焦粉高效活化过硫酸盐对苯胺的降解性能

doi:10.16085/j.issn.1000-6613.2021-2363

摘要/Abstract

摘要：

焦粉作为焦化/煤化企业的低附加值副产物，用作污染控制材料是其高价值应用的一条重要途径。本文对焦粉形貌与成分进行表征分析，通过苯胺降解动力学和影响因素之间的交互作用评估焦粉活化过硫酸盐的催化性能，并初步探讨了相关机理。表征结果显示焦粉表面粗糙，有清晰的孔隙。活性测试结果显示，1g/L焦粉可以高效活化5mmol/L过硫酸盐降解20mg/L苯胺，反应120min后苯胺去除率高于99%，其中灰分对苯胺降解无贡献。增加焦粉剂量和过硫酸盐浓度均可提高苯胺的降解效率。焦粉在pH 3~11范围内均可高效活化过硫酸盐降解苯胺，去除率维持在83%以上。此外，焦粉具有应用于修复复杂水体中有机污染物的潜能，在Cl^-、HCO $_{3}^{-}$ 和SO $_{4}^{2 -}$ 干扰下，体系中苯胺去除率维持在90%以上。响应曲面分析表明，焦粉可以高效活化过硫酸盐降解苯胺，且焦粉剂量与过硫酸钠浓度的交互作用强，二者决定了苯胺的最终去除率。自由基淬灭实验证明焦粉活化过硫酸盐降解苯胺过程中，主要产生的活性氧物种为O $_{2}^{\cdot -}$ 和·OH。本文的研究结果可为低附加值的煤基副产物高价值应用提供指导，并为进一步发展环境友好的水污染控制与资源化技术提供新契机。

关键词: 焦粉, 焦化废水, 污染控制, 活化过硫酸盐

Abstract:

Coke powder is a low-value by-product of coking/coal industries, and the use of coke powder as a pollution control material is an important field for its high-value application. The morphology and elemental composition of coke powder were characterized. The performance of persulfate activated by coke powder was evaluated by the removal efficiency of aniline. The characterization results showed that the coke powder had a rough surface with a pore structure. The activity test results presented that 5mmol/L persulfate could be efficiently activated by 1g/L coke powder, and more than 99% aniline (20mg/L) was degraded after 120min. The ash in CP did not contribute to aniline degradation. The degradation efficiency of aniline could be improved by increasing coke powder dosage and persulfate concentration. Moreover, coke powder could efficiently activate persulfate to degrade aniline in the range of pH 3—11, and the aniline degradation efficiency could be maintained above 83%. Meanwhile, aniline degradation in the system was maintained above 90% in the presence of Cl^-, HCO $_{3}^{-}$ or SO $_{4}^{2 -}$ , indicating that coke powder had the potential to be used to repair organic pollutants in complex wastewater. Response surface analysis showed that coke powder could efficiently activate persulfate to degrade aniline, and the interaction between coke powder dosage and persulfate concentration was strong, both of which contributed to the degradation efficiency of aniline. Furthermore, free radical quenching tests proved that O $_{2}^{\cdot -}$ and ·OH were the dominant radicals generated in the system of coke powder with persulfate. The findings can provide guidance for the high-value application of low-value coal-based by-products, and provide new opportunities for the further development of environmentally friendly wastewater pollution control and resource utilization technologies.

Key words: coke powder, aniline, pollution control, persulfate activation

中图分类号:

徐天缘, 郑茜, 王连娟, 陈婷, 魏鑫鹏. 焦粉高效活化过硫酸盐对苯胺的降解性能[J]. 化工进展, 2022, 41(6): 3314-3323.

XU Tianyuan, ZHENG Xi, WANG Lianjuan, CHEN Ting, WEI Xinpeng. Persulfate activation by coke powder for aniline degradation[J]. Chemical Industry and Engineering Progress, 2022, 41(6): 3314-3323.

图/表 13

表1 BBD设计因素与代码

序号	代码	因素	水平
序号	代码	因素	-1	0	1
1	X1	焦粉/g·L^-1	0.5	1	1.5
2	X2	pH	3	7	11
3	X3	过硫酸钠/mmol·L^-1	2	5	8

图1 焦粉SEM图和EDS图

表2 焦粉的元素组成

元素	质量分数/%	摩尔分数/%
C	35.66	48.06
O	38.37	38.82
Si	12.20	7.03
Al	3.72	2.23
Fe	4.82	1.40
Ca	2.97	1.20
Mg	0.78	0.52
Na	0.63	0.44
Ti	0.64	0.22
K	0.21	0.09

图2 不同实验条件下苯胺降解效果图

图3 苯胺溶液pH对焦粉活化过硫酸盐降解苯胺效率与动力学的影响

图4 不同焦粉剂量对焦粉活化过硫酸钠降解苯胺效率与动力学的影响

图5 过硫酸钠浓度对焦粉活化过硫酸盐苯胺降解效率与动力学的影响

表3 二次回归模型的方差分析（以苯胺去除率为响应对象）

方差来源	平方和	自由度	均方	F	P>F
Model	923.03	9	102.56	24.63	0.0002
A	425.34	1	425.34	102.16	< 0.0001
B	65.25	1	65.25	15.67	0.0055
C	287.98	1	287.98	69.17	< 0.0001
AB	3.12	1	3.12	0.7503	0.4151
AC	42.54	1	42.54	10.22	0.0151
BC	11.29	1	11.29	2.71	0.1436
A2	50.43	1	50.43	12.11	0.0103
B2	32.47	1	32.47	7.80	0.0268
C2	1.06	1	1.06	0.2556	0.6287
残差	29.14	7	4.16
拟合不足	29.14	3	9.71
纯误差	0	4	0
总误差	952.18	16
R²= 0.969

图6 焦粉活化过硫酸盐降解苯胺的响应面分析

图7 不同阴离子对焦粉活化过硫酸盐降解苯胺的影响

图8 不同活性氧物种抑制剂对苯胺降解效果的影响

图9 酸浸后焦粉SEM-EDS、XRD和活化过硫酸钠降解苯胺效果

图10 焦粉重复使用活化过硫酸盐性能测试

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