催化臭氧氧化处理渗滤液RO浓液的氧化特性及光谱分析

doi:10.11949/0438-1157.20210400

化工学报 ›› 2021, Vol. 72 ›› Issue (10): 5362-5371.DOI: 10.11949/0438-1157.20210400

催化臭氧氧化处理渗滤液RO浓液的氧化特性及光谱分析

张正义¹(),张千¹(),楼紫阳^2,³,刘伟³,朱宇楠¹,袁春波¹,于潇¹,赵天涛¹

^1.重庆理工大学化学化工学院，重庆 400054
^2.上海交通大学环境科学与工程学院，上海 200240
^3.上海交通大学重庆研究院，重庆 401147

收稿日期:2021-03-22 修回日期:2021-05-07 出版日期:2021-10-05 发布日期:2021-10-05
通讯作者: 张千
作者简介:张正义（1998—），男，硕士研究生，1299626975@qq.com
基金资助:
国家自然科学基金项目(51908099);国家重点研发计划项目(2018YFC1900704);重庆市教委科学技术研究项目(KJQN20201114)

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

Zhengyi ZHANG¹(),Qian ZHANG¹(),Ziyang LOU^2,³,Wei LIU³,Yunan ZHU¹,Chunbo YUAN¹,Xiao YU¹,Tiantao ZHAO¹

^1.School of Chemistry and Chemical Engineering, Chongqing University of Technology, Chongqing 400054, China
^2.School of Environmental Science and Engineering, Shanghai Jiao Tong University, Shanghai 200240, China
^3.Shanghai Jiao Tong University Chongqing Research Institute, Chongqing 401147, China

Received:2021-03-22 Revised:2021-05-07 Online:2021-10-05 Published:2021-10-05
Contact: Qian ZHANG

摘要/Abstract

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

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

中图分类号:

TQ 032.41

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.

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.

图/表 15

图1 臭氧催化氧化反应装置图

Fig.1 Reaction device diagram of ozone catalytic oxidation

表1 RO浓液的水质特点

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

表1 RO浓液的水质特点

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

图2 AC、Ce-AC的XRD谱图

Fig.2 XRD patterns of Ce-AC and AC

图3 Ce-AC的SEM图、元素映射图和EDS能谱图

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

图4 AC和Ce-AC的N2吸附等温线

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

图5 AC和Ce-AC的孔径分布曲线

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

表2 AC和Ce-AC的孔结构参数

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

图6 不同体系处理RO浓液的COD随时间变化趋势

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

图7 不同体系处理RO浓液对其可生化性的影响

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

图8 不同体系处理RO浓液的紫外-可见光谱图

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

图9 Ce-AC/O3体系处理RO浓液的UV254随时间变化趋势

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

图10 Ce-AC/O3体系处理RO浓液随时间变化的紫外-可见光谱图

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

图11 Ce-AC/O3体系处理RO浓液随时间变化的三维荧光光谱

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

表3 处理前后各区域FRI值对比

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

图12 Ce-AC/O3体系处理RO浓液前（S1）、后（S2）的傅里叶红外光谱

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

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催化臭氧氧化处理渗滤液RO浓液的氧化特性及光谱分析

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

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