Adsorption of yttrium /zirconium bimetallic organic frameworks on organic phosphonate scale inhibitor HEDP

doi:10.19965/j.cnki.iwt.2023-0105

Abstract

Abstract:

A new yttrium zirconium bimetallic organic framework（YZr-MOF） adsorption material was synthesized by solvothermal method for the first time，and the structure and surface properties of adsorbents were characterized. Adsorption behavior and properties on organic phosphonate scale inhibitor 1-hydroxyethylidene-1，1-diphosphonic acid（HEDP） were investigated. Experimental results indicated that the structure of MOFs presented spherical particles of uniform size. The specific surface area of the adsorbent was 912.862 m²/g. At 298 K，the theoretical maximum adsorption capacity of YZr-MOF was 66.293 mg/g（calculated in P）. The adsorption process was fitted well with the pseudo-second-order kinetics equation and the Langmuir model. Moreover，the adsorption process was an endothermic process. The temperature rise was conducive to YZr-MOF adsorption of HEDP. In the adsorption experiments，the optimal amount of YZr-MOF was 0.2 g/L. YZr-MOF had good stability over a wide pH range and maintained a significant adsorption rate after six cycles. Combined with the relevant experiments and the characterization results of FTIR and XPS，electrostatic interaction and ligand exchange were the main adsorption mechanisms.

Key words: metal organic framework, organic phosphonate scale inhibitor, adsorption, ligand exchange

摘要：

采用溶剂热法首次合成了新型钇锆双金属有机框架（YZr-MOF）吸附材料，并对其结构和表面性质进行了表征，研究了YZr-MOF对有机膦阻垢剂羟基亚乙基二膦酸（HEDP）的吸附行为和性质。实验结果表明，YZr-MOF呈现出大小均匀的球形颗粒结构，比表面积为912.862 m²/g；在298 K时，YZr-MOF理论最大吸附量为66.293 mg/g（以P计）。吸附过程符合准二级动力学和Langmuir模型，吸附过程为吸热过程，温度升高有利于YZr-MOF吸附HEDP。在吸附实验中，YZr-MOF的最佳质量浓度为0.2 g/L；YZr-MOF在较宽的pH范围内有着良好的稳定性，并且经过6次循环后，仍保持显著的吸附率。结合相关实验和FTIR、XPS的表征结果表明，静电作用和配体交换为主要吸附机理。

关键词: 金属有机框架, 有机膦阻垢剂, 吸附, 配体交换

CLC Number:

X703
TQ424

Dengke LIU, Qingfeng YANG, Yangqiao LIU. Adsorption of yttrium /zirconium bimetallic organic frameworks on organic phosphonate scale inhibitor HEDP[J]. Industrial Water Treatment, 2024, 44(2): 73-78.

刘登科, 杨庆峰, 刘阳桥. 钇锆双金属MOFs对有机膦阻垢剂HEDP的吸附研究[J]. 工业水处理, 2024, 44(2): 73-78.

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URL: https://www.iwt.cn/EN/10.19965/j.cnki.iwt.2023-0105

https://www.iwt.cn/EN/Y2024/V44/I2/73

Figures/Tables 12

Fig.1 SEM images of YZr-MOF

Fig.2 XRD patterns of YZr-MOF

Fig.3 N₂ adsorption-desorption isotherms of YZr-MOF

Fig.4 The effect of adsorbent dosage on removal rate

Fig.5 Effect of initial pH of solution on adsorption capacity of HEDP

Fig.6 Fitting curve of adsorption kinetics of YZr-MOF

Table 2 Kinetic parameters for adsorption onto the adsorbent

项目	准一级动力学方程				准二级动力学方程
参数	k ₁/h^-1	Q _e/（mg·g^-1）	R ²		k ₂/（g·mg^-1 h^-1）	Q _e/（mg·g^-1）	R ²
数值	0.069	89.233	0.980		0.001 0	94.581	0.991

Fig.7 Isotherm adsorption fitting curve

Table 3 Parameters of isotherm models of adsorbents

T/K	Langmuir			Freundlich
T/K	q _m/（mg·g^-1）	K _L/（L·mg^-1）	R ²	n	K _F	R ²
298	220.264	2.018	0.999	5.299	130.902	0.856
308	236.407	1.748	0.999	5.045	137.266	0.902
318	257.069	2.223	0.999	4.998	154.922	0.921

Fig.8 FTIR spectra before and after adsorption

Fig.9 Full-range XPS of adsorbent before and after adsorption

Fig.10 Zr 3d（a） and Y 3d（b） before and after adsorption

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