Preparation of CaCl2-heat treated coal slime based composite catalytic material and its performance toward phenol degradation by activating peroxymonosulfate
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摘要: 基于我国煤泥当前综合利用现状与煤矿集聚区地下水体污染治理的迫切需求，以煤泥(CS)为原料，添加不同质量的CaCl2作为活化剂，采用混合绝氧煅烧的方式制备了不同配比的煤泥基复合催化材料，利用X射线衍射(XRD)、扫描电镜(SEM)、比表面积测试(BET)、红外光谱(FT-IR)、X射线光电子能谱(XPS)、拉曼光谱等手段对其进行表征，并研究其用于活化过一硫酸氢钾复合盐(PMS)和催化降解水中苯酚的性能。结果表明：CaCl2-热处理煤泥制得的催化材料能高效活化PMS和降解苯酚；当煤泥与CaCl2质量比为4∶3时所制备的复合材料应用效能最优，苯酚降解率可达100 %；降解体系中活性物种1O2起主要作用；催化材料pH值适用范围(3.0~11.0)较广，且水体中各种阴离子对苯酚降解的影响较为有限，展现出良好的应用前景。Abstract: Based on the current situation of comprehensive utilization of coal slime in China and the urgent need for water pollution control in coal mining areas, this paper uses coal slime(CS)as raw material and CaCl2 as the activator, different proportions of coal slime-based catalytic materials were prepared under anaerobic calcination, which were characterized by XRD, SEM, BET, FT-IR, XPS, Raman spectroscopy, etc. This study investigated its ability to activate peroxymonosulfate(PMS)for the catalytic degradation of phenol in wastewater. Results show that the catalytic material prepared by CaCl2-heat treated coal slime can effectively activate PMS to achieve the highly efficient degradation of phenol. In addition, when the mass ratio of coal slime and CaCl2 reach 4∶3, it shows the optimal degradation performance, whose degradation rate of phenol can reach 100 %. The active species 1O2 played a major role in the degradation system. Moreover, the catalytic materials could be applied in a wide pH range(3.0~11.0), and the influence of various anions in water on the degradation of phenol is relatively limited, indicating their good application prospect in wastewater treatment.
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Key words:
- coal slime /
- CaCl2 /
- persulfate activation /
- phenol /
- wastewater treatment
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图 1 不同活化剂用量催化剂苯酚降解曲线
Figure 1. Degradation curves of catalysts with different amount of active agent towards phenol
图 2 煤泥和不同用量CaCl2制备样品XRD图谱
Figure 2. XRD patterns of coal slime and sample prepared with different amounts of CaCl2
图 3 CS/Ca-0.75样品不同放大倍数的SEM照片
Figure 3. SEM images with different magnification of CS/Ca-0.75 sample
图 4 煤泥和不同用量CaCl2制备催化剂样品的N2等温吸脱附曲线以及孔容、孔径分布曲线
Figure 4. N2 adsorption-desorption isotherms and BJH pore size distribution plots of coal slime and catalyst samples prepared with different amounts of CaCl2
图 5 不同CaCl2用量样品红外光谱
Figure 5. FTIR spectra of catalytic materials prepared with different amounts of CaCl2
图 8 不同催化剂用量对活化PMS降解苯酚的影响曲线及其准一级动力学曲线
Figure 8. Degradation curves with different catalyst dosage towards phenol and First order kinetic curves
图 9 CS/Ca-0.75/PMS/苯酚体系中自由基淬灭实验结果
Figure 9. Results of quenching experiment on phenol degradation in CS/Ca-0.75/PMS/Phenol system
图 10 CS/Ca-0.75/PMS/苯酚体系的ESR图谱
Figure 10. ESR spectra of ·OH, SO4·- and 1O2 in CS/Ca-0.75/PMS/Phenol system
图 11 不同初始pH值对催化剂活化PMS降解苯酚的影响曲线
Figure 11. Degradation curves of catalyst with different initial pH values towards phenol
图 12 阴离子种类对CS/Ca-0.75/PMS/苯酚体系的影响
Figure 12. Effects of inorganic anions on phenol degradation in CS/Ca-0.75/PMS/Phenol system
图 13 不同PMS用量对降解苯酚的影响曲线
Figure 13. Degradation curves with different PMS dosages towards phenol
表 1 煤泥及不同用量CaCl2制备催化剂样品的孔结构特性
Table 1. Pore structure characteristics of coal slime and catalytic samples prepared with different amounts of CaCl2
样品 比表面积/(m2·g-1) 孔容/(cm3·g-1) 平均孔径/nm 纯煤泥 10.681 0.037 13.750 CS/Ca-0.25 44.333 0.048 4.344 CS/Ca-0.5 36.412 0.044 4.883 CS/Ca-0.75 21.241 0.034 6.387 CS/Ca-1 18.406 0.032 6.945 CS/Ca-1.5 18.182 0.024 5.599 
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