氯代UiO-66吸附染色纸废水中罗丹明B和刚果红

doi:10.16085/j.issn.1000-6613.2018-1905

摘要/Abstract

摘要：

为了进一步提高金属-有机骨架材料（metal-organic frameworks, MOFs）的吸附性能，本文将有机配体对苯二甲酸替换为2-氯对苯二甲酸，合成了金属-有机骨架化合物UiO-66的衍生物——氯代UiO-66（UiO-66-Cl）。以UiO-66、木质活性炭（AC）和蔗渣作为参照，研究了UiO-66-Cl对染色纸废水中罗丹明B（Rh-B）和刚果红（CR）的吸附性能和对染料废水pH的适应性，优化其吸附工艺条件，基于等温吸附模型（Langmuir和Freundlich）拟合其最大吸附量，最终对该吸附剂的回收、解吸附和再利用性能进行评价。研究结果表明：UiO-66-Cl对两种染料（Rh-B和CR）的吸附性能和对染料溶液pH的适应性均显著高于UiO-66、AC和蔗渣；其对Rh-B和CR的吸附过程符合Freundlich等温吸附模型，属于非均质多位点的多层吸附；在10~1000mg/L的初始染料浓度范围内，该吸附剂对Rh-B和CR的最大吸附容量分别为94.28mg/g和151.84mg/g；与HCl（0.1mol/L）、NaOH（0.1mol/L）和95%（体积分数）乙醇溶液相比，乙醇-HCl溶液（0.1mol/L HCl与95%乙醇溶液的体积比为0.5∶99.5）是UiO-66-Cl的良好再生溶剂体系，染料初始浓度为50mg/L时，再生UiO-66-Cl对Rh-B和CR的移除率均接近90%。由此可见，UiO-66-Cl可作为一种稳定、高效且易再生的吸附剂应用于去除染色纸废水中的Rh-B和CR。

关键词: 氯代UiO-66, 罗丹明B, 刚果红, 吸附, 再生

Abstract:

To improve the adsorption capacity of metal-organic frameworks (MOFs), chlorine-substituted UiO-66 (UiO-66-Cl) was synthesized by replacing terephthalic acid with 2-chloroterephthalic acid as an organic ligand. With UiO-66, wood activated carbon (AC) and Bagasse as references, the adsorption capacity of UiO-66-Cl to Rhodamine B (Rh-B) and Congo Red (CR) in dyeing paper wastewater and its adaptability to pH of two dye solutions were studied. The adsorption process conditions of UiO-66-Cl were optimized. Based on isothermal adsorption models of Langmuir and Freundlich, the maximum adsorption capacity of this adsorbent was fitted. Finally, the performance of recovery, desorption and reuse of this adsorbent was also evaluated. The results showed that the adsorption capacity of UiO-66-Cl to Rh-B and CR and its adaptability to pH of two dye solutions were significantly higher than those of UiO-66, AC and Bagasse. The adsorption processes of UiO-66-Cl to Rh-B and CR were in accordance with the Freundlich isotherm adsorption model, indicating a multi-layer adsorption with heterogeneous multi-sites. Within the initial dye concentration range of 10—1000mg/L, the maximum adsorption capacity of UiO-66-Cl to Rh-B and CR were 94.28mg/L and 151.84mg/L, respectively. Compared with HCl (0.1mol/L), NaOH (0.1mol/L) and 95% (v/v) ethanol solutions, ethanol-HCl solution (volume ratio of 0.1mol/L HCl to 95% ethanol solution was 0.5∶99.5) was a good regeneration solvent system for UiO-66-Cl. When the initial dye concentration was 50mg/L, the removal of Rh-B and CR by regenerated UiO-66-Cl were both close to 90%. Therefore, UiO-66-Cl is a stable, efficient and regenerated adsorbent for the removal of Rh-B and CR from dyeing paper wastewater.

Key words: chlorine-substituted UiO-66, Rhodamine B, Congo Red, adsorption, regeneration

中图分类号:

X793

杨光绪, 龚正刚, 罗小林, 黄六莲, 陈礼辉, 刘婧. 氯代UiO-66吸附染色纸废水中罗丹明B和刚果红[J]. 化工进展, 2019, 38(07): 3434-3442.

Guangxu YANG, Zhenggang GONG, Xiaolin LUO, Liulian HUANG, Lihui CHEN, Jing LIU. Adsorption of Rhodamine B and Congo Red in dyeing paper wastewater by chlorine-substituted UiO-66[J]. Chemical Industry and Engineering Progress, 2019, 38(07): 3434-3442.

图/表 13

图1 Rh-B和CR染料的结构式

图2 UiO-66和UiO-66-Cl的SEM图

表1 Rh-B和CR染料溶液的标准曲线

染料	λ_max/nm	标准曲线参数		R²
染料	λ_max/nm	α	β	R²
Rh-B	554	5.568	0.045	0.992
CR	497	36.879	-0.278	0.996

图3 不同吸附剂吸附染料废水中Rh-B和CR的性能比较

表2 4种吸附剂的比表面积和孔容

样品	BET比表面积/m²·g^-1	孔容/cm³·g^-1
UiO-66	1182.3	0.56
UiO-66-Cl	874.6	0.49
AC	638.7	0.37
蔗渣	3.4	0.01

图4 废液pH对UiO-66-Cl去除Rh-B和CR效率的影响

图5 UiO-66-Cl用量对其吸附去除溶液中Rh-B和CR效率的影响

图6 吸附时间对UiO-66-Cl去除溶液中Rh-B和CR效率的影响

图7 UiO-66-Cl吸附Rh-B和CR过程中qe随Ce的变化关系及其拟合曲线

表3 等温吸附曲线的拟合参数

模型	参数	Rh-B	CR
Freundlich	K_F/(mg·g^-1)·(L·mg^-1)^1/ⁿ	4.101	9.235
	n	2.061	2.342
	R²	0.995	0.982
Langmuir	q_max/mg·L^-1	39.526	68.027
	K_L/L·mg^-1	0.112	0.165
	R²	0.910	0.834

图8 UiO66-Cl吸附Rh-B和CR的颗粒内部扩散曲线

表4 UiO-66-Cl的回收率及Rh-B和CR在不同溶液中的脱附率

样品	R/%		脱附溶液	DES/%
样品	Rh-B	CR	脱附溶液	Rh-B	CR
UiO-66-Cl	95.4	94.1	HCl	85.3	74.4
			NaOH	10.2	1.7
			乙醇	87.1	38.6
			乙醇+HCl	93.5	95.5

图9 UiO66-Cl的再利用性能评价

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