载铜地质聚合物微球的制备及其催化降解双酚S的性能

doi:10.16085/j.issn.1000-6613.2023-1322

摘要/Abstract

摘要：

传统的芬顿反应因在废水处理过程中会产生大量富含金属污泥而应用受限。本研究采用悬浮固化法得到了一种低成本、易回收、绿色的多孔地质聚合物微球（GM），将其作为载体通过浸渍法制备了载铜地质聚合物微球（Cu-GM），作为类芬顿反应催化剂，催化H₂O₂降解水中的双酚S（BPS）。SEM、XRD、BET和XPS等一系列表征结果表明，Cu^+/2+被稳定固定在GM表面。进一步探究了Cu-GM用量、H₂O₂用量、BPS浓度和溶液初始pH对催化降解的影响。结果表明，在优化条件下，Cu-GM在480min内对BPS的去除率可达99.3%，催化降解过程符合一级反应动力学。通过自由基淬灭实验发现，在催化降解过程中·OH和¹O₂是主要活性物质。循环实验表明Cu-GM具有良好的重复利用性，在去除水中有机污染物方面有着极大的应用潜力。

关键词: 地质聚合物微球, 铜基类芬顿, 双酚S, 催化降解, 降解机理

Abstract:

The traditional Fenton reaction has limited its application due to the generation of large amounts of metal-rich sludge during wastewater treatment. In this study, a low-cost, easy-to-recycle and green porous geopolymer microsphere (GM) was obtained by suspension curing method, and the copper-loaded geopolymer microsphere (Cu-GM) was prepared as a carrier by impregnation method as a catalyst for Fenton-like reaction, which catalyzed the degradation of bisphenol S (BPS) in water with H₂O₂. A series of characterization results, such as SEM, XRD, BET and XPS, showed that that Cu^+/2+ was stably immobilized on the GM surface. The effects of Cu-GM dosage, H₂O₂ dosage, BPS concentration and initial pH of the solution on the catalytic degradation were further investigated. The results indicated that under the optimized conditions, the removal of BPS by Cu-GM could reach 99.3% within 480min, and the catalytic degradation process conformed to the first-order reaction kinetics. The free radical burst experiment revealed that ·OH and ¹O₂ were the main active substances in the catalytic degradation process. The bad-cycle experiments showed that Cu-GM had good reusability and great potential for application in removing organic pollutants in water.

Key words: geopolymer microspheres, copper-based Fenton-like, bisphenol S, catalytic degradation, degradation mechanism

中图分类号:

TQ426.6

张政, 刘琳, 李子晨, 王梦琦, 黄春燕, 葛圆圆. 载铜地质聚合物微球的制备及其催化降解双酚S的性能[J]. 化工进展, 2024, 43(9): 5290-5301.

ZHANG Zheng, LIU Lin, LI Zichen, WANG Mengqi, HUANG Chunyan, GE Yuanyuan. Preparation of copper-loaded geopolymer microspheres and their catalytic degradation of bisphenol S[J]. Chemical Industry and Engineering Progress, 2024, 43(9): 5290-5301.

图/表 19

图1 CuSO4溶液浓度对催化剂性能的影响（m=0.04g、pH=4.0、c0=10mg/L、V=50mL、T=298K、VH2O2=0.5mL、t=480min）

图2 SEM图和元素映射图

图3 GM和Cu-GM的表征分析

图4 不同体系对BPS的去除率（m=0.04g、pH=4、c0=10mg/L、V=50mL、T=298K、VH2O2=0.5mL、t=480min）

图5 Cu-GM添加量对BPS去除率的影响和TOC去除率

图6 不同Cu-GM添加量下催化降解BPS的反应动力学（pH=4、c0=10mg/L、V=50mL、VH2O2=0.5mL、T=298K）

表1 不同Cu-GM添加量下催化降解BPS的动力学参数

催化剂添加量 /g	一级动力学模型参数		二级动力学模型参数
催化剂添加量 /g	k₁×10³/min^-1	R²	k₂×10⁴/L·mg^-1·min^-1	R²
0.02	3.78	0.995	8.24	0.938
0.04	5.82	0.985	21.5	0.849
0.06	6.75	0.980	31.8	0.814
0.08	8.22	0.960	57.4	0.707

图7 H2O2添加量对BPS去除率的影响（m=0.04g、pH=4、c0=10mg/L、V=50mL、T=298K）

图8 不同H2O2添加量下催化降解BPS的反应动力学（m=0.04g、pH=4、c0=10mg/L、V=50mL、T=298K）

表2 不同H2O2添加量下催化降解BPS的动力学参数

H₂O₂添加量 /mL	一级动力学模型		二级动力学模型
H₂O₂添加量 /mL	k₁×10³/min^-1	R²	k₂×10⁴/L·mg^-1·min^-1	R²
0.25	4.05	0.992	8.06	0.931
0.50	5.82	0.985	21.5	0.848
0.75	7.05	0.972	34. 6	0.774
1.00	9.16	0.937	77.9	0.605

图9 BPS浓度对Cu-GM去除BPS的影响（m=0.04g、pH=4、V=50mL、VH2O2=0.5mL、T=298K）

图10 BPS浓度对Cu-GM去除BPS的反应动力学（m=0.04g、pH=4、c0=10mg/L、V=50mL、VH2O2=0.5mL、T=298K）

表3 不同BPS浓度下催化降解BPS的动力学参数

BPS浓度 /mg·L^-1	一级动力学模型`		二级动力学模型
BPS浓度 /mg·L^-1	k₁×10³/min^-1	R²	k₂×10⁴/L·mg^-1·min^-1	R²
5	9.22	0.896	77. 7	0.530
10	5.82	0.985	21.5	0.848
20	4.45	0.969	10.9	0.860
30	3.45	0.971	6.46	0.900
40	2.72	0.973	4.28	0.920

图11 pH对去除BPS的影响（m=0.04g、c0=10mg/L、V=50mL、VH2O2=0.5mL、T=298K）

图12 不同pH下催化降解BPS的反应动力学（m=0.04g、c0=10mg/L、V=50mL、VH2O2=0.5mL、T=298K）

表4 不同pH下催化降解BPS的动力学参数

pH	一级动力学模型		二级动力学模型
pH	k₁×10³/min^-1	R²	k₂×10⁴/L·mg^-1·min^-1	R²
2	9.51	0.938	414.8	0.376
3	6.42	0.986	44.0	0.676
4	5.35	0.991	21.5	0.848
5	4.70	0.989	1.68	0.899
6	4.58	0.985	4.87	0.921

图13 淬灭实验和反应动力学（m=0.04g、pH=4、c0=10mg/L、V=50mL、T=298K、VH2O2=0.5mL、cp-BQ=cTBA=cFFA=10mmol/L)

图14 催化剂的可重复使用性能（m=0.04g、pH=4、c0=10mg/L、V=50mL、T=298K、t=480min、VH2O2=0.5mL）

表5 Cu-GM与文献中其他催化剂催化降解BPS实验效果的对比

催化剂	外观形貌	pH	浓度/mg·L^-1	去除率/%	参考文献
Cu-GM	微米级球形	4	10	99.3	本文
CuFe₂O₄/SBC	纳米级颗粒	7	20	84.5	[37]
CoFe-PBA	纳米级颗粒	5.89	20	73.77	[38]
A-boron	纳米级颗粒	7	10	97.0	[39]
S-nZVI	纳米级颗粒	5.6	5	92.8	[40]
CuCo₂S₄	纳米片	7.2	10μmol/L	100	[41]

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