浓液的氧化特性及光谱分析[J]. 化工学报, 2021, 72(10): 5362-5371.

Figures/Tables 15

Fig.1 Reaction device diagram of ozone catalytic oxidation

Table 1 Water quality characteristics of leachate reverse osmosis concentrate

指标	数值
COD/(mg/L)	2090
BOD₅/(mg/L)	120.5
$N H 4 +$ /(mg/L)	182
TN/(mg/L)	510
pH	8.69

Table 1 Water quality characteristics of leachate reverse osmosis concentrate

指标	数值
COD/(mg/L)	2090
BOD₅/(mg/L)	120.5
$N H 4 +$ /(mg/L)	182
TN/(mg/L)	510
pH	8.69

Fig.2 XRD patterns of Ce-AC and AC

Fig.3 SEM image, elemental mapping and EDS of Ce-AC

Fig.4 N2 adsorption isotherms of AC and Ce-AC

Fig.5 Pores size distribution curves of AC and Ce-AC

Table 2 Pore structure parameters of AC and Ce-AC

样品名称	S_BET/(m²/g)	平均孔径/nm	孔容积/(cm³/g)
AC	1432	3.5578	1.0310
Ce-AC	1359	4.0484	0.9770

Fig.6 Variation trend of COD with time in RO concentrate treated by different systems

Fig.7 Effect of RO concentrate treated by different systems on biodegradability

Fig.8 UV-Vis spectra of RO concentrate treated by different systems

Fig.9 UV254 of RO concentrate treated with Ce-AC/O3 system over time

Fig.10 UV-Vis spectra of RO concentrate treated with Ce-AC/O3 system over time

Fig.11 Three-dimensional fluorescence spectra of RO concentrate treated with Ce-AC/O3 system over time

Table 3 Comparison of FRI values of each region before and after processing

区域	原液Φ_i,_n/ (au·nm²)	原液P_i,_n/ %	处理后Φ_i,_n/ (au·nm²)	处理后P_i,_n/ %
区域Ⅰ	28366154	22.1	20050717	31.2
区域Ⅱ	34839219	27.1	13617790	21.2
区域Ⅲ	16503733	12.9	14286136	22.3
区域Ⅳ	48637041	37.9	16207813	25.3

Fig.12 Fourier transform infrared spectroscopy of RO concentrate before ( S1 ) and after ( S2 ) treatment with Ce-AC/O3 system

References 32

1	薛晓冬. 膜组合工艺在垃圾渗滤液处理中的应用[J]. 环境与发展, 2019, 31(2): 102,105.
	Xue X D. Application of membrane combination process in landfill leachate treatment[J]. Environment and Development, 2019, 31(2): 102,105.
2	艾恒雨, 孟棒棒, 李娜, 等. 我国垃圾渗滤液膜浓缩液处理现状与污染控制建议[J]. 环境工程技术学报, 2016, 6(6): 553-558.
	Ai H Y, Meng B B, Li N, et al. Treatment status and pollution control suggestions for membrane concentrated leachate in China[J]. Journal of Environmental Engineering Technology, 2016, 6(6): 553-558.
3	徐蘇士. UV-Fenton工艺对垃圾渗滤液纳滤浓缩液的处理研究[D]. 北京: 清华大学, 2012.
	Xu S S. Research on UV-Fenton treatment of concentrated water from nanofiltration of landfill leachate[D]. Beijing: Tsinghua University, 2012.
4	王洪庆, 乐晨. 混凝沉淀-Fenton氧化法处理垃圾渗滤液纳滤浓缩液的研究[J]. 广东化工, 2016, 43(6): 116-117.
	Wang H Q, Le C. Study on the treatment of concentrated water from nanofiltration of bio-treated landfill leachate by coagulation-sedimentation and Fenton oxidation process [J]. Guangdong Chemical Industry, 2016, 43(6): 116-117.
5	黄力彦, 吕逵弟, 谭艳来, 等. 铁碳微电解法预处理垃圾渗滤液膜滤浓缩液[J]. 工业安全与环保, 2015, 41(7): 37-39.
	Huang L Y, Lyu K D, Tan Y L, et al. Pretreatment of concentrated leachate from RO system by iron carbon micro- electrolysis[J]. Industrial Safety and Environmental Protection, 2015, 41(7): 37-39.
6	Chen T, Gu W, Li G, et al. Significant enhancement in catalytic ozonation efficacy: from granular to super-fine powdered activated carbon[J]. Frontiers of Environmental Science and Engineering, 2018, 12(1): 6-11.
7	骆沁沁. 催化氧化法提标减排印染废水COD的中试研究[D]. 杭州: 浙江大学, 2012.
	Luo Q Q. Pilotscale experiment to reduce COD of dyeing and printing wastewater using catalyzed oxidation[D]. Hangzhou: Zhejiang University, 2012.
8	何帅明, 莫立焕, 徐峻, 等. 活性炭负载铈催化臭氧处理桉木制浆废水[J]. 中国造纸, 2016, 35(3): 1-6.
	He S M, Mo L H, Xu J, et al. Catalytic ozonation of eucalyptus pulping effluent by cerium loaded on activated carbon[J]. China Pulp and Paper, 2016, 35(3): 1-6.
9	Jouanneau S, Recoules L, Durand M J, et al. Methods for assessing biochemical oxygen demand (BOD): a review[J]. Water Research, 2014, 49(1): 62-82.
10	陈炜鸣, 张爱平, 李民, 等. O₃/H₂O₂降解垃圾渗滤液浓缩液的氧化特性及光谱解析[J]. 中国环境科学, 2017, 37(6): 2160-2172.
	Chen W M, Zhang A P, Li M, et al. Decomposition of organics in concentrated landfill leachate with ozone/hydrogen peroxide system: oxidation characteristics and spectroscopic analyses[J]. China Environmental Science, 2017, 37(6): 2160-2172.
11	Stedmon C A, Bro R. Characterizing dissolved organic matter fluorescence with parallel factor analysis: a tutorial[J]. Limnology and Oceanography: Methods, 2008, 6(11): 572-579.
12	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 and Technology, 2003, 37(24): 5701-5710.
13	王佳琴, 李卫华, 申慧彦, 等. 污水厂进出水中DOM的三维荧光和FTIR光谱解析[J]. 环境科学与技术, 2018, 41(1): 71-76.
	Wang J Q, Li W H, Shen H Y, et al. Analysis of dissolved organic matter of the sewage influent and effluents from wastewater treatment plant using EEM fluorescence and FTIR spectroscopy[J]. Environmental Science and Technology, 2018, 41(1): 71-76.
14	毛锡嵩, 夏雪雯, 兰苑培, 等. 不同气氛加热过程中CeO₂晶体结构的原位研究[J]. 中国稀土学报, 2020, 38(4): 483-489.
	Mao X S, Xia X W, Lan Y P, et al. In situ study of CeO₂ crystal structure during heating in different atmospheres[J]. Journal of the Chinese Society of Rare Earths, 2020, 38(4): 483-489.
15	高晓慧, 杨儒. 萤石型层状介孔CeO₂的合成[C]//中国化工学会年会暨全国化工新材料学术技术报告会. 中国化工学会, 北京化工大学, 北京工业大学, 2006.
	Gao X H, Yang R. Synthesis of fluorite layered mesoporous CeO₂[C]//Annual Conference of Chinese Chemical Society and National Academic and Technical Report on New Chemical Materials. The Chemical Industry and Engineering Society of China, Beijing University of Chemical Technology, Beijing University of Technology, 2006.
16	张涛, 马军, 陈忠林, 等. 有机酸在金属氧化物上的吸附对催化臭氧氧化的影响[J]. 环境科学, 2005, 26(5): 85-88.
	Zhang T, Ma J, Chen Z L, et al. Effect of organic acids adsorption on catalytic ozonation with metal oxides[J]. Environmental Science, 2005, 26(5): 85-88.
17	王群, 杨一, 刘娟昉, 等. 二氧化铈催化分解水中臭氧的性能研究[J]. 中国给水排水, 2010, 26(11): 130-132.
	Wang Q, Yang Y, Liu J F, et al. Study on ozone decomposition catalyzed by cerium dioxide[J]. China Water and Wastewater, 2010, 26(11): 130-132.
18	Di T M, Zhu B C, Cheng B, et al. A direct Z-scheme g-C₃N₄/SnS₂ photocatalyst with superior visible-light CO₂ reduction performance[J]. Journal of Catalysis, 2017, 352: 532-541.
19	Imai A, Onuma K, Inamori Y, et al. Effects of pre-ozonation in refractory leachate treatment by the biological activated carbon fluidized bed process[J]. Environmental Technology (United Kingdom), 1998, 19(2): 213-221.
20	Cortez S, Teixeira P, Oliveira R, et al. Evaluation of Fenton and ozone-based advanced oxidation processes as mature landfill leachate pre-treatments[J]. Journal of Environmental Management, 2011, 92(3): 749-755.
21	邱松凯, 范举红, 黄开坚, 等. 臭氧-曝气生物滤池深度处理垃圾焚烧渗滤液可行性研究[J]. 中国环境科学, 2014, 34(10): 2513-2521.
	Qiu S K, Fan J H, Huang K J, et al. A study on municipal waste leachate treatment with ozonation-biological aerated filter[J]. China Environmental Science, 2014, 34(10): 2513-2521.
22	Tizaoui C, Bouselmi L, Mansouri L, et al. Landfill leachate treatment with ozone and ozone/hydrogen peroxide systems[J]. Journal of Hazardous Materials, 2007, 140(1/2): 316-324.
23	Beltrán F J, Rivas J, Álvarez P, et al. Kinetics of heterogeneous catalytic ozone decomposition in water on an activated carbon[J]. Ozone: Science and Engineering, 2002, 24(4): 227-237.
24	Deng R Y, He Q, Yang D X, et al. Enhanced synergistic performance of nano-Fe⁰-CeO₂ composites for the degradation of diclofenac in DBD plasma[J]. Chemical Engineering Journal, 2021, 406: 126884.
25	Anumol T, Sgroi M, Park M, et al. Predicting trace organic compound breakthrough in granular activated carbon using fluorescence and UV absorbance as surrogates[J]. Water Research, 2015, 76(1): 76-87.
26	姚磊, 马涛, 张列宇, 等. 厌氧共代谢处理晚期垃圾渗滤液中难降解有机物的研究[J]. 水处理技术, 2019, 45(8): 30-34.
	Yao L, Ma T, Zhang L Y, et al. Study on anaerobic co-metabolism for treatment of refractory organic matter in late landfill leachate[J]. Technology of Water Treatment, 2019, 45(8): 30-34.
27	程亮, 张保林, 徐丽, 等. 腐殖酸热分解动力学[J]. 化工学报, 2014, 65(9): 3470-3478.
	Cheng L, Zhang B L, Xu L, et al. Thermal decomposition kinetics of humic acid[J]. CIESC Journal, 2014, 65(9): 3470-3478.
28	隆佳君, 彭澍晗, 褚华强, 等. 铈类催化剂催化臭氧化的研究进展[J]. 环境污染与防治, 2019, 41(5): 596-601, 607.
	Long J J, Peng S H, Chu H Q, et al. Research progress of cerium catalysts for catalytic ozonation[J]. Environmental Pollution and Control, 2019, 41(5): 596-601, 607.
29	张丽丽, 庄媛, 胡春, 等. 多相催化技术的固液微界面调控原理及应用进展[J]. 环境科学学报, 2020, 40(12): 4225-4233.
	Zhang L L, Zhuang Y, Hu C, et al. Control mechanism of solid-liquid micro-interface and application progress for heterogeneous catalysis technology[J]. Acta Scientiae Circumstantiae, 2020, 40(12): 4225-4233.
30	王家德, 袁通斌, 周丹飞, 等. 基于原位红外光谱的水相苯酚电氧化机理研究[J]. 化工学报, 2019, 70(12): 4821-4827.
	Wang J D, Yuan T B, Zhou D F, et al. Mechanism of phenol electro-oxidation in aqueous solution based on in situ infrared spectroscopy[J]. CIESC Journal, 2019, 70(12): 4821-4827.
31	Tian Y, Chen L, Jiang T L. Characterization and modeling of the soluble microbial products in membrane bioreactor[J]. Separation and Purification Technology, 2011, 76(3): 316-324.
32	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[J]. 环境工程学报, 2013, 7(2): 451-456.
	Jia C Z, Liu S, Zhang C X, et al. Degradation of dissolved organic matter in landfill leachate during photocatalytic treatment process[J]. Chinese Journal of Environmental Engineering, 2013, 7(2): 451-456.

[1]	Longyi LYU, Wenbo JI, Muda HAN, Weiguang LI, Wenfang GAO, Xiaoyang LIU, Li SUN, Pengfei WANG, Zhijun REN, Guangming ZHANG. Enhanced anaerobic removal of halogenated organic pollutants by iron-based conductive materials: research progress and future perspectives [J]. CIESC Journal, 2023, 74(8): 3193-3202.
[2]	Yuanhao QU, Wenyi DENG, Xiaodan XIE, Yaxin SU. Study on electro-osmotic dewatering of sludge assisted by activated carbon/graphite [J]. CIESC Journal, 2023, 74(7): 3038-3050.
[3]	Gang WANG, Xiaoping CHE, Shiyong WANG, Jieshan QIU. Carbon electrodes modified with water-soluble charged polymer binder for enhanced capacitive deionization performance [J]. CIESC Journal, 2022, 73(4): 1763-1771.
[4]	Li LIU, Peng JIANG, Wei WANG, Tonghuan ZHANG, Liwen MU, Xiaohua LU, Jiahua ZHU. Coupling process simulation and random forest model for analyzing and predicting biomass-to-hydrogen conversion [J]. CIESC Journal, 2022, 73(11): 5230-5239.
[5]	Chao ZHANG, Jian CHEN, Wenhua YIN, Yuanhui SHEN, Zhaoyang NIU, Xiuxin YU, Donghui ZHANG, Zhongli TANG. Transient analysis of pressure swing adsorption hydrogen purification process [J]. CIESC Journal, 2022, 73(1): 308-321.
[6]	LUO Weili, WANG Wenwen, PAN Quanwen, GE Tianshu, WANG Ruzhu. Heat storage performance of composite adsorbent with activated carbon fiber [J]. CIESC Journal, 2021, 72(S1): 554-559.
[7]	Kang YAN, Song YANG, Shoujun LIU, Chao YANG, Huiling FAN, Ju SHANGGUAN. In-situ preparation of ZnO-based activated carbon desulfurizer from low-rank coal [J]. CIESC Journal, 2021, 72(9): 4921-4930.
[8]	JIANG Wenwen, NIE Pengfei, HU Bin, LI Jingjing, LIU Jianyun. Selective capacitive adsorption of fluoride ions with Al₂O₃/AC anode [J]. CIESC Journal, 2021, 72(5): 2817-2825.
[9]	JIAO Shuai, YANG Lei, WU Tingting, LI Hongqiang, LYU Huihong, HE Xiaojun. Synthesis of nitrogen doped hierarchically porous carbon nanosheets for supercapacitor by mixed salt template [J]. CIESC Journal, 2021, 72(5): 2869-2877.
[10]	WANG Jing, HAN Qiaoning, LEI Yiting, TANG Man, CHEN Lihong, CHE Junda, LIU Zuguang. One-step preparation of oxygen-enriched lignin activated carbon and its methylene blue adsorption performance [J]. CIESC Journal, 2021, 72(5): 2826-2836.
[11]	Yinhai SU,Shuping ZHANG,Lingqin LIU,Yuanquan XIONG. Synergetic production of phenols and syngas from the catalytic pyrolysis of cellulose on activated carbon [J]. CIESC Journal, 2021, 72(10): 5206-5217.
[12]	Yi ZHOU,Yonghong WANG,Xinru ZHANG,Jinping LI. Preparation of PEBA/N, S co-doped porous carbon sphere mixed matrix membrane for CO₂ separation [J]. CIESC Journal, 2021, 72(10): 5237-5246.
[13]	Qingsi LI, Lei ZHANG. Progress of hemoadsorbent materials for hemoperfusion [J]. CIESC Journal, 2020, 71(S2): 12-23.
[14]	Honghui BI, Shuai JIAO, Feng WEI, Xiaojun HE. Preparation of coral-like nitrogen-doped porous carbons and its supercapacitive properties [J]. CIESC Journal, 2020, 71(6): 2880-2888.
[15]	Tao HU, Xiong ZHANG, Yabin AN, Chen LI, Yanwei MA. Research progress of carbon cathode materials for Li-ion capacitors [J]. CIESC Journal, 2020, 71(6): 2530-2546.