不同结构铝氧化物对磷的吸附特征

doi:10.15541/jim20190444

无机材料学报 ›› 2020, Vol. 35 ›› Issue (9): 1005-1010.DOI: 10.15541/jim20190444

所属专题：环境材料论文精选(2020)；【虚拟专辑】污染物吸附水处理(2020~2021)

不同结构铝氧化物对磷的吸附特征

李敬^1,²(),刘晓月²,邱千峰²,李苓²,曹晓燕^1,^2,³()

1.中国海洋大学海洋化学理论与工程技术教育部重点实验室/海洋高等研究院, 青岛 266100
2.中国海洋大学化学化工学院, 青岛 266100
3.中国海洋大学青岛海洋科学与技术国家实验室海洋生态与环境科学功能实验室, 青岛 266100

收稿日期:2019-08-28 修回日期:2020-01-13 出版日期:2020-09-20 网络出版日期:2020-03-03
作者简介:李敬(1995-), 女, 硕士研究生. E-mail: 840609162@qq.com
LI Jing(1995-), female, Master candidate. E-mail:840609162@qq.com
基金资助:
国家自然科学基金(41676064);国家重点研发计划项目(2016YFA0601301)

Phosphorus Sorption Characteristics on Aluminum Oxides with Different Structures

LI Jing^1,²(),LIU Xiaoyue²,QIU Qianfeng²,LI Ling²,CAO Xiaoyan^1,^2,³()

1. Key Laboratory of Marine Chemistry Theory and Technology, Ministry of Education /Institute for Advanced Ocean Study, Ocean University of China, Qingdao 266100, China
2. College of Chemistry and Chemical Engineering, Ocean University of China, Qingdao 266100, China
3. Laboratory for Marine Ecology and Environmental Science, Qingdao National Laboratory for Marine Science and Technology, Qingdao 266100, China

Received:2019-08-28 Revised:2020-01-13 Published:2020-09-20 Online:2020-03-03
Supported by:
National Natural Science Foundation of China(41676064);National Key Research and Development Program of China(2016YFA0601301)

摘要/Abstract

摘要：

磷是影响藻类生长的重要营养元素, 它在沉积物界面上的吸附是海洋环境中磷循环的重要环节, 金属氧化物是吸附磷沉积物的重要活性组分之一。采用批量实验法研究不同结构的氧化铝对无机磷的吸附特征, 分别使用二段一级动力学方程和Freundlich等方程对其动力学曲线和平衡吸附等温线进行定量描述, 并对介质盐度、温度等影响因素进行研究。结果发现, 无定型氧化铝结晶弱且比表面积大, 该特点使其吸附容量大于γ-Al₂O₃, 结合表面酸碱滴定的结果, 可知吸附也与铝氧化物的表面酸碱性质相关。分析影响因素可知, 与NaNO₃介质相比, 氧化铝吸附海水中的磷受到阻滞, 且随着介质离子强度增大, 吸附量均呈现降低趋势; pH显著影响磷的吸附量, 在pH=5左右, 两种氧化铝表面对磷酸根的吸附达到最大值; 温度升高, 有利于吸附的进行, 该吸附为吸热、自发、熵增加的过程, 两种结构氧化铝的吸附热力学参数无显著差异。

关键词: 富营养化, 磷, 铝氧化物, 结构, 吸附

Abstract:

Phosphorus is an important nutrient element that affects the growth of algae. The sorption of phosphorus on the sediments plays an important role in its bio-geochemical cycle, with metal oxides such as alumina being one of the important active components for the process. The sorption behavior of phosphorus on two kinds of alumina (γ-Al₂O₃, amorphous alumina) was studied through batch methods. Both kinetics and thermodynamics of the process were investigated, as well as the effects of temperature, salinity, and pH of the medium on the process. The sorption kinetic curves could be described by a two-compartment first order equation, and the isotherms fit Freundlich equation well. The amorphous alumina has a larger specific surface area, and its sorption ability is stronger than that of γ-Al₂O₃. Based on the results of surface acid-base titration, the sorption behavior is also considered to be related to the surface acidity and alkalinity of the aluminum oxides. Compared with NaNO₃ medium, the sorption of phosphorus in seawater was weakened. The sorption capacity decreases with the increase of the ionic strength. pH significantly affected the sorption ability of the oxides with the maximum capacity at pH=5. Higher temperatures are favorable to the sorption progress, which is endothermic and spontaneous with entropy increasing. The difference in the thermodynamic parameters of the two alumina seemed unremarkable.

Key words: eutrophication, phosphorus, aluminum oxides, structure, sorption

中图分类号:

X703

李敬,刘晓月,邱千峰,李苓,曹晓燕. 不同结构铝氧化物对磷的吸附特征[J]. 无机材料学报, 2020, 35(9): 1005-1010.

LI Jing,LIU Xiaoyue,QIU Qianfeng,LI Ling,CAO Xiaoyan. Phosphorus Sorption Characteristics on Aluminum Oxides with Different Structures[J]. Journal of Inorganic Materials, 2020, 35(9): 1005-1010.

图/表 11

图1 γ-Al2O3、无定形氧化铝的XRD图谱

Fig. 1 XRD patterns of γ-Al2O3 and amorphous alumina

图2 γ-Al2O3(a)、无定形氧化铝(b)的傅里叶红外光谱图

Fig. 2 Fourier infrared spectra of γ-Al2O3 (a) and amorphous alumina (b)

图3 γ-Al2O3(a)和无定型氧化铝(b)的SEM照片

Fig. 3 SEM images of γ-Al2O3 (a) and amorphous alumina (b)

表1 不同离子强度介质中两种铝氧化物的表面酸碱性质

Table 1 Surface acid-base properties of two aluminum oxides in different ionic strength media

NaNO₃ concentration/ (mol·L^-1)	H_S concentration/(mol·L^-1)		TOTH_pH=8/(mmol·L^-1)		pH_PZNPC^*
NaNO₃ concentration/ (mol·L^-1)	γ-Al₂O₃	Amorphous alumina	γ-Al₂O₃	Amorphous alumina	γ-Al₂O₃	Amorphous alumina
0.01	3.35×10^-3	2.69×10^-3	-	-	4.52	4.25
0.10	2.94×10^-3	1.79×10^-3	-	-
0.70	2.75×10^-3	1.09×10^-3	-0.809	-1.380

图4 无定形氧化铝对磷酸盐的吸附动力学及拟合曲线

Fig. 4 Sorption kinetics curves of phosphate on amorphous alumina Dot: experimental data; Line:two-compartment first-order model fitting

表2 磷酸盐在无定形氧化铝上的吸附动力学参数

Table 2 Sorption kinetic parameters of phosphorus on amorphous alumina

Medium	F_rap	F_slow	k_slow/h^-1	k_rap/h^-1	Q_e/(mg·g^-1)	r²
0.7 mol·L^-1 NaNO₃	0.813	0.187	0.977	26.32	21.42	0.977
NSW	0.740	0.260	0.193	20.23	16.56	0.988

图5 在不同离子强度NaNO3介质中, 磷酸盐在γ-Al2O3(a)和无定形氧化铝(b)上的等温吸附曲线

Fig. 5 Sorption isotherms of phosphate on γ-Al2O3 (a) and amorphous alumina (b) in NaNO3 with different concentrations Dot: experimental data; Line: Freundlich model fitting

表3 不同离子强度介质中磷酸盐在γ-Al2O3和无定形氧化铝上的等温吸附参数

Table 3 Isothermal sorption parameters of phosphates on γ-Al2O3 and amorphous alumina

Sorbent	I/(mol·L^-1)	Freundlich			Langmuir
Sorbent	I/(mol·L^-1)	K_F/(mg·g^-1) (L·mg^-1)^1/ⁿ	n	r²	Q_m/(mg·g^-1)	K_L/(L·mg^-1)	r²
γ-Al₂O₃	0.7	12.39	4.52	0.942	14.93	5.288	0.848
	0.1	13.20	6.08	0.912	13.47	18.29	0.702
	0.01	14.37	7.20	0.896	14.28	27.90	0.485
Amorphous alumina	0.7	26.28	3.27	0.933	34.70	3.828	0.838
	0.1	27.66	4.09	0.933	34.60	4.888	0.820
	0.01	28.36	3.24	0.907	43.22	2.046	0.817

图6 不同温度下, 磷酸盐在γ-Al2O3(a)和无定形氧化铝(b)上的等温吸附曲线

Fig. 6 Sorption isotherms of phosphate on γ-Al2O3 (a) and amorphous alumina (b) at different femperatures Dot: experimental data; Line: Freundlich model fitting

表4 磷酸盐在γ-Al2O3和无定形氧化铝的吸附热力学参数

Table 4 Sorption thermodynamic parameters of phosphate on γ-Al2O3 and amorphous alumina

Adsorbent	T/K	K_F/(mg·g^-1) (L·mg^-1)^1/ⁿ	n	r²	ΔG^θ/(kJ·mol^-1)	ΔH^θ/(kJ·mol^-1)	ΔS^θ/(J·mol^-1·K^-1)
γ-Al₂O₃	298	11.55	5.18	0.938	-23.18	9.007	108.0
	303	12.22	4.40	0.948	-23.71
	308	12.99	4.98	0.952	-24.26
Amorphous alumina	298	26.28	3.27	0.933	-25.21	11.96	124.8
	303	28.84	3.60	0.947	-25.87
	308	30.73	3.64	0.951	-26.46

图7 磷酸盐在γ-Al2O3和无定形氧化铝上的吸附pH边曲线

Fig. 7 Sorption pH edges curves of P on γ-Al2O3 and amorphous alumina

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不同结构铝氧化物对磷的吸附特征

Phosphorus Sorption Characteristics on Aluminum Oxides with Different Structures

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