La/FeOOH@PAC对反渗透浓缩液中有机膦酸盐阻垢剂HEDP的吸附性能研究

doi:10.15541/jim20200512

无机材料学报 ›› 2021, Vol. 36 ›› Issue (8): 841-846.DOI: 10.15541/jim20200512

La/FeOOH@PAC对反渗透浓缩液中有机膦酸盐阻垢剂HEDP的吸附性能研究

李创¹^,²(), 杨庆峰¹(), 陆盛森¹, 刘阳桥³()

1.中国科学院上海高等研究院, 上海 201210
2.中国科学院大学, 北京 100049
3.中国科学院上海硅酸盐研究所, 上海 200050

收稿日期:2020-09-02 修回日期:2020-11-23 出版日期:2021-08-20 网络出版日期:2021-01-25
通讯作者: 杨庆峰, 研究员. E-mail: yangqf@sari.ac.cn; 刘阳桥, 研究员. E-mail: yqliu@mail.sic.ac.cn
作者简介:李创(1991-), 男, 博士研究生. E-mail: lichuang740@163.com
基金资助:
国家自然科学基金(51878647);国家自然科学基金(61574148)

Adsorption of Phosphonate Antiscalant HEDP from Reverse Osmosis Concentrates by La/FeOOH@PAC

LI Chuang¹^,²(), YANG Qingfeng¹(), LU Shengsen¹, LIU Yangqiao³()

1. Shanghai Advanced Research Institute, Chinese Academy of Sciences, Shanghai 201210, China
2. University of Chinese Academy of Sciences, Beijing 100049, China
3. Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050, China

Received:2020-09-02 Revised:2020-11-23 Published:2021-08-20 Online:2021-01-25
Contact: YANG Qingfeng, professor. E-mail: yangqf@sari.ac.cn; LIU Yangqiao, professor. E-mail: yqliu@mail.sic.ac.cn
About author:LI Chuang(1991-), male, PhD candidate. E-mail: lichuang740@163.com
Supported by:
National Natural Science Foundation of China(51878647);National Natural Science Foundation of China(61574148)

摘要/Abstract

摘要：

在反渗透脱盐过程中, 为了避免矿物质结垢广泛使用膦酸盐阻垢剂, 但这会对环境和浓缩液脱硬度产生不利影响, 需要在反渗透浓缩液处理前去除膦酸盐阻垢剂。本工作以活性炭(PAC)为载体, 采用共沉淀法制备了含有氢氧化镧与羟基氧化铁的复合材料(La/FeOOH@PAC), 利用La/Fe的协同作用提高吸附剂的吸附性能。采用不同手段对复合材料的结构和表面性质进行了表征, 并研究了其对模拟反渗透浓缩液中膦酸盐阻垢剂HEDP的吸附行为和性能, 考察了镧铁摩尔比、吸附时间、HEDP浓度和温度对其吸附性能的影响。实验结果表明: 制备的复合材料在298 K、pH=8.0和吸附剂用量为0.4 g/L的条件下, 其吸附等温线符合Langmuir模型, 理论最大吸附量为65.359 mg·g^-1, 吸附动力学可用拟二级动力学方程来描述, 同时吸附过程为自发放热过程。XPS分析表明吸附剂的主要吸附机理为与镧/铁连接的羟基基团和HEDP之间的配体交换作用。

关键词: 羟基氧化铁, 氢氧化镧, 粉末活性炭, HEDP, 阻垢剂

Abstract:

Phosphonate antiscalants are commonly used in reverse osmosis (RO) membrane desalination to prevent fouling by mineral scale. However, due to its adverse effects on the ecosystem and the removal of hardness from RO concentrates, it is necessary to remove phosphonate antiscalants before RO concentrates disposal. In this work, using powder activated carbon (PAC) as carrier, La/FeOOH@PAC composite material was prepared via co-precipitation of lanthanum hydroxide and iron oxyhydroxide. The synergistic effect of La/Fe enhanced the adsorption capability of the composite material. Morphology and structure of the adsorbents were characterized by different methods. Adsorption behavior and properties of this composites for phosphonate antiscalant 1-hydroxyethylidene-1,1-diphosphonic acid (HEDP) in simulated reverse osmosis concentrates were also investigated. The effect of molar ratio of La to Fe, adsorption time, initial concentration of HEDP and temperature on the adsorption performance were investigated in details. The results showed that La/FeOOH@PAC composites was successfully synthesized by co-precipitation method. Under the adsorption conditions of 298 K, pH=8.0 and dosage of 0.4 g·L^-1, the adsorption isothermal was in accordance with the Langmuir model, and the theoretical maximum adsorption capacity was 65.359 mg·g^-1. Its adsorption kinetics could be fitted well with the pseudo-second-order kinetics equation, and adsorption behavior was an exothermic and spontaneous process. XPS analysis showed that the main adsorption mechanism of the adsorbent was the ligand exchange between hydroxyl groups linked with La/Fe and HEDP.

Key words: iron oxyhydroxide, lanthanum, powder activated carbon, HEDP, antiscalant

中图分类号:

O647

李创, 杨庆峰, 陆盛森, 刘阳桥. La/FeOOH@PAC对反渗透浓缩液中有机膦酸盐阻垢剂HEDP的吸附性能研究[J]. 无机材料学报, 2021, 36(8): 841-846.

LI Chuang, YANG Qingfeng, LU Shengsen, LIU Yangqiao. Adsorption of Phosphonate Antiscalant HEDP from Reverse Osmosis Concentrates by La/FeOOH@PAC[J]. Journal of Inorganic Materials, 2021, 36(8): 841-846.

图/表 12

表1 模拟反渗透浓缩液组成

Table 1 Simulation solution of RO concentrates

Concentration/(mg·L^-1)							T/K	Initial pH
HEDP	Ca²⁺	Mg²⁺	Na⁺	Cl^-	SO₄^2-	HCO^-	T/K	Initial pH
18.00	298	8.00	204.54	397.86	407.62	542.46	298	8.00

图1 不同摩尔比掺杂的La/FeOOH@PAC吸附剂对阻垢剂HEDP的吸附性能

Fig. 1 Variation of HEDP adsorption capacity on La/FeOOH@PAC with different molar ratios of the La/Fe Absorbent dosage: 0.4 g/L, Absorption time: 12 h

图2 PAC和La/FeOOH@PAC的XRD图谱

Fig. 2 XRD patterns of PAC and La/FeOOH@PAC

图3 不同放大倍率La/FeOOH@PAC粉末的FE-SEM照片

Fig. 3 Different magnification FE-SEM images of La/FeOOH@PAC composite

表2 吸附剂主要的元素含量

Table 2 Elemental composition of the adsorbent

Element	C	O	Fe	La
wt%	86.27	12.04	1.05	0.64

图4 吸附材料对HEDP的吸附动力学

Fig. 4 Adsorption kinetics of HEDP onto the adsorbent

表3 La/FeOOH@PAC复合材料的吸附动力学参数

Table 3 Parameters of kinetic models for HEDP adsorption onto the La/FeOOH@PAC composite

T/K	Q_e,exp/(mg·g^-1)	Pseudo-first-order equation			Pseudo-second-order equation
T/K	Q_e,exp/(mg·g^-1)	k₁/h^-1	Q_e/(mg·g^-1)	R²	k₂/(g·mg^-1·h^-1)	Q_e/(mg·g^-1)	R²
298	41.600	0.476	24.143	0.983	0.0659	42.553	0.999

图5 HEDP在吸附剂上的吸附等温线

Fig. 5 Adsorption isotherm of HEDP onto the adsorbent

表4 吸附剂对HEDP的等温吸附拟合参数

Table 4 Parameters of isotherm models for HEDP adsorption onto the adsorbent

T/K	Langmuir model parameters			Freundlich model parameters
T/K	Q_m/ (mg·g^-1)	K_L/ (L·mg^-1)	R²	n	K_F	R²
298	65.359	0.455	0.974	1.880	19.249	0.864
308	56.818	0.674	0.992	2.446	21.509	0.949
318	56.689	0.512	0.993	2.211	18.571	0.940

图6 不同温度下吸附剂对HEDP吸附的lnKd与Ce的线性拟合曲线(a)和 lnK0与1/T的线性曲线(b)

Fig. 6 Linear plots fit of lnKd versus Cefor the adsorption HEDP onto the adsorbent at different temperatures (a); linear plots of lnK0 versus 1/T for the adsorption of HEDP onto the adsorbent (b)

表5 吸附剂对HEDP吸附的热力学参数

Table 5 Thermodynamic parameters for HEDP adsorption onto the adsorbent

T/K	ΔG^o/(kJ·mol^-1)	ΔH^o/(kJ·mol^-1)	ΔS^o/(J·mol^-1 K^-1)
298	-7.579	-9.632	-6.834
308	-7.567
318	-7.440

图7 吸附前后XPS谱图的全谱(a)、P2p(b)和O1s(c, d)分谱图

Fig. 7 Wide scan (a), P2p (b) and O1s (c, d) XPS spectra of the adsorbent before and after adsorption

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La/FeOOH@PAC对反渗透浓缩液中有机膦酸盐阻垢剂HEDP的吸附性能研究

Adsorption of Phosphonate Antiscalant HEDP from Reverse Osmosis Concentrates by La/FeOOH@PAC

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