α-Fe<sub>2</sub>O<sub>3</sub>催化臭氧氧化耦合陶瓷膜处理含酚废水

王勇; 张耀宗; 毕莹莹; 杜明辉; 孙晓明

doi:10.12153/j.issn.1674-991X.20210816

α-Fe₂O₃催化臭氧氧化耦合陶瓷膜处理含酚废水

doi: 10.12153/j.issn.1674-991X.20210816

王勇^{1, 2,},
张耀宗²,
毕莹莹¹,
杜明辉²,
孙晓明^1, ,

1.
中国环境科学研究院, 国家环境保护生态工业重点实验室
2.
华北理工大学建筑工程学院

基金项目: 国家水体污染控制与治理科技重大专项（2017ZX07402-002），国家环境保护生态工业重点实验室开放基金（2022KFF-15），中央级公益性科研院所基本科研业务费专项（2022YSKY-09）

详细信息

作者简介:
王勇（1997—），男，硕士研究生，主要从事水污染控制与废水资源化研究，1833055310@qq.com

通讯作者:
孙晓明（1978—），男，研究员，博士，主要从事水污染控制与废水资源化研究，sunxm52@126.com

中图分类号: X703
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出版历程
- 收稿日期: 2021-12-09

α-Fe₂O₃ catalytic ozonation coupled with ceramic membrane for phenol wastewater treatment

1.
State Environmental Protection Key Laboratory of Ecological Industry, Chinese Research Academy of Environmental Sciences
2.
School of Architecture and Civil Engineering, North China University of Science and Technology

摘要

摘要:
催化臭氧氧化是处理含酚废水的有效手段，为研究α-Fe₂O₃催化氧化含酚废水的降解效能同时有效回收催化剂，采用微米级α-Fe₂O₃催化臭氧氧化苯酚模拟废水，并耦合陶瓷膜对分散在反应体系的催化剂进行截留、回收，实现工艺的连续运行。结果表明：在间歇运行条件下，催化氧化反应30 min时废水COD去除率达到97%以上，高COD去除率的主要原因是α-Fe₂O₃对臭氧具有较强的催化活性，在催化氧化过程中产生了强氧化性产物·OH；在恒压条件下，通过膜污染模型拟合和串联阻力模型进行验证，R_r占总阻力的50%以上，但当操作压力超过30 kPa，一部分可逆污染向不可逆污染逐渐转化，R_ir显著增加；通过动力学拟合探究膜污染形成机制，运行过程中陶瓷膜污染模型为中间堵塞或滤饼堵塞，膜污染主要发生在膜表面，膜可以对α-Fe₂O₃进行有效拦截并通过反冲洗恢复通量；连续进水6个周期运行过程中，模拟废水COD去除率保持在85%以上，陶瓷膜不可逆阻力控制在总阻力的13%以下，反应体系保持了稳定运行。
- α-Fe₂O₃ /
- 催化臭氧氧化 /
- 苯酚 /
- 陶瓷膜 /
- 膜污染 /
- 膜阻力
Abstract:
Catalytic ozonation is an effective method for the treatment of phenolic wastewater. In order to study the degradation efficiency of phenolic wastewater by α-Fe₂O₃ catalytic oxidation and effectively recover the catalyst, micron-sized α-Fe₂O₃ catalytic ozonation was applied to the simulated phenol wastewater, and the catalyst dispersed in the reaction system was intercepted and recovered by the ceramic membrane to realize the continuous operation of the process. The results showed that: Under the condition of intermittent operation, COD removal rate of wastewater reached more than 97% after catalytic oxidation reaction for 30 min. The main reason for the high COD removal rate was that α-Fe₂O₃ had strong catalytic activity for ozone and strong oxidizing product ·OH was produced during catalytic oxidation.Under the condition of constant pressure, R_r accounted for more than 50% of the total resistance, which was verified by membrane fouling model fitting and series resistance model. However, when the operating pressure exceeded 30 kPa, some reversible fouling gradually transformed into irreversible fouling, and R_ir increased significantly. The formation mechanism of membrane fouling was explored by kinetic fitting. The ceramic membrane fouling model during operation was intermediate blockage or filter cake blockage. Membrane fouling mainly occurred on the membrane surface. The membrane could effectively intercept α-Fe₂O₃ and recover the flux through backwashing. During the six-cycle operation of continuous influent, COD removal rate of simulated wastewater remained above 85%, the irreversible resistance of ceramic membrane was controlled below 13% of the total resistance, and the reaction system maintained stable operation.
- α-Fe₂O₃ /
- catalytic ozonation /
- phenol /
- ceramic membrane /
- membrane fouling /
- membrane resistance

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图 1 试验装置

1—氧气瓶；2—臭氧发生器；3—臭氧浓度检测器；4—反应器；5—粉末催化剂/废水混合体系；6—陶瓷膜；7—曝气头；8—磁转子；9—磁力搅拌器；10—集水瓶；11—电子天平；12—给水池；13—水泵。

Figure 1. Experimental apparatus

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图 2 膜污染堵塞模型

Figure 2. Membrane fouling blocking model

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图 3 催化氧化效果

Figure 3. Catalytic oxidation effect

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图 4 α-Fe₂O₃和陶瓷膜吸附去除COD差异

Figure 4. Difference of COD removal by α-Fe₂O₃ and ceramic membrane adsorption

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图 5 催化氧化和陶瓷膜对O₃的分解作用

Figure 5. Catalytic oxidation and decomposition of ozone by ceramic membrane

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图 6 TBA捕获·OH对COD去除率的影响

Figure 6. Effect of TBA capture ·OH on COD removal rate

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图 7 操作压力对纯水渗透通量的影响

Figure 7. Effect of operating pressure on pure water permeation flux

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图 8 操作压力对陶瓷膜过滤影响

Figure 8. Effect of operating pressure on ceramic membrane filtration

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图 9 膜污染堵塞模型拟合结果

Figure 9. Fitting results of membrane fouling blockage model

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图 10 连续进水过程COD去除率和陶瓷膜阻力变化

Figure 10. COD removal rate and ceramic membrane resistance change in continuous influent process

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表 1 膜堵塞模型公式

Table 1. Formula of membrane blocking model

污染模型	模型公式
完全堵塞	$\dfrac{P}{ { {P_0} } } = \dfrac{1}{ {1 - {k_{\rm{b}}}t} }$
中间堵塞	$\dfrac{P}{ { {P_0} } } = \exp ({k_{\rm{i}}}{J_0}t)$
滤饼堵塞	$\dfrac{P}{ { {P_0} } } = 1 + {k_{\rm{c}}}{J_0}^2t$
标准堵塞	$\dfrac{P}{ { {P_0} } } = {\left(1 - \dfrac{ { {k_{\rm{s}}}{J_0}t} }{2}\right)^{ - 2} }$
注：P和P₀当前状态的跨膜压差(TMP)，kPa；$ {k_{\rm{b}}} $、${k_{\rm{i}}}$、$ {k_{\rm{c}}} $及$ {k_{\rm{s}}} $为污染模型的拟合参数。

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表 2 催化氧化准一级动力学参数

Table 2. Pseudo-first-order kinetics parameters of catalytic oxidation

反应条件	动力学参数
反应条件	k/s⁻¹	R²	S
O₃	−0.110	0.986	0.993
O₃-膜	−0.118	0.987	0.993
O₃-α-Fe₂O₃	−0.304	0.990	0.995
O₃-α-Fe₂O₃-膜	−0.356	0.994	0.997

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表 3 连续运行过程COD去除率变化

Table 3. Change of COD removal rate during continuous operation

时间/min	30	60	90	120	150	180
COD去除率/%	86.91	86.25	85.28	86.33	86.13	86.01

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