粉末活性炭基复合材料制备及净化含油污水的性能和机制

doi:10.6023/A22080375

摘要/Abstract

针对粉末活性炭对亲水小分子有机物吸附效率低和固液分离速度慢的问题, 本研究以粉末活性炭(PAC)、腐植酸盐(HS)、聚合氯化铝(PACl)为原料, 通过融合法成功制备了粉末活性炭基复合材料PACMC (powdered activated carbon matrix composites), 将其作为含油污水的净化吸附剂. 扫描电子显微镜-X射线能量色散谱仪(SEM-EDS)和傅里叶红外光谱(FT-IR)等表征分析确认了PACMC的微观形貌和化学组成, 证实了PAC、HS和PACl是通过化学反应生成了PACMC. PACMC具有层状多孔结构和活性官能团, 有利于含油污水分子的传输扩散和化学吸附. 通过静态吸附实验研究了PACl、PAC和PACMC对含油污水中有机物的吸附性能, 结果表明: PACMC对含油污水中有机污染物的吸附能力是PAC和PACl的2~3倍(q_e=23.04 mg•g^‒1, C₀=300 mg•L^‒1); 当吸附时间达到120 min 时, PACMC上的活性位点与含油污水中有机污染物的结合已基本达到饱和(q_e=23.04 mg•g^‒1, C₀=300 mg•L^‒1). 溶液pH值对PACMC吸附去除含油污水中有机物的影响显著, pH=3时, 吸附效果最好(q_e=27.6 mg•g^‒1, C₀=300 mg•L^‒1); 伪二级动力学方程能很好地描述含油污水中有机物在PACMC上的吸附行为, 动力学拟合结果表明其吸附过程分多步进行, 化学吸附和内扩散均具有重要作用. 等温吸附数据符合Dubinin-Radushkevich模型, 证明其吸附机理为化学吸附. 因此, PACMC吸附含油污水的机理包括化学结合/螯合作用、疏水力作用和静电吸附作用.

关键词: 粉末活性炭, 吸附, 含油污水, 粉末活性炭基复合材料

In order to solve the problems of low adsorption efficiency and slow precipitation rate for powdered activated carbon (PAC) in the process of removing hydrophilic organics with low molecular weight, this study successfully prepare a kind of powdered activated carbon matrix composites (PACMC) by reaction of mixed powdered activated carbon (PAC), potassium humate (HS), and polyaluminium chloride (PACl) raw materials in oily sewage as the purification adsorbent. We confirmed the micro-morphology and chemical composition of PACMC by scanning electron microscopy-X-ray energy dispersive spectroscopy (SEM-EDS) and Fourier transform infrared spectroscopy (FT-IR), certifying that PACMC was synthesized by chemical reaction of PAC, HS and PACl. PACMC has layered porous structure and functional groups, which is beneficial to the transport, diffusion and chemical adsorption of oily sewage molecules. The static adsorption experiments were carried out to investigate the adsorption properties of organic pollutants in oily sewage by PACl, PAC and PACMC respectively. The results showed that the adsorption capacity of PACMC for organic pollutants in oily sewage was 2~3 times as high as that of PAC and PACl (q_e=23.04 mg•g^‒1, C₀=300 mg•L^‒1). When the adsorption time reached 120 min, the binding of the active site on PACMC and organic pollutants in oily sewage had basically reached saturation (q_e=23.04 mg•g^‒1, C₀=300 mg•L^‒1). The pH value of the solution has a significant effect on the adsorption of organic pollutants in oily sewage by PACMC, and the best adsorption effect was observed at pH=3 (q_e=27.6 mg•g^‒1, C₀=300 mg•L^‒1). The adsorption of organic pollutants in oily sewage by PACMC can be well described by the pseudo-second-order kinetics. The kinetic fitting results revealed that the adsorption process involved several steps, where the chemical adsorption and intra-particle diffusion both played the important roles. The isothermal adsorption data were in accordance with the Dubinin-Radushkevich model, which indicated that the adsorption mechanism was chemical adsorption. Therefore, the mechanism of PACMC adsorption of oily sewage included chemical binding/chelation effect, hydrophobic effect and electrostatic adsorption effect.

Key words: powdered activated carbon, adsorption, oily sewage, powdered activated carbon matrix composites

引用此文

宋亚瑞, 王凯升, 安广宇, 赵法军, 门彬, 杜昭兮, 王东升. 粉末活性炭基复合材料制备及净化含油污水的性能和机制[J]. 化学学报, 2022, 80(12): 1592-1599.

Yarui Song, Kaisheng Wang, Guangyu An, Fajun Zhao, Bin Men, Zhaoxi Du, Dongsheng Wang. Preparation of Powdered Activated Carbon Matrix Composites and Their Decontamination Performance and Mechanisms for Oily Sewage[J]. Acta Chimica Sinica, 2022, 80(12): 1592-1599.

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图/表 9

图1. 复合材料与各单一组分的FT-IR谱图

Figure 1. Infrared spectra of composite material and ingredient

图2. (a) PACMC的制备路线简图; (b) PACMC的微观结构示意图

Figure 2. (a) Preparation route of PACMC; (b) schematic microstructure for PACMC

图3. PACMC和PAC的SEM图片及其元素分析. (a) PACMC-SEM; (b) PAC-SEM; (c) PACMC-EDS; (d) PAC-EDS

Figure 3. SEM and EDS maps of PACMC and PAC. (a) PACMC-SEM; (b) PAC-SEM; (c) PACMC-EDS; (d) PAC-EDS

图4. 不同pH值下PACMC空白吸附实验上清液的EEMs图谱

Figure 4. EEMs maps of supernatant of PACMC blank adsorption experiment at different pH conditions

图5. (a) PACMC的粒径分布图; (b) PACMC的零电位随pH值的变化曲线

Figure 5. (a) Particle size distribution of PACMC; (b) zero potential of PACMC at different pH

图6. (a) PACMC、PAC、PACl对含油污水的TOC去除率随吸附剂投加量的变化曲线; (b) PACMC对含油污水的TOC去除率随时间变化曲线; (c) 不同pH值条件下PACMC对含油污水TOC去除率的变化

Figure 6. (a) Influence of adsorbent dosage for TOC removal efficiency of oily sewage on PACMC, PAC and PACl; (b) influence of reaction time for TOC removal efficiency of oily sewage on PACMC; (c) influence of solution pH for TOC removal efficiency of oily sewage on PACMC

图7. (a) PACMC对含油污水的吸附动力学模型拟合; (b) PACMC吸附含油污水的颗粒内膜扩散模型拟合; (c, d) PACMC吸附等温线模型拟合

Figure 7. (a) Kinetics of oily sewage adsorption on PACMC; (b) particle diffusion model for oily sewage adsorption on PACMC; (c, d) fitting of adsorption isotherms of PACMC

图8. 确定热力学参数的ln Kb与温度倒数关系

Figure 8. The relationship between ln Kb and reciprocal temperature of determining thermodynamic parameters

图9. PACMC和PAC吸附后的SEM图片及其元素分析结果. (a) PACMC吸附后的SEM; (b) PAC吸附后的SEM; (c) PACMC吸附后的EDS; (d) PAC吸附后的EDS

Figure 9. SEM and EDS maps of PACMC and PAC after adsorption. (a) SEM of PACMC after adsorption; (b) SEM of PAC after adsorption; (c) EDS of PACMC after adsorption; (d) EDS of PAC after adsorption

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