中空纤维膜臭氧接触式反应器传质机理分析

doi:10.16085/j.issn.1000-6613.2023-0307

化工进展 ›› 2024, Vol. 43 ›› Issue (2): 1089-1097.DOI: 10.16085/j.issn.1000-6613.2023-0307

• 资源与环境化工 • 上一篇

中空纤维膜臭氧接触式反应器传质机理分析

姚福春¹^,²(), 毕莹莹¹, 唐晨², 杜明辉¹, 李泽莹¹, 张耀宗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，北京 100012
^2.华北理工大学建筑工程学院，河北唐山 063000

收稿日期:2023-03-01 修回日期:2023-05-23 出版日期:2024-02-25 发布日期:2024-03-07
通讯作者: 张耀宗,孙晓明
作者简介:姚福春（1996—），男，硕士研究生，研究方向为水污染控制与废水资源化。E-mail：386439071@qq.com。
基金资助:
国家重点研发计划(2022YFC3901301);黄河流域生态保护和高质量发展联合研究一期项目(2022-YRUC-01-0404);中央级公益性科研院所基本科研业务费专项(2022YSKY-09);中国环境科学研究院国家环境保护生态工业重点实验室开放基金(2022KFF-15)

Analysis of the mass transfer mechanism in a hollow fiber membrane ozone contact reactor

YAO Fuchun¹^,²(), BI Yingying¹, TANG Chen², DU Minghui¹, LI Zeying¹, ZHANG Yaozong²(), SUN Xiaoming¹()

^1.Key Laboratory of Ecological Industry, Chinese Research Academy of Environmental Sciences State Environmental Protection, Beijing 100012, China
^2.School of Architecture and Civil Engineering, North China University of Science and Technology, Tangshan 063000, Hebei, China

Received:2023-03-01 Revised:2023-05-23 Online:2024-02-25 Published:2024-03-07
Contact: ZHANG Yaozong, SUN Xiaoming

摘要/Abstract

摘要：

将疏水性聚四氟乙烯（PTFE）中空纤维膜组装成膜接触器，开发了膜接触式臭氧（O₃）传质技术。对比了气泡传质和膜接触传质的差异，通过O₃传质模型和阻力模型对该技术的主要影响因素和传质机理进行了研究。结果表明，O₃可以有效地通过疏水性PTFE膜进行传质，当搅拌速度达到1500r/min时，膜传质的表观传质系数（0.3049min^-1）与气泡传质（0.3109min^-1）相当。同时，膜表面的疏水结构将尾气的湿度降低到0.8g/m³以下，远低于气泡传质（>11.5g/m³），符合进入臭氧发生器的标准，具备回收氧气的可行性。O₃的传质通量受液体流速、pH、污染物浓度、气体流量以及进气O₃浓度的影响。在pH=11、苯酚浓度为0或pH=7、苯酚浓度为20mg/L时，传质通量达到了0.16g/(m²·h)。O₃传质过程的传质阻力主要由膜阻力和液相阻力组成，而通过液相条件控制可以有效减小液相阻力，因此进一步降低传质阻力需要膜技术的发展。

关键词: 疏水性聚四氟乙烯中空纤维膜, 臭氧, 接触式反应器, 传质

Abstract:

A membrane-contact ozone (O₃) mass transfer technology was developed by assembling hydrophobic PTFE hollow fiber membrane into a membrane contactor. The differences between bubble mass transfer and membrane contact mass transfer were compared. The main influencing factors and mass transfer mechanism of the technology were studied by O₃ mass transfer model and resistance model. The results showed that O₃ can be effectively transferred through the hydrophobic PTFE membrane. When the stirring speed reached 1500r/min, the apparent mass transfer coefficient of membrane mass transfer (0.3049min^-1) was comparable to that of bubble mass transfer (0.3109min^-1). At the same time, the hydrophobic structure of the membrane surface reduced the humidity of the exhaust gas to below 0.8g/m³, which was much lower than the bubble mass transfer (>11.5g/m³), which met the standard of entering the ozone generator and had the feasibility of recovering oxygen. The mass transfer flux of O₃ was affected by liquid flow rate, pH value, pollutant concentration, gas flow rate and inlet O₃ concentration. When pH=11, phenol concentration was 0 or pH=7, phenol concentration was 20mg/L, the mass transfer flux reached 0.16g/(m²·h). The mass transfer resistance of the O₃ mass transfer process was mainly composed of membrane resistance and liquid phase resistance, and the liquid phase resistance can be effectively reduced by controlling the liquid phase conditions. Therefore, further reducing the mass transfer resistance required the development of membrane technology.

Key words: hydrophobic PTFE hollow fiber membrane, ozone, contact reactor, mass transfer

中图分类号:

X703

姚福春, 毕莹莹, 唐晨, 杜明辉, 李泽莹, 张耀宗, 孙晓明. 中空纤维膜臭氧接触式反应器传质机理分析[J]. 化工进展, 2024, 43(2): 1089-1097.

YAO Fuchun, BI Yingying, TANG Chen, DU Minghui, LI Zeying, ZHANG Yaozong, SUN Xiaoming. Analysis of the mass transfer mechanism in a hollow fiber membrane ozone contact reactor[J]. Chemical Industry and Engineering Progress, 2024, 43(2): 1089-1097.

图/表 13

图1 O3膜传质和O2富集过程示意图

图2 疏水PTFE中空纤维膜横截面和外表面的扫描电镜（SEM）图

表1 疏水性PTFE中空纤维膜参数

参数名称	数值
膜参数
内径/mm	1.3
外径/mm	2.3
膜厚/mm	0.5
表面孔径分布/μm	5~10
接触角/(°)	105.7
起泡压力/MPa	0.025
膜接触反应器参数
膜丝数量/根	20
有效长度/mm	933
有效接触面积/mm²	134762.5

图3 实验装置图

图4 不同搅拌速度下膜传质和气泡传质时液相O3浓度随时间的变化情况

表2 基于Fick第一定律的拟合结果

搅拌速度 /r·min^-1	传质参数
	膜传质		气泡传质
	K_La/s^-1	R²	K_La/s^-1	R²
0	1.6×10^-3	0.9942	3.0×10^-3	0.9931
500	2.2×10^-3	0.9904	4.2×10^-3	0.98321
1000	4.4×10^-3	0.9913	5.2×10^-3	0.9909
1500	5.1×10^-3	0.9927	5.2×10^-3	0.9937

图5 不同气体流量下膜传质和气泡传质的尾气湿度变化情况

图6 液相条件控制下O3的传质通量随液体流速的变化情况

图7 10mg/L苯酚溶液在不同液体流速下的变化情况

图8 气相条件控制下O3传质通量随液体流速的变化情况

图9 四种影响因素控制下的尾气O3质量流量变化情况

图10 不同气体流量下的Wilson图

图11 四种影响因素控制下Rg+m+l和Rg+m随液体流速的变化情况

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中空纤维膜臭氧接触式反应器传质机理分析

Analysis of the mass transfer mechanism in a hollow fiber membrane ozone contact reactor

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