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

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

Abstract

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

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

CLC Number:

X703

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.

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.

Figures/Tables 17

References 32

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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	—

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	—

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

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

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

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

纳米球状LaAlO₃的制备及其在酸性条件下的除氟性能

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Figures/Tables 17

References 32

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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

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]

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