程福龙,张祚,胡雯雯,等. 镧改性生物炭高效去除水中磷酸盐特征与机理分析[J]. 农业工程学报,2024,40(4):235-244. DOI: 10.11975/j.issn.1002-6819.202310210
    引用本文: 程福龙,张祚,胡雯雯,等. 镧改性生物炭高效去除水中磷酸盐特征与机理分析[J]. 农业工程学报,2024,40(4):235-244. DOI: 10.11975/j.issn.1002-6819.202310210
    CHENG Fulong, ZHANG Zuo, HU Wenwen, et al. Characterization and mechanism of lanthanum-modified biochar for efficient phosphate removal from water[J]. Transactions of the Chinese Society of Agricultural Engineering (Transactions of the CSAE), 2024, 40(4): 235-244. DOI: 10.11975/j.issn.1002-6819.202310210
    Citation: CHENG Fulong, ZHANG Zuo, HU Wenwen, et al. Characterization and mechanism of lanthanum-modified biochar for efficient phosphate removal from water[J]. Transactions of the Chinese Society of Agricultural Engineering (Transactions of the CSAE), 2024, 40(4): 235-244. DOI: 10.11975/j.issn.1002-6819.202310210

    镧改性生物炭高效去除水中磷酸盐特征与机理分析

    Characterization and mechanism of lanthanum-modified biochar for efficient phosphate removal from water

    • 摘要: 生物炭(biochar,BC)应用于水体中磷的去除不仅有助于缓解水体富营养化,还有利于解决固体废物处理问题,达到以废治废的目的。然而,吸附性能较差严重限制了生物炭在水体除磷方面的应用。因此,该研究采用热解-水热法成功合成了一种镧(La)改性生物炭(La-modified biochar,LBC)除磷吸附剂,考察了制备参数(包括La与BC质量比、水热时间和水热温度)、吸附时间、初始磷浓度、pH值、共存离子对LBC吸附磷酸盐性能的影响,并分析了饱和吸附磷酸盐的LBC在水中的磷酸盐缓释性能。此外,采用X射线衍射(X-ray diffraction,XRD)、傅里叶红外光谱(Fourier transform infrared spectroscopy,FTIR)和X射线光电子能谱(X-ray photoelectron spectroscopy,XPS)表征技术研究了LBC对磷酸盐的吸附机理。试验结果表明,LBC对磷酸盐的吸附能在1 h内快速达到平衡,由Langmuir模型拟合得到的最大吸附量可达136.4 mg/g,吸附速率和吸附量优于大多数已报道的镧改性生物炭吸附剂,这可能主要是因为LBC表面的镧物种呈球状多孔结构,能够提供丰富的磷酸盐吸附位点。此外,LBC在pH值为3~7范围能保持稳定的磷酸盐吸附性能,而在碱性环境下会受到抑制。LBC在含有常见共存阴离子的溶液中,对磷酸盐表现出较高的选择性。XRD、FTIR和XPS表征结果证实,LBC对磷酸盐的吸附机理包括静电吸引、LaPO4沉淀和La-O-P内球络合。饱和吸附磷酸盐的LBC在15 d内可以有效进行连续的磷酸盐释放,且La浸出量可忽略不计。该研究可为农林业废物资源化利用、富营养化水体缓解和高效镧改性生物炭除磷吸附材料的合成设计提供新的思路。

       

      Abstract: Biochar (BC) can be applied for the removal of phosphorus in water bodies. The eutrophication of water bodies can also be alleviated in the disposal of solid wastes. However, the low adsorption capability has seriously limited the application of biochar in phosphate removal from water bodies. In this study, a novel La-modified biochar (LBC) adsorbent was successfully synthesized by a pyrolysis-hydrothermal method, in order to efficiently remove the phosphate from water. A systematic investigation was implemented to explore the effects of preparation parameters (including La to BC mass ratio, hydrothermal time and temperature), adsorption time, initial phosphate concentration, solution pH, and coexisting ions on the phosphate adsorption performance of LBC. The adsorption behavior of LBC on the phosphate was characterized by X-ray diffraction (XRD), Fourier infrared spectroscopy (FTIR), and X-ray photoelectron spectroscopy (XPS) techniques. In addition, the slow-release performance of LBC in water was also evaluated after the saturated adsorption of phosphate. Scanning electron microscopy (SEM) demonstrated that the lanthanum species on the surface of LBC exhibited a spherical porous structure, providing for the abundant adsorption sites of phosphate. Meanwhile, the adsorption equilibrium of LBC rapidly reached within 1 h, indicating the superior adsorption rate for phosphate, compared with the as-reported ones. The pseudo-secondary kinetic model was more suitable to represent the adsorption of phosphate by LBC, compared with the pseudo-first ones. In addition, there were no fitting lines of the intraparticle diffusion model that passed through the origin. It infers that the adsorption rate of phosphate by LBC was controlled by both surface chemisorption and intraparticle diffusion. The maximum phosphate adsorption of LBC fitted by the Langmuir model reached 136.4 mg/g. LBC also exhibited a favorable adsorption capacity for phosphate. The rapid adsorption rate and high adsorption capacity of LBC were attributed to the spherical porous structure of La species on the surface of LBC, indicating the abundant adsorption sites of phosphate. In addition, the value of 1/n in the Freundlich model was below 0.5, indicating that the adsorption of phosphate by LBC was easy to occur, owing to the strong affinity of LBC for phosphate. The pH experiments showed that the LBC maintained the stable performance of phosphate adsorption in the pH range of 3.0-7.0, whereas the phosphate adsorption of LBC was inhibited at pH above 7.0. The reduced capacity of phosphate adsorption under alkaline conditions was attributed mainly to the variation in the phosphate ion species, competitive adsorption of hydroxide ions, and the declined electrostatic attraction. There were negligible effects of Cl- and NO3- on the phosphate adsorption by LBC. The presence of SO42- slightly inhibited the phosphate adsorption, whereas HCO3-, Mg2+, and Ca2+ promoted the phosphate adsorption by LBC. The ion coexistence experiment demonstrated that the high selectivity of LBC was achieved in the phosphate. Therefore, the LBC shared the promising potential for the treatment of actual aqueous environments. The main mechanisms of phosphate adsorption on the LBC included electrostatic attraction, LaPO4 precipitation, and La-O-P inner-sphere complexation. In addition, the LBC that saturated with adsorbed phosphate was proceeded with the continuous phosphate release over 15 d. There was a negligible amount of La released from LBC into the water in the pH range of 3.0-11.0, indicating a low risk of La leaching. As such, the phosphate-adsorbed LBC can be expected to serve as a slow-release phosphate fertilizer for hydroponic crops. This finding can provide new ideas for the resource utilization of forestry wastes and the synthetic design of efficient lanthanum-modified biochar adsorbent materials for phosphate removal.

       

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