Ce-La双金属氧化物同步去除酸性废水中磷酸盐和氟的性能与机理

李含; 赵雨; 陈嘉超; 许海民; 朱雅娴; 陈志辉; 申萌萌; 杨文澜

PDF(927 KB)

中国环境科学 ›› 2023, Vol. 43 ›› Issue (10) : 5148-5156.

水污染与控制

Ce-La双金属氧化物同步去除酸性废水中磷酸盐和氟的性能与机理

李含¹, 赵雨¹, 陈嘉超¹, 许海民², 朱雅娴¹, 陈志辉¹, 申萌萌¹, 杨文澜^1,2

作者信息 +

Simultaneous removal of phosphate and fluoride from acid wastewater by Ce-La bimetal oxides: Performance and mechanism

LI Han¹, ZHAO Yu¹, CHEN Jia-chao¹, XU Hai-min², ZHU Ya-xian¹, CHEN Zhi-hui¹, SHEN Meng-meng¹, YANG Wen-lan^1,2

Author information +

文章历史 +

摘要

采用共沉淀法制备出能同步吸附磷酸盐和氟的Ce-La双金属氧化物纳米吸附剂（CLBOs）.结果表明，CLBOs主要以粒径20~50nm的纳米颗粒或纳米团簇的形式存在，比表面积为117.9m²/g.CLBOs在pH为4~12的范围内具有良好的稳定性，且酸性条件有利于CLBOs的除磷除氟；在pH = 4.0、磷酸盐和氟初始浓度为30、10mg/L的条件下，CLBOs最大磷、氟吸附量分别可达59.14，19.25mg/g.得益于静电吸引、配体交换和内配位络合的综合作用，CLBOs表现出优异的同步除磷除氟性能，且在高浓度竞争离子体系中能实现磷酸盐和氟的选择性吸附.CLBOs除磷除氟过程符合准二级动力学，且对氟的吸附速率显著快于磷酸盐，其中磷酸盐的吸附平衡时间约为240min，氟达到吸附平衡仅需100min.吸附饱和的CLBOs具有较好的再生性能，可长期重复使用，在含磷、氟酸性废水的深度处理领域具备良好的应用潜力.

Abstract

A novel Ce-La bimetal oxides nano-adsorbent (CLBOs) capable of simultaneous phosphate and fluoride removal from water was successfully synthesized by coprecipitation method. The CLBOs existed primarily as nanoparticles or nanoclusters, with a particle size range of 20~50nm and a specific surface area of 117.9m²/g. Notably, the CLBOs displayed excellent chemical stability across a wide pH range (4~12), with acidic conditions proving beneficial for the adsorption of phosphate and fluoride. Under experimental condition of pH 4.0and initial concentrations of 30mg/L for phosphate and 10mg/L for fluoride, the CLBOs exhibited a remarkable maximum adsorption capacity of 59.14mg/g for phosphate and 19.25mg/g for fluoride. This outstanding adsorption performance was attributed to the combined effects of electrostatic attraction, ligand exchange, and inner-sphere complexation. Furthermore, the presence of competing anions had minimal impact on the removal efficiency of CLBOs. The adsorption process of phosphate and fluoride onto CLBOs followed a pseudo-second-order kinetic model, with fluoride being adsorbed significantly faster than phosphate. Equilibrium was achieved in approximately 100 minutes for fluoride and 240 minutes for phosphate. Importantly, the exhausted CLBOs could be efficiently regenerated through a simple alkaline treatment, enabling their cyclic utilization while maintaining consistent adsorption performance. In conclusion, the results demonstrate that CLBOs is a highly efficient adsorbent with significant potential for practical applications in the simultaneous removal of phosphate and fluoride from wastewater.

导出引用

李含, 赵雨, 陈嘉超, 许海民, 朱雅娴, 陈志辉, 申萌萌, 杨文澜. Ce-La双金属氧化物同步去除酸性废水中磷酸盐和氟的性能与机理[J]. 中国环境科学. 2023, 43(10): 5148-5156

LI Han, ZHAO Yu, CHEN Jia-chao, XU Hai-min, ZHU Ya-xian, CHEN Zhi-hui, SHEN Meng-meng, YANG Wen-lan. Simultaneous removal of phosphate and fluoride from acid wastewater by Ce-La bimetal oxides: Performance and mechanism[J]. China Environmental Science. 2023, 43(10): 5148-5156

中图分类号： X703

参考文献

[1] Sinha E, Michalak A M, Balaji V. Eutrophication will increase during the 21st century as a result of precipitation changes[J]. Science, 2017,357:405-408.
[2] 韩梅香,尹洪斌,唐婉莹.热改性凹土钝化底泥对水体磷的吸附特征研究[J]. 中国环境科学, 2016,36(1):100-108. Han M X, Yin H B, Tang W Y. Study on phosphorus adsorption characteristics of thermal modified attapulgite passivated sediment in water[J]. China Environmental Science, 2016,36(1):100-108.
[3] Mumtaz N, Pandey G, Labhasetwar P K. Global fluoride occurrence, available technologies for fluoride removal, and electrolytic defluoridation:A Review[J]. Critical Reviews in Environmental Science and Technology, 2015,45(21):2357-2389.
[4] 章萍,杨陈凯,马若男,等.碳纳米管/羟基磷灰石复合材料对水体F^-的去除研究[J]. 中国环境科学, 2019,39(1):179-187. Zhang P, Yang C K, Ma R N et al. Removal of F^- from water by carbon nanotubes/hydroxyapatite composites[J]. China Environmental Science, 2019,39(1):179-187.
[5] Kong L C, Tian Y, Pang Z, et al. Synchronous phosphate and fluoride removal from water by 3D rice-like lanthanum-doped La@MgAl nanocomposites[J]. Chemical Engineering Journal, 2019,371:893-902.
[6] Park J Y, Byun H J, Choi W H, et al. Cement paste column for simultaneous removal of fluoride, phosphate, and nitrate in acidic wastewater[J]. Chemosphere, 2008,70(8):1429-1437.
[7] Warmadewanthi B, Liu J C. Selective separation of phosphate and fluoride from semiconductor wastewater[J]. Water Science and Technology, 2009,59(10):2047-2053.
[8] Li F H, Jin J, Shen Z Y, et al. Removal and recovery of phosphate and fluoride from water with reusable mesoporous Fe₃O₄@mSiO₂@mLDH composites as sorbents[J]. Journal of Hazardous Materials, 2020,388:121734.
[9] Huang H M, Liu J H, Zhang P, et al. Investigation on the simultaneous removal of fluoride, ammonia nitrogen and phosphate from semiconductor wastewater using chemical precipitation[J]. Chemical Engineering Journal, 2017,307:696-706.
[10] Wan K L, Huang L, Yan J, et al. Removal of fluoride from industrial wastewater by using different adsorbents:A review[J]. Science of the Total Environment, 2021,773:145535.
[11] Huang W Y, Zhang Y M, Li D. Adsorptive removal of phosphate from water using mesoporous materials:A review[J]. Journal of Environmental Management, 2017,193:470-482.
[12] Li M X, Liu J Y, Xu Y F, et al. Phosphate adsorption on metal oxides and metal hydroxides:A comparative review[J]. Environmental Reviews, 2016,24(3):319-332.
[13] Ni C Q, Liu C, Xie Y, et al. A critical review on adsorption and recovery of fluoride from wastewater by metal-based adsorbents[J]. Environmental Science and Pollution Research, 2022,29(55):82740-82761.
[14] Yu Y, Yu L, Koh K Y, et al. Rare-earth metal based adsorbents for effective removal of arsenic from water:A critical review[J]. Critical Reviews in Environmental Science and Technology, 2018,48(22):1127-1164.
[15] Wang L, Wang J Y, He C, et al. Development of rare earth element doped magnetic biochars with enhanced phosphate adsorption performance[J]. Colloids and Surfaces a-Physicochemical and Engineering Aspects, 2019,561:236-243.
[16] He Y X, Zhang L M, An X, et al. Enhanced fluoride removal from water by rare earth (La and Ce) modified alumina:Adsorption isotherms, kinetics[J]. thermodynamics and mechanism. Science of the Total Environment, 2019,688:184-198.
[17] Vences-Alvarez E, Chazaro-Ruiz L F, Rangel-Mendez J R. New bimetallic adsorbent material based on cerium-iron nanoparticles highly selective and affine for arsenic(V)[J]. Chemosphere, 2022,297:134177.
[18] Zhang Y, Yang M, Dou X M, et al. Arsenate adsorption on an Fe-Ce bimetal oxide adsorbent:role of surface properties[J]. Environmental Science & Technology, 2005,39(18):7246-7253.
[19] Guo Y L, Xing X, Shang Y A, et al. Multiple bimetallic (Al-La or Fe-La) hydroxides embedded in cellulose/graphene hybrids for uptake of fluoride with phosphate surroundings[J]. Journal of Hazardous Materials, 2019,379:120634.
[20] Mukhopadhyay K, Naskar A, Ghosh U C, et al. One-pot synthesis of beta-cyclodextrin amended mesoporous cerium(IV) incorporated ferric oxide surface towards the evaluation of fluoride removal efficiency from contaminated water for point of use[J]. Journal of Hazardous Materials, 2020,384(C):121235.
[21] Pan B J, Wu J, Pan B C, et al. Development of polymer-based nanosized hydrated ferric oxides (HFOs) for enhanced phosphate removal from waste effluents[J]. Water Research, 2009,43(17):4421-4429.
[22] Zhang L, Wang Z H, Xu X, et al. Insights into the phosphate adsorption behavior onto 3D self-assembled cellulose/graphene hybrid nanomaterials embedded with bimetallic hydroxides[J]. Science of the Total Environment, 2019,653:897-907.
[23] Pan B C, Xu J S, Wu B, et al. Enhanced removal of fluoride by polystyrene anion exchanger supported hydrous zirconium oxide nanoparticles[J]. Environmental Science & Technology, 2013,47(16):9347-9354.
[24] Dong H, Tang H, Shi X X, et al. Enhanced fluoride removal from water by nanosized cerium oxides impregnated porous polystyrene anion exchanger[J]. Chemosphere, 2022,287(P1):131932.
[25] Yang W L, Shi X X, Dong H, et al. Fabrication of a reusable polymer-based cerium hydroxide nanocomposite with high stability for preferable phosphate removal[J]. Chemical Engineering Journal, 2021, 405:126649.
[26] Marcus Y. Thermodynamics of solvation of ions -part 5. gibbs free energy of hydration at 298.15K. Journal of the Chemical Society[J]. Faraday Transactions, 1991,87(18):2995-2999.
[27] Tang D D, Zhang G K. Efficient removal of fluoride by hierarchical Ce-Fe bimetal oxides adsorbent:Thermodynamics, kinetics and mechanism[J]. Chemical Engineering Journal, 2016,283:721-729.
[28] Dong C J, Wu X M, Gao Z Y, et al. A novel and efficient metal oxide fluoride absorbent for drinking water safety and sustainable development[J]. Sustainability, 2021,13(2):883.
[29] Thathsara S K T, Cooray P, Mudiyanselage T K, et al. A novel Fe-La-Ce tri-metallic composite for the removal of fluoride ions from aqueous media[J]. Journal of Environmental Management, 2018,207:387-395.
[30] Feng Y F, Lu H Y, Liu Y, et al. Nano-cerium oxide functionalized biochar for phosphate retention:Preparation, optimization and rice paddy application[J]. Chemosphere, 2017,185:816-825.
[31] He Y X, Zhang L M, An X, et al. Enhanced fluoride removal from water by rare earth (La and Ce) modified alumina:Adsorption isotherms, kinetics, thermodynamics and mechanism[J]. Science of the Total Environment, 2019,688:184-198.
[32] Zhang Y Y, Qian Y, Li W, et al. Fluoride uptake by three lanthanum based nanomaterials:Behavior and mechanism dependent upon lanthanum species[J]. Science of the Total Environment, 2019,683:609-616.
[33] Zhang Y Y, Pan B C, Shan C, et al. Enhanced phosphate removal by nanosized hydrated la(iii) oxide confined in cross-linked polystyrene networks[J]. Environmental Science & Technology, 2016,50(3):1447-1454.
[34] Yang W L, Shi X X, Wang J C, et al. Fabrication of a novel bifunctional nanocomposite with improved selectivity for simultaneous nitrate and phosphate removal from water[J]. Acs Applied Materials & Interfaces, 2019,11:35277-35285.
[35] Chigondo M, Paumo H K, Bhaumik M, et al. Hydrous CeO₂-Fe₃O₄ decorated polyaniline fibers nanocomposite for effective defluoridation of drinking water[J]. Journal of Colloid and Interface Science, 2018,532:500-516.
[36] Zhang Q R, Bolisetty S, Cao Y P, et al. Selective and efficient removal of fluoride from water:in situ engineered amyloid Fibril/ZrO₂ hybrid membranes[J]. Angewandte Chemie-International Edition, 2019,58:6012-6016.
[37] Kong L C, Tian Y, Pang Z, et al. Needle-like Mg-La bimetal oxide nanocomposites derived from periclase and lanthanum for cost-effective phosphate and fluoride removal:Characterization. performance and mechanism[J]. Chemical Engineering Journal, 2020, 382:122963.
[38] Sikha S, Mandal B. Ultrasound-Assisted facile synthesis of Ce/Fe nanoparticles impregnated activated carbon for fluoride remediation[J]. Separation and Purification Technology, 2022,289:120785.
[39] Shi W M, Fu Y W, Jiang W, et al. Enhanced phosphate removal by zeolite loaded with Mg-Al-La ternary (hydr)oxides from aqueous solutions:Performance and mechanism[J]. Chemical Engineering Journal, 2019,357:33-44.
[40] Cai J G, Zhang Y Y, Qian Y, et al. Enhanced defluoridation using novel millisphere nanocomposite of La-Doped Li-Al layered double hydroxides supported by polymeric anion exchanger[J]. Scientific Reports, 2018,8:11741.
[41] Wu B L, Wan J, Zhang Y Y, et al. Selective phosphate removal from water and wastewater using sorption:process fundamentals and removal mechanisms[J]. Environmental Science & Technology, 2020,54(1):50-66