Treatment of wastewater containing 1,3-DHB by laccase immobilized in modified ZSM-5 molecular sieves assisted by ultrosonic

doi:10.16085/j.issn.1000-6613.2017-1845

Abstract

Abstract: Using the modified ZSM-5 molecular sieve (ZSM-5_m) with micro-mesoporous structure as a support, the laccase was immobilized by physical adsorption method (Lac/ZSM-5_m). The morphology structure, pore size distribution and immobilization of laccase on the support were characterized by scanning electron microscopy, surface area and pore size analyzer, and the laser scanning confocal fluorescence microscopy. The results showed that Lac/ZSM-5_m had large number of micro nano pores on the support surface with a most probable pore size of 24.8nm. The specific surface area of the ZSM-5_m decreased slightly after the laccase was successfully adsorbed and immobilized in ZSM-5_m. Compared with the free laccase, the immobilized one had a better tolerance to the pH and temperature. The optimal temperature and pH were 50℃ and 3.0-7.0, respectively. It had good operation stability and kept at 69.2% after 10 batch reactions. Taking resorcinol (1,3-DHB) as the target pollutant, the influence of Lac/ZSM-5_m on 1,3-DHB degradation at different initial concentrations was investigated. It was further found that the system conforms to the heterogeneous enzyme reactionkinetics model α(1-α)=(K·t)^χ. Under the following conditions:the ultrasonic power of 120W(45kHz), the temperature of 50℃, pH of 4.0, the initial concentration of 1,3-DHB of 30mg/L, and the dosage of Lac/ZSM-5_m of 8.0g/L, the degradation rate of 1,3-DHB reached 79.4%, which showed a better catalytic activity. The contact reaction assisted by the ultrasonic ZSM-5_m with porous structure can provide the channel for laccase and pollutants, shorten the diffusion of substrate and intermediates in the molecular sieve in the distance, and significantly improve the performance of mass transfer and have a potential commercial value for the treatment of toxic and harmful industrial organic wastewaters.

Key words: ZSM-5, laccase, immobilized enzyme, 1,3-DHB, ultrasonic

摘要： 采用具有微介双孔结构改性ZSM-5分子筛（ZSM-5_m）为载体，以物理吸附法固定化漆酶（Lac/ZSM-5_m），利用扫描电子显微镜、比表面及孔径分析仪和激光扫描共聚焦荧光显微镜对Lac/ZSM-5_m的形貌结构、孔径分布及漆酶在载体上固定化进行表征。结果表明Lac/ZSM-5_m表面有大量微纳米级孔道，最可几孔径为24.8nm，漆酶成功吸附固定于ZSM-5_m内部，Lac/ZSM-5_m比表面积略有减小。与游离漆酶相比，对pH和温度均表现出较好的耐受性，最适温度为50℃，在pH=3.0～7.0较稳定，具有良好的操作稳定性，循环使用10次后，仍能保持初始酶活的69.2%。以间苯二酚（1，3-DHB）为目标污染物，考察不同1，3-DHB初始浓度下Lac/ZSM-5_m对其降解性能的影响，发现该体系下符合非均相酶催反应动力学模型α（1–α）=（K·t）^χ。在超声功率为120W（45kHz），温度为50℃、pH为4.0、1，3-DHB的初始浓度为30mg/L、Lac/ZSM-5_m用量8.0g/L条件下，反应8h，对1，3-DHB的降解率达到79.4%，表现较好的催化活性。超声辅助下ZSM-5_m多孔结构可以为漆酶与污染物的接触反应提供通道，缩短底物和中间产物在分子筛孔道中的扩散距离，能显著提高传质性能，对有毒有害的工业有机废水的处理有潜在的商业应用价值。

关键词: ZSM-5, 漆酶, 固定化酶, 间苯二酚, 超声

CLC Number:

X703

ZHANG Haonan, TANG Hai, LIU Fangzhou, WANG Dandan, ZHOU Qinghua, YAN Youbin. Treatment of wastewater containing 1,3-DHB by laccase immobilized in modified ZSM-5 molecular sieves assisted by ultrosonic[J]. Chemical Industry and Engineering Progress, 2018, 37(08): 3214-3221.

张昊楠, 唐海, 刘方舟, 王丹丹, 周清华, 颜酉斌. 超声辅助改性ZSM-5分子筛固定化漆酶处理间苯二酚废水[J]. 化工进展, 2018, 37(08): 3214-3221.

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