Fe/Ag催化臭氧氧化降解苯酚的研究

doi:10.19657/j.geoscience.1000-8527.2020.061

现代地质 ›› 2021, Vol. 35 ›› Issue (03): 711-719.DOI: 10.19657/j.geoscience.1000-8527.2020.061

Fe/Ag催化臭氧氧化降解苯酚的研究

侯颖¹(), 徐锦明²(), 李平¹, 毛君妍³, 张原浩¹, 宿俊杰¹, 陈男¹, 胡伟武¹

1.中国地质大学(北京) 水资源与环境学院,北京 100083
2.中国地质大学(北京) 数理学院,北京 100083
3.南京理工大学材料科学与工程学院,江苏南京 210094

收稿日期:2019-01-18 修回日期:2020-06-23 出版日期:2021-06-23 发布日期:2021-06-24
通讯作者: 徐锦明
作者简介:徐锦明,男,讲师,1975年出生,应用化学专业,主要从事基础化学课程教学与教育研究。Email: xujm@cugb.edu.cn。
侯颖,女,本科生,1998年出生,水文与水资源工程专业,主要从事水文学的研究。Email: hyymsh@foxmail.com。
基金资助:
中国地质大学(北京)大学生创新创业训练计划项目(2018AX101)

Fe/Ag Catalytic Ozonation for the Degradation of Phenol

HOU Ying¹(), XU Jinming²(), LI Ping¹, MAO Junyan³, ZHANG Yuanhao¹, SU Junjie¹, CHEN Nan¹, HU Weiwu¹

1. School of Water Resources and Environment, China University of Geosciences, Beijing 100083, China
2. School of Science, China University of Geosciences, Beijing 100083, China
3. School of Materials Science and Engineering, Nanjing University of Science and Technology, Nanjing,Jiangsu 210094, China

Received:2019-01-18 Revised:2020-06-23 Online:2021-06-23 Published:2021-06-24
Contact: XU Jinming

摘要/Abstract

摘要：

为研究双金属催化剂去除有机污染物的效果,采用自制Fe/Ag催化剂对模拟苯酚废水进行了臭氧催化氧化处理。通过扫描电子显微镜(SEM)、比表面积分析仪(BET)和X射线衍射(XRD)对催化剂进行表征,并考察了催化剂类型、催化剂投加量和溶液初始pH值对降解效果的影响规律。结果表明:与Fe相比,Fe/Ag比表面积减少了22.8%,在Fe/Ag/O₃与含苯酚废水的反应体系中,反应遵循臭氧直接作用和活性自由基(·OH、·O₂、H₂O₂)共同作用的机理;Fe/Ag在反应过程中体现出良好的协同作用;300 mg/L的苯酚模拟废水在pH=6.3、Fe/Ag投加量为1.00 g的最优反应条件下经60 min反应,苯酚与化学需氧量(COD)去除率比单独臭氧氧化分别提高了18.4%和29.4%。

关键词: 臭氧催化氧化, Fe/Ag, 苯酚, 协同作用, 自由基

Abstract:

To study the effect of bimetallic catalysts on the removal of organic pollutants, the simulated phenol wastewater was subjected to Fe/Ag catalytic ozonation treatment. The catalyst was characterized by various characterization methods (SEM, BET and XRD), and the degradation effects due to the different catalyst types and dosages and initial pH were evaluated. The results show that compared with Fe, the specific surface area of Fe/Ag is reduced by 22.8%. In the reaction system of Fe/Ag/O₃ and phenol-containing wastewater, the reaction follows the mechanism of direct action of ozone and the free radicals (·OH, ·O₂, H₂O₂). Fe/Ag and ozone show good synergistic effects in the reaction. The phenol and COD removal rate were, respectively, 18.4% and 29.4% higher than that of ozone oxidation alone (initial phenol concentration=300 mg/L, catalysts dosage=1.00 g, and initial solution pH=6.3).

Key words: Catalytic ozonation, Fe/Ag, phenol degradation, synergistic effect, free radical

中图分类号:

侯颖, 徐锦明, 李平, 毛君妍, 张原浩, 宿俊杰, 陈男, 胡伟武. Fe/Ag催化臭氧氧化降解苯酚的研究[J]. 现代地质, 2021, 35(03): 711-719.

HOU Ying, XU Jinming, LI Ping, MAO Junyan, ZHANG Yuanhao, SU Junjie, CHEN Nan, HU Weiwu. Fe/Ag Catalytic Ozonation for the Degradation of Phenol[J]. Geoscience, 2021, 35(03): 711-719.

图/表 10

图1 臭氧化反应装置图 A.尾气吸收装置;B.反应发生器;C.臭氧发生器;D.流量计;E.氧气瓶

Fig.1 Schematic diagram showing the ozonation reactor setup

图2 Fe/Ag和Fe的XRD衍射图

Fig.2 XRD pattern of Fe/Ag and Fe

表1 Fe和Fe/Ag的BET数据

Table 1 BET data of Fe and Fe/Ag

催化剂类型	比表面积/(m²/g)	孔隙体积/(cm²/g)	孔径/nm
Fe	5.159	0.012	2.708
Fe/Ag	3.985	0.006	2.708

图3 Fe和Fe/Ag的SEM图像 (a)Fe,5 000倍;(b)Fe/Ag,5 000倍

Fig.3 SEM images of Fe and Fe/Ag

表2 单独臭氧氧化与催化臭氧化影响下去除苯酚和COD的反应速率常数(K)

Table 2 Reaction rate constant (K) for the removal of phenol and COD, with added catalyst and ozone alone

类型	苯酚		COD
类型	K/min^-1	R²	K/min^-1	R²
单独臭氧	0.027	0.990	0.010	0.940
Fe	0.037	0.994	0.016	0.935
Fe/Ag	0.098	0.973	0.022	0.952

图4 单独臭氧氧化与催化臭氧化的影响 (a)对苯酚去除率的影响;(b)苯酚降解反应动力学;(c)对COD去除率的影响;(d)COD降解反应动力学;(e)对pH的影响

Fig.4 Effects of ozone oxidation alone and catalyst ozonation

表3 Fe/Ag投加量影响下去除苯酚和COD的反应速率常数(K)

Table 3 Fe/Ag ozonation reaction rate constant (K) for the removal of phenol and COD with different catalyst dosage

投加量/g	苯酚		COD
投加量/g	K/min^-1	R²	K/min^-1	R²
0.25	0.086	0.971	0.012	0.902
0.50	0.065	0.977	0.016	0.928
1.00	0.098	0.973	0.022	0.952
2.50	0.061	0.985	0.022	0.936

图5 Fe/Ag投加量的影响 (a)对苯酚去除率的影响;(b)苯酚降解反应动力学;(c)对COD去除率的影响;(d)COD降解反应动力学;(e)对pH的影响

Fig.5 Effect of Fe/Ag dosage

图6 初始pH对苯酚和COD去除效果的影响 (a)对苯酚去除率的影响;(b)苯酚降解反应动力学;(c)对COD去除率的影响;(d)COD降解反应动力学;(e)对pH的影响

Fig.6 Effect of initial pH on the removal of phenol and COD

图7 投加自由基捕获剂对苯酚和COD去除率的影响

Fig.7 Removal of phenol and COD by three different radical traps

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Fe/Ag催化臭氧氧化降解苯酚的研究

Fe/Ag Catalytic Ozonation for the Degradation of Phenol

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