臭氧氧化动力学模型及反应器建模研究进展

doi:10.16085/j.issn.1000-6613.2021-2291

摘要/Abstract

摘要：

臭氧化技术可以实现对有机污染物的有效去除，同时兼具绿色环保、工艺流程简单等特点而被广泛应用，而臭氧化模型的构建可以实现对污染物减排的有效预测，对于臭氧化处理污水的工程应用意义重大。本文介绍了臭氧化技术的基本原理，并着重综述了臭氧氧化的动力学模型和反应器建模的研究进展。在臭氧氧化模型的建立中，臭氧的传质和反应是两个最重要的因素。本文首先讨论了臭氧的传质过程，并对其气液两相模型进行了阐述。然后针对忽略臭氧传质的液-液或液-固体系，并根据反应机理，分别总结了常规臭氧氧化、均相催化臭氧氧化和非均相催化臭氧氧化的动力学模型。在充分研究了臭氧氧化的动力学模型后，将其应用到具体反应器的建模中，并总结出模型建立的基本假设。最后指出现有模型存在的一些问题并给出相关的建议，提出臭氧化模型构建的出处是优化工业反应器，实现工程应用。

关键词: 臭氧, 传质过程, 动力学, 模型预测控制, 化学反应器

Abstract:

Ozonation can effectively remove organic pollutants, and thus has been widely used because of its environmental protection and simple process. Ozonation model can effectively predict the pollutant emission reduction, which is of great significance to the engineering application of ozonation in wastewater treatment. This article introduced the basic principle of ozonation, and emphatically reviewed the latest research progress of the kinetics model and reactor modeling of ozonation. The mass transfer and reaction of ozone are the two most important factors in the establishment of ozone oxidation model. The article first introduced the mass transfer process of ozone between gas and liquid phase and expounded the associated models. Then, according to the reaction mechanism, the kinetics models of common ozonation, homogeneous catalytic ozonation, and heterogeneous catalytic ozonation were summarized respectively for liquid-liquid or liquid-solid systems without considering ozone mass transfer. Subsequently, the models were applied to model specific reactors, and the basic assumptions of the models were summarized. Finally, the article pointed out some problems in the existing models and gave some relevant suggestions. It is suggested that the construction of ozonation model should always aim at optimizing the industrial reactors and realizing its engineering applications.

Key words: ozone, mass transfer process, kinetics, model-predictive control, chemical reactors

中图分类号:

X703

马云飞, 王建兵, 贾超敏, 邢懿心, 柯述, 张先. 臭氧氧化动力学模型及反应器建模研究进展[J]. 化工进展, 2022, 41(S1): 556-570.

MA Yunfei, WANG Jianbing, JIA Chaomin, XING Yixin, KE Shu, ZHANG Xian. Recent progress of kinetics model and reactor modeling of ozonation[J]. Chemical Industry and Engineering Progress, 2022, 41(S1): 556-570.

图/表 8

图1 臭氧分子的共振结构

表1 不同催化臭氧氧化体系处理有机物具体机理

催化臭氧体系	催化剂	催化机理/反应式	参考文献
均相催化体系	亚铁离子Fe²⁺	$F e 2 + + O 3 → F e O 2 + + O 2$ $F e O 2 + + H 2 O → F e 3 + + · O H + O H -$ $F e O 2 + + F e 2 + + 2 H + → 2 F e 3 + + H 2 O$	［32］
非均相催化体系	镍基层状双氢氧化物Ni^Ⅱ(OH)₂	$N i Ⅱ O H 2 + O 3 → N i Ⅳ O O H 2 + O 2$ $2 N i Ⅳ O O H 2 → 2 N i Ⅱ O H 2 + O 2$ $3 N i Ⅳ O O H 2 → N i Ⅱ O H 2 + 2 N i Ⅲ O (O H) 2 + H 2 O + O 2$	［33］
均相催化体系	亚钴离子Co²⁺	$C o 2 + + C 2 O 4 2 - → C o C 2 O 4$ $C o C 2 O 4 + O 3 → C o C 2 O 4 + + O 3 -$ $C o C 2 O 4 + → C o 2 + + · C 2 O 4 -$ $· C 2 O 4 - + O 2 + O 3 + · O H → 2 C O 2 + O 2 - + O 3 - + O H -$	［34］
非均相催化体系	负载贵金属催化剂 Ag-Fe₂O₄	$A g I N i Ⅱ F e 2 O 4 - O H - + O 3 → A g I N i Ⅱ F e 2 O 4 - O H - - O 3$ $A g I N i Ⅱ F e 2 O 4 - O H - - O 3 → A g 0 N i Ⅲ F e 2 O 4 - O H - - O 3$ $A g 0 N i I I I F e 2 O 4 - O H - - O 3 → A g I N i Ⅲ F e 2 O 4 + · H O 2 - + O 2 -$ $· H O 2 - + O 3 → · O 2 - + O 2 + · O H$	［35］
非均相催化体系	多金属氧化物 MnFe₂O₄	$M n Ⅱ F e 2 O 4 - O H - + O 3 → M n Ⅱ F e 2 O 4 - O H - - O 3$ $M n Ⅱ F e 2 O 4 - O H - - O 3 → M n Ⅲ F e 2 O 4 + H O 2 · + O 2 - ·$ $O 3 + H O 2 · - → · O H + O 2 · - + O 2$ $4 M n Ⅲ + 2 O 2 - → 4 M n Ⅱ + O 2$	［36］

表1 不同催化臭氧氧化体系处理有机物具体机理

催化臭氧体系	催化剂	催化机理/反应式	参考文献
均相催化体系	亚铁离子Fe²⁺	$F e 2 + + O 3 → F e O 2 + + O 2$ $F e O 2 + + H 2 O → F e 3 + + · O H + O H -$ $F e O 2 + + F e 2 + + 2 H + → 2 F e 3 + + H 2 O$	［32］
非均相催化体系	镍基层状双氢氧化物Ni^Ⅱ(OH)₂	$N i Ⅱ O H 2 + O 3 → N i Ⅳ O O H 2 + O 2$ $2 N i Ⅳ O O H 2 → 2 N i Ⅱ O H 2 + O 2$ $3 N i Ⅳ O O H 2 → N i Ⅱ O H 2 + 2 N i Ⅲ O (O H) 2 + H 2 O + O 2$	［33］
均相催化体系	亚钴离子Co²⁺	$C o 2 + + C 2 O 4 2 - → C o C 2 O 4$ $C o C 2 O 4 + O 3 → C o C 2 O 4 + + O 3 -$ $C o C 2 O 4 + → C o 2 + + · C 2 O 4 -$ $· C 2 O 4 - + O 2 + O 3 + · O H → 2 C O 2 + O 2 - + O 3 - + O H -$	［34］
非均相催化体系	负载贵金属催化剂 Ag-Fe₂O₄	$A g I N i Ⅱ F e 2 O 4 - O H - + O 3 → A g I N i Ⅱ F e 2 O 4 - O H - - O 3$ $A g I N i Ⅱ F e 2 O 4 - O H - - O 3 → A g 0 N i Ⅲ F e 2 O 4 - O H - - O 3$ $A g 0 N i I I I F e 2 O 4 - O H - - O 3 → A g I N i Ⅲ F e 2 O 4 + · H O 2 - + O 2 -$ $· H O 2 - + O 3 → · O 2 - + O 2 + · O H$	［35］
非均相催化体系	多金属氧化物 MnFe₂O₄	$M n Ⅱ F e 2 O 4 - O H - + O 3 → M n Ⅱ F e 2 O 4 - O H - - O 3$ $M n Ⅱ F e 2 O 4 - O H - - O 3 → M n Ⅲ F e 2 O 4 + H O 2 · + O 2 - ·$ $O 3 + H O 2 · - → · O H + O 2 · - + O 2$ $4 M n Ⅲ + 2 O 2 - → 4 M n Ⅱ + O 2$	［36］

图2 用户操作界面示意图[42]

表2 臭氧传质系数计算的经验公式

表示参数	经验表达式	参考文献
气相流速	$K L a = 0.0344 U g 0.8692$	［46］
气泡粒径上升速度进气流量	$K L a = 2.357 g ρ L - ρ G d b 2 σ 0.735 4 D L v g π d b 6 U g d b v g$	［47］
气相流速、微孔孔径	$K L a = 0.018 e 0.7595 d u g 0.0017 d 2 + 0.1024 d + 0.3277$	［48］
水质指标pH	$K L a = 0.2497 p H 0.0634 × 48 3.9 × 10 - 3 p H 1.365$	［49］
进水流量、进气流量	$K L a = 3.96 × 108 Q l 1.53 Q g 0.4$	［50］
气泡粒径、上升速度	$K L = 1.10 × 10 - 7 μ L ρ L d b σ 0.5 - 2.74 4 D L v g π d b$	［47］
气泡粒径、上升速度	$K L = 4 D L v g π d b$	［51］

表2 臭氧传质系数计算的经验公式

表示参数	经验表达式	参考文献
气相流速	$K L a = 0.0344 U g 0.8692$	［46］
气泡粒径上升速度进气流量	$K L a = 2.357 g ρ L - ρ G d b 2 σ 0.735 4 D L v g π d b 6 U g d b v g$	［47］
气相流速、微孔孔径	$K L a = 0.018 e 0.7595 d u g 0.0017 d 2 + 0.1024 d + 0.3277$	［48］
水质指标pH	$K L a = 0.2497 p H 0.0634 × 48 3.9 × 10 - 3 p H 1.365$	［49］
进水流量、进气流量	$K L a = 3.96 × 108 Q l 1.53 Q g 0.4$	［50］
气泡粒径、上升速度	$K L = 1.10 × 10 - 7 μ L ρ L d b σ 0.5 - 2.74 4 D L v g π d b$	［47］
气泡粒径、上升速度	$K L = 4 D L v g π d b$	［51］

图3 污染物去除的机理及预测图示[66]

图4 动力学模型

表3 不同类型反应器和流型对应的动力学方程

反应器运行方式	流型	动力学公式	公式编号
理想反应器	PMF/PF/AMD	$F i 0 - F i + G i β Δ V = Δ n i Δ t$	（24）
	完全混合流	$1 τ C i 0 - C i + G i = d C i d t$	（25）
	推流流型	$- U i 0 ∂ C i ∂ h + G i = ∂ C i ∂ t$	（26）
非理想反应器	轴向扩散流型	$- U i ∂ C i ∂ h + D i ∂ 2 C i ∂ h 2 + G i = ∂ C i ∂ t$	（27）
非理想反应器	N级串联完全混合流	$1 τ i k C i k - 1 - C i k + G i k = d C i k d t$	（28）

表3 不同类型反应器和流型对应的动力学方程

反应器运行方式	流型	动力学公式	公式编号
理想反应器	PMF/PF/AMD	$F i 0 - F i + G i β Δ V = Δ n i Δ t$	（24）
	完全混合流	$1 τ C i 0 - C i + G i = d C i d t$	（25）
	推流流型	$- U i 0 ∂ C i ∂ h + G i = ∂ C i ∂ t$	（26）
非理想反应器	轴向扩散流型	$- U i ∂ C i ∂ h + D i ∂ 2 C i ∂ h 2 + G i = ∂ C i ∂ t$	（27）
非理想反应器	N级串联完全混合流	$1 τ i k C i k - 1 - C i k + G i k = d C i k d t$	（28）

表4 具体反应器动力学建模实例

臭氧氧化系统	反应器	反应体系	两相模型/流型	参考文献
O₃/GO/TiO₂/乙酸	0.5L电磁搅拌管式玻璃制半间歇式反应器	慢速动力学体系/非稳态条件	气相O₃，液相O₃、TOC（总有机碳）/气液两相均为完全混合流型	［93］
O₃/偶氮染料橙Ⅱ	5L圆柱形气泡塔，高1m、直径0.095m，半批式操作	快速反应体系/非稳态条件	气液（O₃、TOC）非理想混合/带回流的串联罐模型	［94］
O₃/TiO₂/GAC/苯胺	2L电磁搅拌半间歇式反应器	慢速动力学体系/非稳态条件	液相O₃、总有机碳/液相完全混合流型	［83］
O₃/Fe²⁺/垃圾渗滤液	改进的连续流管式反应器	恒容/稳态操作条件	液相TOC、化合物（O₃、O₂、Fe²⁺、Fe³⁺）/理想的推流流型	［95］
O₃/邻苯二酸二甲酯	玻璃柱半间歇式搅拌反应器，高1.2m，直径50mm	慢速动力学体系/非稳态条件	气相O₃，液相O₃、有机物/气液两相均为完全混合流型	［96］
O₃/氯化物水溶液	连续搅拌釜反应器	慢速动力学体系/非稳态条件	涉及气液传质，气液相O₃/液相完全混合流型	［97］
O₃/VisLED/GO/TiO₂/药物	0.5L半批次磁性搅拌圆柱形反应器，直径6.2cm	慢速、快速动力学体系/非稳态	气相O₃，液相TOC/气液两相均为完全混合流型	［98］
O₃微气泡/药物	体积为1dm³的半间歇玻璃反应器	慢速动力学体系/稳态操作条件	气相O₃，液相O₃ /气液两相均为轴向扩散模型	［99］
O₃ /靛蓝三磺酸钾溶液	带有多孔陶瓷板气体分布器的气泡柱，长80cm、内径4cm	快速动力学体系/稳态操作条件	考虑液相O₃/液相为完全混合流型	［100］

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