软锰矿-含油污泥基活性炭对亚甲基蓝的吸附特性

doi:10.16085/j.issn.1000-6613.2022-0304

摘要/Abstract

摘要：

以含油污泥为原料，添加适量软锰矿制备活性炭，用于吸附水中的亚甲基蓝并探究其吸附性能与吸附机制。采用SEM、BET、XPS、FTIR表征活性炭的微观形貌和物相结构，利用二维红外相关光谱探究活性炭与亚甲基蓝的吸附点位及吸附机制。结果表明，活性炭是比表面积达464.409m²/g的介孔材料，且表面含有大量的含氧官能团，活性炭吸附亚甲基蓝的过程符合准二级动力学方程和Langmuir模型，主要受化学吸附控制的单分子层吸附。结合移动窗口二维红外相关光谱分析发现，在活性炭吸附亚甲基蓝的过程中吸附较低浓度的亚甲基蓝参与的官能团较多，以各种含氧官能团为主，当亚甲基蓝浓度升高，以π-π相互作用为主；吸附机制包括氢键作用、含氧官能团参与和π-π相互作用等。

关键词: 含油污泥, 亚甲基蓝, 吸附, 吸附机理, 移动窗口二维相关光谱

Abstract:

Activated carbon was prepared from oily sludge and pyrolusite, which was used to adsorb methylene blue in water, and its adsorption performance and mechanism were explored. SEM, BET, XPS and FTIR were used to characterize the micro-morphology and phase structure of activated carbon. Two-dimensional correlation spectroscopy (2D-COS) in combination with FITR was used to explore the adsorption point and mechanism of activated carbon and methylene blue. The results showed that activated carbon was a mesoporous material with a specific surface area of 464.4m²/g, which contained a large number of oxygen-containing functional groups. The adsorption process of methylene blue by activated carbon, which was monolayer adsorption controlled by chemical adsorption, accorded with pseudo-second-order kinetic equation and Langmuir model. Combined with the results of FTIR and moving-window 2D-COS analysis, more functional groups participated in the adsorption process of methylene blue with lower concentrations, in which contain oxygen was dominant. The π-π interaction played a primary role in higher concentrations of methylene blue. The adsorption mechanism included hydrogen bonding, oxygen-containing functional groups and π-π interaction.

Key words: oil-bearing sludge, methylene blue, adsorption, adsorption mechanism, moving-window 2D-correlation spectroscopy (COS)

中图分类号:

X703

樊相汝, 羊依金, 郭旭晶, 张全碧. 软锰矿-含油污泥基活性炭对亚甲基蓝的吸附特性[J]. 化工进展, 2022, 41(12): 6664-6671.

FAN Xiangru, YANG Yijin, GUO Xujing, ZHANG Quanbi. Study on the adsorption characteristics of methylene blue by soft manganese ore-oil sludge-based activated carbon[J]. Chemical Industry and Engineering Progress, 2022, 41(12): 6664-6671.

图/表 10

图1 0-活性炭、活性炭的SEM图

表1 活性炭的孔隙结构

样品	比表面积/m²·g^-1	平均孔径/nm	孔容/cm³·g^-1
活性炭	464.409	4.190	0.449
0-活性炭	421.718	4.810	0.354

图2 活性炭的XPS谱图和FTIR谱图

图3 活性炭投加量(a)、亚甲基蓝浓度(b)以及pH(c)对亚甲基蓝吸附量的影响

图4 活性炭对亚甲基蓝的吸附动力学(a)、颗粒内扩散(b)和等温吸附(c)拟合曲线

表2 吸附动力学拟合数据

准一级动力学模型				准二级动力学
q_e/mg·g^-1	K₁/min^-1	R²		q_e/mg·g^-1	K₂/min^-1	R²
156.3393	0.1186	0.9628		170.3181	0.0011	0.9914

表3 吸附等温线拟合数据

Langmuir				Freundlich
q_m/mg·g^-1	b/L·mg^-1	R²		K_f	n	R²
209.1995	0.0343	0.9820		38.9821	3.2814	0.9596

图5 吸附后活性炭(a)和亚甲基蓝(b)的FTIR谱图

图6 活性炭吸附亚甲基蓝后的二维同步相关(a)和二维异步相关(b)光谱

图7 移动窗口二维红外相关光谱同步(a)和异步光谱图(b)

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