纳米球状LaAlO3的制备及其在酸性条件下的除氟性能

doi:10.16085/j.issn.1000-6613.2023-0743

化工进展 ›› 2024, Vol. 43 ›› Issue (6): 3199-3208.DOI: 10.16085/j.issn.1000-6613.2023-0743

• 材料科学与技术 • 上一篇

纳米球状LaAlO₃的制备及其在酸性条件下的除氟性能

刘京都¹(), 余关龙¹^,², 龙志奇³, 周璐¹^,², 包璞瑞¹, 滕骏毅¹, 杜春艳¹^,²()

^1.长沙理工大学水利与环境工程学院，湖南长沙 410114
^2.洞庭湖水环境治理与生态修复湖南省重点实验室，湖南省环境保护河湖疏浚污染控制工程技术中心，湖南长沙 410114
^3.有研资源环境技术研究院（北京）有限公司，北京 101400

收稿日期:2023-05-06 修回日期:2023-09-17 出版日期:2024-06-15 发布日期:2024-07-02
通讯作者: 杜春艳
作者简介:刘京都（1999—），男，硕士研究生，研究方向为水处理新材料。E-mail：1582804854@qq.com。
基金资助:
湖南省教育厅重点项目(21A0188);湖南省环境保护河湖疏浚污染控制工程技术中心开放基金(EPD202104);湖南省自然科学基金(2021JJ30728)

Preparation of nano-spherical LaAlO₃ and its fluoride removal performance under acidic environment

LIU Jingdu¹(), YU Guanlong¹^,², LONG Zhiqi³, ZHOU Lu¹^,², BAO Purui¹, TENG Junyi¹, DU Chunyan¹^,²()

^1.College of Water and Environmental Engineering, Changsha University of Science and Technology, Changsha 410114, Hunan, China
^2.Hunan Key Laboratory of Dongting Lake Water Environment Management and Ecological Restoration, Hunan Environmental Protection River and Lake Dredging Pollution Control Engineering Technology Center, Changsha 410114, Hunan, China
^3.GRINM Resources and Environment Tech. Co. , Ltd. , Beijing 101400, China

Received:2023-05-06 Revised:2023-09-17 Online:2024-06-15 Published:2024-07-02
Contact: DU Chunyan

摘要/Abstract

摘要：

为实现在较低的pH及煅烧温度下合成表面性能良好的LaAlO₃晶相，解决废水的深度除氟问题（<1.5mg/L），采用共沉-水热法制备了纳米球状钙钛矿LaAlO₃，考察了影响LaAlO₃表面性能的制备因素，通过SEM（扫描电子显微镜）、XRD（X射线衍射）、ICP-MS（电感耦合等离子体质谱）、BET等分析发现形成碱式碳酸沉淀的水热前体可使Al³⁺和La³⁺均匀沉淀、结合紧密，得到LaAlO₃的最佳制备条件：共沉淀pH=6，水热温度=160℃，煅烧温度850℃。通过静态吸附实验系统分析了LaAlO₃吸附F^-的行为，结果表明，LaAlO₃可以在酸性（pH<3）条件下实现深度除氟，在pH=2时，除氟效率达到93.22%。吸附过程符合Langmuir等温吸附模型和准二级动力学模型，属于化学单层吸附、放热反应。在初始氟浓度为200mg/L条件下，8min LaAlO₃吸附容量达到53.8mg/g，4h平衡吸附容量可达66.5mg/g。以明矾作为脱附剂，LaAlO₃能够在循环4次后仍保持原有90%以上的除氟性能，具有良好的再生性能及实际利用价值。

关键词: LaAlO₃, 含氟废水, 深度除氟, 吸附剂, 纳米双金属氧化物

Abstract:

In order to solve the problem of synthesizing LaAlO₃ crystalline phase with good surface properties by lowering the calcination temperature at lower pH for application in deep fluoride removal in wastewater (<1.5mg/L), the nano-spherical perovskite LaAlO₃ by co-precipitation hydrothermal method was prepared and the preparation factors affecting the surface properties of LaAlO₃ was investigated. It was found by SEM, XRD, ICP-MS and BET that the formation of hydrothermal precursors of alkali carbonic acid precipitation can make Al³⁺ and La³⁺ precipitation more tightly bound and the optimal preparation conditions for LaAlO₃ were obtained: co-precipitation pH=6, hydrothermal temperature=160℃ and calcination temperature of 850℃. The behavior of F^- adsorption by LaAlO₃ was analyzed by static adsorption experiments and regeneration experiments systematically, and the results showed that LaAlO₃ could achieve deep fluoride removal under acidic (pH<3) conditions and the fluoride removal rate reached 93.22% at pH=2. The adsorption process conformed to the Langmuir adsorption isotherm model and pseudo-second-order kinetic model, which was a chemical monolayer adsorption with exothermic reaction. Under the condition of initial fluorine concentration of 200mg/L, the adsorption capacity of LaAlO₃ adsorption reached 53.8mg/g in 8min and the equilibrium adsorption capacity reached 66.5mg/g in 4h. By using alum as desorbent, LaAlO₃ can maintain more than 90% of the original fluoride removal rate after 4 cycles with excellent regeneration performance and high utilization value.

Key words: LaAlO₃, fluorinated wastewater, deep defluorination, adsorbent, nano bimetallic oxides

中图分类号:

X703

刘京都, 余关龙, 龙志奇, 周璐, 包璞瑞, 滕骏毅, 杜春艳. 纳米球状LaAlO₃的制备及其在酸性条件下的除氟性能[J]. 化工进展, 2024, 43(6): 3199-3208.

LIU Jingdu, YU Guanlong, LONG Zhiqi, ZHOU Lu, BAO Purui, TENG Junyi, DU Chunyan. Preparation of nano-spherical LaAlO₃ and its fluoride removal performance under acidic environment[J]. Chemical Industry and Engineering Progress, 2024, 43(6): 3199-3208.

图/表 17

表1 Al3+和La3+的沉淀pH

沉淀物质	K_sp	开始沉淀pH	完全沉淀pH
Al(OH)₃	1.3×10^-33	3.42	4.70
La(OH)₃	2.67×10^-30	4.52	5.81
La₂(CO₃)₃	1.1×10^-30	7.51	8.80
LaCO₃OH	—	>7.51	—

图1 不同共沉淀pH下吸附剂的XRD衍射图（制备条件：La、Al摩尔比=1∶1，沉淀温度=80℃，水热温度=160℃，水热时长=16h，煅烧温度=850℃，共沉淀pH=5、5.5、6、7、8、9）

图2 水热后前体的XRD衍射图（制备条件：La、Al摩尔比=1∶1，共沉淀pH=6，沉淀温度=80℃，水热温度=160℃，水热时长=16h）

图3 水热后前体的SEM图（制备条件：La、Al摩尔比=1∶1，共沉淀pH=6，沉淀温度=80℃，水热温度=160℃，水热时长=16h）(a) 形貌；(b)~(d) 面扫描

图4 不同pH下LaAlO3的SEM图像

表2 不同pH下LaAlO3的特征变化对比

pH	晶粒粒径/nm	比表面积/m²·g^-1	孔径/nm	晶粒特征
5	240	9.352	3.408	密集
6	220	13.540	3.072	疏松
9	300	3.761	3.840	结块

图5 不同水热温度下LaAlO3的XRD衍射图（制备条件：La、Al摩尔比=1∶1，共沉淀pH=6，沉淀温度=80℃，水热时长=16h，煅烧温度=850℃，水热温度=140℃、160℃、180℃、200℃）

图6 不同水热温度下LaAlO3的SEM图(a)、(e) 140℃；(b)、(f) 160℃；(c)、(g) 180℃；(d)、(h) 200℃

图7 不同煅烧温度下吸附剂的XRD衍射图（制备条件：La、Al摩尔比=1∶1，共沉淀pH=6，沉淀温度=80℃，水热温度=160℃，水热时长=16h，煅烧温度=700℃、750℃、800℃、850℃）

图8 不同煅烧温度下吸附剂的SEM图(a)、(c) 800℃；(b)、(d) 850℃

图9 pH对LaAlO3除氟性能的影响

表3 LaAlO3的吸附动力学拟合参数

准一级动力学模型					准二级动力学模型						Elovich模型
C₀/mg·L^-1	k₁/min^-1		R²		C₀/mg·L^-1	K₂/g·mg^-1·min^-1		q_e/mg·g^-1		R²	C₀/mg·L^-1		α/mg·g^-1·min^-1		β/g·mg^-1	R²
10	0.3291		0.9108		10	0.1555		4.25		0.9904	10		58871.4042		2.17	0.8583
200	0.3615		0.9771		200	0.0082		66.34		0.9995	200		119606.6163		0.04	0.8618
内扩散模型										外扩散模型
C₀/mg·L^-1		K_id/mg·g^-1·min^-0.5		C			R²		C₀/mg·L^-1			K_p/min^-1		R²
10		0.4614		1.9674			0.5208		10			0.0051		0.5639
200		9.2286		23.0950			0.5234		200			0.0026		0.5113

图10 LaAlO3的吸附动力学拟合

表4 LaAlO3的吸附等温线拟合参数

温度 /℃	Langmuir			Freundlich			Temkin
温度 /℃	R²	q_m/mg·g^-1	b/L·mg^-1	R²	K_F/mg^1-(1/ⁿ⁾·L^1/ⁿ ·g^-1	n	R²	B_T/J·mol^-1		K_T/L·mg^-1
30	0.994	85.21	0.052	0.968	8.116	1.939	0.9688	14.94	0.9734
40	0.991	75.74	0.050	0.966	7.225	1.973	0.9844	14.12	0.8125
50	0.991	69.43	0.039	0.973	8.008	2.281	0.9779	12.53	0.6995

图11 LaAlO3的吸附热力学拟合

表5 LaAlO3与其他相关吸附剂除氟性能的比较

吸附剂	pH	吸附剂剂量/g·L^-1	吸附容量/mg·g^-1	参考文献
LaAlO₃	3	2	66.50	本实验
Mg-Al-Ce	6	5	26.12	[29]
La/MA	6	2	26.45	[30]
Ce-Fe	5.5	0.5	60.97	[31]
TiO₂-ZrO₂	5	0.5	27.80	[32]

图12 LaAlO3的吸附-再生循环

参考文献 32

1	LACSON Carl Francis Z, LU Mingchun, HUANG Yaohui. Fluoride-containing water: A global perspective and a pursuit to sustainable water defluoridation management—An overview[J]. Journal of Cleaner Production, 2021, 280: 124236.
2	PETERS RUDOLPH, SHORTHOUSE M. Fluoride metabolism in plants[J]. Nature, 1964, 202(4927): 21-22.
3	HE Junyong, YANG Ya, WU Zijian, et al. Review of fluoride removal from water environment by adsorption[J]. Journal of Environmental Chemical Engineering, 2020, 8(6): 104516.
4	HE Xiaodong, LI Peiyue, JI Yujie, et al. Groundwater arsenic and fluoride and associated arsenicosis and fluorosis in China: Occurrence, distribution and management[J]. Exposure and Health, 2020, 12(3): 355-368.
5	张广瑞, 任彬, 李海松. 煤化工废水除氟及尾水脱氮除磷性能[J]. 中国环境科学, 2023, 43(4): 1655-1662.
	ZHANG Guangrui, REN Bin, LI Haisong. Defluorination of coal chemical wastewater and nitrogen and phosphorus removal performance of tailwater[J]. China Environmental Science, 2023, 43(4): 1655-1662.
6	杨为森, 刘毅飞, 史丰硕, 等. 电纺La₂O₃-CeO₂纳米纤维的除氟性能[J]. 复合材料学报, 2023, 40(6): 3385-3395.
	YANG Weisen, LIU Yifei, SHI Fengshuo, et al. Defluoridation performance of electrospun La₂O₃-CeO₂ nanofibers[J]. Acta Materiae Compositae Sinica, 2023, 40(6): 3385-3395.
7	CHEN Xin, WAN Caixia, YU Rui, et al. A novel carboxylated polyacrylonitrile nanofibrous membrane with high adsorption capacity for fluoride removal from water[J]. Journal of Hazardous Materials, 2021, 411: 125113.
8	武鑫霞, 曹占平, 苏婷, 等. Ce改性金属有机骨架材料对氟的吸附[J]. 复合材料学报, 2020, 37(10): 2636-2644.
	WU Xinxia, CAO Zhanping, SU Ting, et al. Adsorption of Ce modified metal organic framework to fluorine[J]. Acta Materiae Compositae Sinica, 2020, 37(10): 2636-2644.
9	LI Xilin, YU Xiaowan, LIU Ling, et al. Preparation, characterization serpentine-loaded hydroxyapatite and its simultaneous removal performance for fluoride, iron and manganese[J]. RSC Advances, 2021, 11(27): 16201-16215.
10	MUKHERJEE Arnab, ADAK Mrinal K, DHAK Prasanta, et al. A simple chemical method for the synthesis of Cu²⁺ engrafted MgAl₂O₄ nanoparticles: Efficient fluoride adsorbents, photocatalyst and latent fingerprint detection[J]. Journal of Environmental Sciences, 2020, 88: 301-315.
11	魏永, 李贤建, 罗政博, 等. 氧化铝改性活性炭纤维电吸附除氟效能及机理[J]. 中国环境科学, 2023, 43(8): 3974-3982.
	WEI Yong, LI Xianjian, LUO Zhengbo, et al. Efficiency and mechanism of fluoride removal by electroadsorption of alumina modified activated carbon fiber[J]. China Environmental Science, 2023, 43(8): 3974-3982.
12	GITARI Wilson M, IZUAGIE Anthony A, GUMBO Jabulani R. Synthesis, characterization and batch assessment of groundwater fluoride removal capacity of trimetal Mg/Ce/Mn oxide-modified diatomaceous earth[J]. Arabian Journal of Chemistry, 2020, 13(1): 1-16.
13	ZHANG Bo, LIU Chengjun, LI Chunlong, et al. A novel approach for recovery of rare earths and niobium from Bayan Obo tailings[J]. Minerals Engineering, 2014, 65: 17-23.
14	AOUDJ S, KHELIFA A, DROUICHE N, et al. Removal of fluoride and turbidity from semiconductor industry wastewater by combined coagulation and electroflotation[J]. Desalination and Water Treatment, 2016, 57(39): 18398-18405.
15	HUANG Lei, YANG Zhihui, LEI Dongxue, et al. Experimental and modeling studies for adsorbing different species of fluoride using lanthanum-aluminum perovskite[J]. Chemosphere, 2021, 263: 128089.
16	LI W, ZHUO M W, SHI J L. Synthesizing nano LaAlO₃ powders via co-precipitation method[J]. Materials Letters, 2004, 58(3/4): 365-368.
17	KUO Chia-Liang, WANG Chengli, CHEN Teyuan, et al. Low temperature synthesis of nanocrystalline lanthanum monoaluminate powders by chemical coprecipitation[J]. Journal of Alloys and Compounds, 2007, 440(1/2): 367-374.
18	BRYLEWSKI Tomasz, BUĆKO Mirosław M. Low-temperature synthesis of lanthanum monoaluminate powders using the co-precipitation-calcination technique[J]. Ceramics International, 2013, 39(5): 5667-5674.
19	HARON Wankassama, WISITSORAAT Anurat, WONGNAWA Sumpun. Nanostructured perovskite oxides-LaMO₃ (M=Al, Co, Fe) prepared by co-precipitation method and their ethanol-sensing characteristics[J]. Ceramics International, 2017, 43(6): 5032-5040.
20	宋立. 高分散性纳米YAG荧光粉的制备及性能研究[D]. 南京: 东南大学, 2018.
	SONG Li. Preparation and properties of high dispersion nano-YAG phosphor[D].Nanjing: Southeast University, 2018.
21	Yujin SIM, YOO Jihoon, Jeong-Myeong HA, et al. Oxidative coupling of methane over LaAlO₃ perovskite catalysts prepared by a co-precipitation method: Effect of co-precipitation pH value[J]. Journal of Energy Chemistry, 2019, 35: 1-8.
22	WALTON Prof Richard I. Frontispiece: Perovskite oxides prepared by hydrothermal and solvothermal synthesis: A review of crystallisation, chemistry, and compositions[J]. Chemistry-A European Journal, 2020, 26(42): 9041-9069.
23	ZHANG Lianjie, CUI Meisheng, WANG Hao, et al. Effects of co-precipitation temperature on structure and properties of La and Y doped cerium zirconium mixed oxides[J]. Transactions of Nonferrous Metals Society of China, 2022, 32(2): 618-628.
24	GAYER K H, THOMPSON L C, ZAJICEK O T. The solubility of aluminum hydroxide in acidic and basic media at 25℃[J]. Canadian Journal of Chemistry, 1958, 36(9): 1268-1271.
25	LEE Gihoon, KANG Ji Yeon, YAN Ning, et al. Simple preparation method for Mg-Al hydrotalcites as base catalysts[J]. Journal of Molecular Catalysis A: Chemical, 2016, 423: 347-355.
26	刘文斌. Nd: YAG透明陶瓷的制备、显微结构及激光性能研究[D]. 上海: 上海交通大学, 2012.
	LIU Wenbin. Preparation, microstructure and laser properties of Nd: YAG transparent ceramics[D]. Shanghai: Shanghai Jiao Tong University, 2012.
27	SOLANGI Imam Bakhsh, MEMON Shahabuddin, BHANGER M I. An excellent fluoride sorption behavior of modified amberlite resin[J]. Journal of Hazardous Materials, 2010, 176(1/2/3): 186-192.
28	ISLAM Mahamudur, MISHRA Prakash Chandra, PATEL Rajkishore. Fluoride adsorption from aqueous solution by a hybrid thorium phosphate composite[J]. Chemical Engineering Journal, 2011, 166(3): 978-985.
29	WANG Aihe, ZHOU Kanggen, CHEN Wei, et al. Adsorption of fluoride by the calcium alginate embedded with Mg-Al-Ce trimetal oxides[J]. Korean Journal of Chemical Engineering, 2018, 35(8): 1636-1641.
30	HE Yuxuan, ZHANG Liming, AN Xiao, 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.
31	TANG Dandan, ZHANG Gaoke. Efficient removal of fluoride by hierarchical Ce-Fe bimetal oxides adsorbent: Thermodynamics, kinetics and mechanism[J]. Chemical Engineering Journal, 2016, 283: 721-729.
32	YU Yaqin, ZHOU Zhen, DING Zhaoxia, et al. Simultaneous arsenic and fluoride removal using{201}TiO₂-ZrO₂: Fabrication, characterization, and mechanism[J]. Journal of Hazardous Materials, 2019, 377: 267-273.

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纳米球状LaAlO₃的制备及其在酸性条件下的除氟性能

Preparation of nano-spherical LaAlO₃ and its fluoride removal performance under acidic environment

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