由单层薄水铝石制备的活性氧化铝处理水中氟离子

doi:10.3866/PKU.WHXB201911009

物理化学学报 >> 2021, Vol. 37 >> Issue (10): 1911009.doi: 10.3866/PKU.WHXB201911009

由单层薄水铝石制备的活性氧化铝处理水中氟离子

孙建川¹, 王旭辉¹, 陈帅奇¹, 廖艳清¹, 郜阿旺¹, 胡雨昊¹, 杨涛¹, 徐向宇¹, 王颖霞², 宋家庆¹^,*()

¹ 北京化工大学，化工资源有效利用国家重点实验室，北京 100029
² 北京大学化学与分子工程学院无机化学研究所，北京 100871

收稿日期:2019-11-05 录用日期:2019-12-14 发布日期:2019-12-20
通讯作者: 宋家庆 E-mail:songjq@126.com
基金资助:
华东师范大学上海绿色化学与化学过程重点实验室(H2016107)

Defluoridation of Water Using Active Alumina Derived from Single-Layer Boehmite

Jianchuan Sun¹, Xuhui Wang¹, Shuaiqi Chen¹, Yanqing Liao¹, Awang Gao¹, Yuhao Hu¹, Tao Yang¹, Xiangyu Xu¹, Yingxia Wang², Jiaqing Song¹^,*()

¹ State Key Laboratory of Chemical Resource Engineering, Beijing University of Chemical Technology, Beijing 100029, China
² Institute of Inorganic Chemistry, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, China

Received:2019-11-05 Accepted:2019-12-14 Published:2019-12-20
Contact: Jiaqing Song E-mail:songjq@126.com
About author:Jiaqing Song, Email:songjq@126.com; Tel: +86-10-64423325
Supported by:
the Shanghai Key Laboratory of Green Chemistry and Chemical Processes, East China Normal University, China(H2016107)

摘要/Abstract

摘要：

合成高效低成本的氟离子吸附剂仍是具有挑战的研究课题。本文采用无有机物的方法制备了单层结构的薄水铝石，并以此薄水铝石得到大比表面积的活性氧化铝。活性氧化铝的大比表面积保证了很高的吸附效率，合成过程无有机表面活性剂或模板剂的使用，控制了成本。采用X射线衍射(XRD)及扫面电镜(SEM)等方法对样品进行了表征，发现制备的氧化铝前体为单层结构的薄水铝石，其比表面积为789.4 m²·g^-1，焙烧后得到活性氧化铝的比表面积为678.4 m²·g^-1，孔体积为3.20 cm³·g^-1。并系统研究了吸附剂用量、吸附时间等因素对活性氧化铝吸附水中氟离子的影响。研究结果表明，本文制备活性氧化铝对水中氟离子的吸附量可达67.6 mg·g^-1。仅分别需0.6、1.0或2.6 g·L^-1活性氧化铝就可将10、20或50 mg·L^-1的氟离子溶液处理至中国饮用水标准(1.0 mg·L^-1)以下。并且此活性氧化铝在pH = 4–9的范围内均可用于水中氟离子的处理，对吸附有较大影响的共存离子为SO₄^2-及PO₄^3-，进一步研究表明，活性氧化铝对氟离子的吸附遵循准二级模型和朗格缪尔等温模型。

关键词: 除氟, 活性氧化铝, 单层, 大比表面积, 吸附, 高吸附量, 无有机物

Abstract:

The preparation of high-efficiency and low-cost adsorbents for the defluoridation of drinking water remains a huge challenge. In this study, single-layer and multi-layer boehmite were first synthesized via an organic-free method, and active alumina used for fluoride removal from water was obtained from the boehmite. The advantage of a single layer is that more aluminum is exposed to the surface, which can provide more adsorption sites for fluoride. The active alumina adsorbent derived from single-layer boehmite exhibits a high specific surface area and excellent adsorption capacity. The high surface area ensures a high adsorption capacity, and the organic-free synthesis method lowers the preparation cost. The as-prepared adsorbent was characterized by X-ray powder diffraction (XRD), scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HRTEM), Fourier-transform infrared spectroscopy (FTIR) and nitrogen adsorption-desorption analysis. The single-layer structure of boehmite was determined from the simulated XRD diffraction pattern of single-layer boehmite. The disappearance of the (020) diffraction peak of boehmite illustrates that the dimensions in the b direction are extremely small, and according to the XRD simulation results, the single-layer structure of boehmite could be determined. Single-layer boehmite with a surface area of 789.4 m²·g^-1 was formed first. The active alumina obtained from the boehmite had a surface area of 678.4 m²·g^-1, and the pore volume was 3.20 cm³·g^-1. The fluoride adsorption of the active alumina was systematically studied as a function of the adsorbent dosage, contact time, concentration, co-existing anions, and pH. The fluoride adsorption capacity of the active alumina obtained from the single-layer boehmite reached up to 67.6 mg·g^-1, which is higher than those of most alumina adsorbents reported in the literature. The adsorption capacities of the active alumina are related to the specific surface area and the number of hydroxyl groups on the surface. Dosages of 0.6, 1.0, and 2.6 g·L^-1 of active alumina were able to lower the 10, 20, and 50 mg·L^-1 fluoride solutions, respectively, below the maximum permissible limit of fluoride in drinking water in China (1.0 mg·L^-1), suggesting that the active alumina synthesized in this work is a promising adsorbent for defluoridation of drinking water. In addition, the fluoride adsorption is applicable in a wide pH range from 4 to 9 and is mainly interfered by SO₄^2- and PO₄^3-. Further investigation suggested that the fluoride adsorption of the active alumina follows the pseudo second-order model and Langmuir isotherm model

Key words: Defluoridation, Active alumina, Single layer, High surface area, Adsorption, High adsorption capacity, Organic-free

孙建川, 王旭辉, 陈帅奇, 廖艳清, 郜阿旺, 胡雨昊, 杨涛, 徐向宇, 王颖霞, 宋家庆. 由单层薄水铝石制备的活性氧化铝处理水中氟离子[J]. 物理化学学报, 2021, 37(10), 1911009. doi: 10.3866/PKU.WHXB201911009

Jianchuan Sun, Xuhui Wang, Shuaiqi Chen, Yanqing Liao, Awang Gao, Yuhao Hu, Tao Yang, Xiangyu Xu, Yingxia Wang, Jiaqing Song. Defluoridation of Water Using Active Alumina Derived from Single-Layer Boehmite[J]. Acta Phys. -Chim. Sin. 2021, 37(10), 1911009. doi: 10.3866/PKU.WHXB201911009

链接本文: https://www.whxb.pku.edu.cn/CN/10.3866/PKU.WHXB201911009

https://www.whxb.pku.edu.cn/CN/Y2021/V37/I10/1911009

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Sample	D₍₂₀₀₎/nm	D₍₀₂₀₎/nm	D₍₀₀₂₎/nm
S1	1.25	–	4.21
S2	1.43	–	4.70
SB	8.1	4.89	10.35

Sample	Surface area/(m²?g^?1)	Pore volume/(cm³?g^?1)
S1	789.4	3.12
S2	572.8	1.72
SB	286.7	0.42
S1-500	678.4	3.20
S2-500	450.9	1.87
SB-500	217.9	0.53

adsorbent	q_{e exp}/(mg?g^-1)	Pseudo ?rst-order			Pseudo second-order
adsorbent	q_{e exp}/(mg?g^-1)	q_{e, cal}/(mg?g^-1)	k₁/min^-1	R²	q_{e, cal}/(mg?g^-1)	k₂/(g?mg^-1?min^-1)	R²
S1-500	63.1	48.7	0.0352	0.9615	66.2	0.002727	0.9988
S2-500	34.3	30.8	0.0474	0.9782	35.4	0.006838	0.9987
SB-500	8.7	8.4	0.0107	0.9191	8.8	0.051029	0.9999

Adsorbent	Langmuir model			Freundlich model
Adsorbent	q_m/(mg?g^?1)	b/(L?mg^?1)	R²	K_f/(mg?g^?1)	1/n	R²
S1-500	67.6	0.1205	0.9992	22.5	0.2155	0.9598
S2-500	40.7	0.1326	0.9940	22.1	0.1069	0.9669

Adsorbent	Initial concentration/(mg?L^?1)	Surface area/(m²?g^?1)	q_m/(mg?g^?1)	Reference
AlOOH	3–35	–	3.26	35
AlOOH	5–50	–	2.06	41
γ-Al₂O₃	20–250	650	14.26	26
alkoxide origin alumina	5.4–24	100	2.35	15
nano-alumina	1–100	151.7	14.0	42
La/alumina	1–200	236.9	26.45	36
acidic alumina	2–15	144.3	8.4	18
alumina S1-500	10–200	678.4	67.6	This study
alumina S2-500	10–200	450.9	40.7

由单层薄水铝石制备的活性氧化铝处理水中氟离子

Defluoridation of Water Using Active Alumina Derived from Single-Layer Boehmite

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Adsorbent	concentration/(mg?L^-1)	Dose/(g?L^?1)	Reference
Mg-Al-Zr triple-metal composite	1.4	1.5	34
	2.0	2.6
AlOOH	13	> 16	35
Zr-Al-Ca Nanohybride	50	5	36
alkoxide origin alumina	5.4	6	15
Manganese dioxide-coated activated alumina	10	4	16
Alum-impregnated activated alumina	25	> 8	17
Acidic alumina	5	1.5	18
	10	3
	15	4.5
Active alumina	10	0.6	This study
	20	1.0
	50	2.6
Commercial alumina	10	35

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