Preparation of Amino Modified Coal Gangue and its Adsorption of Pb (II)
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摘要:
煤矸石吸附剂的开发不仅可以对其进行有效利用，还可以降低重金属离子废水的处理成本。以晋能塔山选煤厂煤矸石为原料，通过插层、盐酸预处理以及氨基修饰的方法制备了一系列吸附材料，利用Box-Behnken对实验条件进行优化，考查了其对水中Pb（Ⅱ）的吸附性能，通过XRD、FTIR、BET、Zeta电位等手段对吸附材料的物理化学性质进行分析。结果表明：煤矸石经插层、盐酸预处理和氨基修饰后对Pb（Ⅱ）的吸附容量增大，从原矿的1.89 mg/g提升至23.02 mg/g。煤矸石表面氨基的接枝率是吸附性能的关键；吸附剂对Pb（Ⅱ）的吸附符合准二级动力学模型，等温吸附符合Langmuir 吸附模型。以煤矸石为原料制备的氨基修饰后的煤矸石具有价廉易得、吸附性能好等优点，具有潜在的工业应用价值。
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关键词:
- 煤矸石 /
- 硅烷偶联剂 /
- 吸附剂 /
- Pb(Ⅱ) /
- Box-Behnken 实验设计
Abstract:The development of coal gangue adsorbent can not only effectively utilize it, but also reduce the treatment cost of heavy metal ion wastewater. A series of adsorbent materials were prepared by intercalation, hydrochloric acid pretreatment and amino modification using coal gangue from JinnengTashan Coal Preparation Plant as raw materials. The experimental conditions were optimized by Box-Behnken experimental design method. The adsorption properties of Pb ( II ) in water were investigated. The physical and chemical properties of the adsorption materials were analyzed by XRD, FTIR, BET and Zeta potential. The results showed that the adsorption capacity of Pb ( II ) by coal gangue after intercalation, hydrochloric acid pretreatment and amino modification was increased from 1.89 mg/g of the raw ore to 23.02 mg/g. The grafting rate of amino groups on the surface of coal gangue is the key to adsorption performance. The adsorption of Pb ( II ) by the adsorbent conforms to the pseudo-second-order kinetic model, and the isothermal adsorption conforms to the Langmuir adsorption model. The amino-modified coal gangue prepared from coal gangue has the advantages of low cost, good adsorption performance, and potential industrial application value.
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Key words:
- coalgangue /
- silane coupling agent /
- adsorbent /
- Box-Behnken experimental design /
- Pb (II).
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表 1 Box-Behnken实验方案设计及结果
Table 1. Box-Behnken test design and results
序号 Factor 1 Factor 2 Factor 3 反应 X1投用量/g X2温度/℃ X3时间/h 吸附量/（mg/g） 1 1 0 -1 19.276 2 0 0 0 22.926 3 0 1 1 20.920 4 -1 1 0 17.245 5 0 0 0 22.880 6 1 0 1 20.000 7 0 0 0 22.325 8 -1 0 1 18.805 9 0 1 -1 20.397 10 0 -1 1 22.953 11 1 -1 0 19.366 12 0 0 0 23.142 13 -1 -1 0 17.844 14 0 -1 -1 21.730 15 0 0 0 22.932 16 -1 0 -1 18.129 17 1 1 0 18.950 
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表 2 实验结果方差分析表（ANOVA）
Table 2. Analysis of variance (ANOVA) for the test results
方差来源 平方和 自由度 均方 F值 P值 显著性 Model 65.79 9 7.31 43.46 < 0.000 1 ** X1-添加量 3.87 1 3.88 23.05 0.002 0 * X2-温度 2.39 1 2.39 14.26 0.006 9 * X3-时间 1.23 1 1.24 7.36 0.030 1 * X1X2 0.008 1 0.008 0.05 0.829 9 X1X3 0.000 6 1 0.000 6 0.003 0.952 2 X2X3 0.12 1 0.12 0.73 0.421 2 X1² 50.66 1 50.66 301.2 < 0.000 1 ** X2² 4.39 1 4.39 26.11 0.001 4 * X3² 0.43 1 0.43 2.56 0.153 7 残差 1.18 7 0.17 失拟项 0.8 3 0.27 2.87 0.167 6 不显著 纯误差 0.37 4 0.09 总和 66.98 16 方差 Adjust-R2 = 0.959 8 R2 = 0.982 4 注：*差异显著（P<0.05），**差异极显著（P<0.01）。
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表 3 煤矸石和氨基修饰后的煤矸石的孔结构特性
Table 3. Pore structure characteristics of coal gangue and amino modified coal gangue
比表面积/
（m2/g）总孔容积/
（cm3/g）平均孔径/
nm煤矸石 18.970 0.079 16.176 氨基修饰后的煤矸石 16.895 0.089 20.751
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表 4 氨基修饰后的煤矸石吸附Pb（Ⅱ）的Langmuir和Freundlich的吸附等温线方程常数
Table 4. Langmuir and Freundlich adsorption isotherm equation constants of Pb ( II ) adsorption on amino- modified coal gangue
Langmuir Freundlich qm/（mg/g） 29. 274 n 4.040 KL/（L/mg） 0.030 KF（mg/g） 6.723 R2 0.999 R2 0.948
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表 5 氨基修饰后的煤矸石吸附Pb（Ⅱ）的吸附动力学常数
Table 5. Adsorption kinetic constants of Pb ( II ) on amino-modified coal gangue
准一级 准二级 qe/（mg/g） 7.98 qe/（mg/g） 23.98 K1/（l/mg） 0.020 K2/（g/（mg×min）） 0.005 R2 0.979 R2 0.999
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表 6 氨基修饰后的煤矸石吸附Pb（Ⅱ）的热力学参数
Table 6. Thermodynamic parameters of Pb ( II ) adsorption on amino-modified coal gangue
反应温度/K ΔG/（kJ/mol） ΔH/（kJ/mol） ΔS/（J/mol） 298.15 -16.64 308.15 -18.57 40.69 192.31 318.15 -20.49
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