不同亲疏水性腐殖酸对磁性离子交换树脂吸附去除水中溴离子的影响

doi:10.12034/j.issn.1009-606X.220217

过程工程学报 ›› 2021, Vol. 21 ›› Issue (7): 807-816.DOI: 10.12034/j.issn.1009-606X.220217CSTR: 32067.14.jproeng.220217

不同亲疏水性腐殖酸对磁性离子交换树脂吸附去除水中溴离子的影响

李凌¹(), 丁磊¹^,²(), 薛岗¹, 贾韫翰¹, 钟梅英¹^,², 张德伟²^,³

^1.安徽工业大学建筑工程学院，安徽马鞍山 243032
^2.生物膜法水质净化及利用技术教育部工程研究中心，安徽马鞍山 243032
^3.安徽华骐环保科技股份有限公司，安徽马鞍山 243071

收稿日期:2020-07-09 修回日期:2020-09-04 出版日期:2021-07-28 发布日期:2021-07-27
通讯作者: 丁磊 17375087687@163.com;dinglei1978@163.com
作者简介:李凌(1997-)，男，安徽省合肥市人，硕士研究生，建筑与土木工程专业，E-mail: 17375087687@163.com
丁磊，通讯联系人，E-mail: dinglei1978@163.com.
基金资助:
国家自然科学基金资助项目(51308001);安徽省高校优秀拔尖人才培育资助项目(gxyqZD2017036)

Effects of hydrophilicity/hydrophobicity of humic acid components on the removal of bromide adsorbed on magnetic ion exchange resin

LI Ling¹(), Lei DING¹^,²(), Gang XUE¹, Yunhan JIA¹, Meiying ZHONG¹^,², Dewei ZHANG²^,³

^1.School of Civil Engineering and Architecture, Anhui University of Technology, Ma′anshan, Anhui 243032, China
^2.Engineering Research Center of Biomembrane Water Purification and Utilization Technology, Ministry of Education, Ma′anshan, Anhui 243032, China
^3.Anhui Huaqi Environmental Protection Technology Co. Ltd. , Ma′anshan, Anhui 243071, China

Received:2020-07-09 Revised:2020-09-04 Online:2021-07-28 Published:2021-07-27
Contact: Lei DING 17375087687@163.com;dinglei1978@163.com

摘要/Abstract

摘要：

研究了不同亲疏水性腐殖酸对磁性离子交换(MIEX)树脂吸附去除溴离子的影响。溶液pH=7.0条件下，四种腐殖酸组分(强疏水性、弱疏水性、极性亲水、中性亲水)对溴离子的去除表现出不同程度的抑制作用。相较而言疏水性组分的不利影响较为显著。腐殖酸的存在减弱了溴离子在MIEX树脂上吸附过程对pH值的依赖性。腐殖酸组分能加速溴离子的吸附速率，溴离子在树脂上达到吸附平衡所需的时间被显著缩短。无论溶液中是否存在腐殖酸，拟二级动力学模型均能很好地拟合溴离子在树脂上的吸附过程，并且由于竞争吸附作用，腐殖酸组分导致溴离子在MIEX树脂上的平衡吸附容量显著减少。溴离子在MIEX树脂上的吸附平衡均可以通过Langmuir和Freundlich模型进行拟合。腐殖酸组分的存在会降低溴离子吸附体系的自发性，强疏水性组分的影响较为显著。该研究结果对于有效控制水源中溴离子具有重要意义。

关键词: 磁性离子交换树脂, 腐殖酸, 疏水性, 溴离子, 亲水性, 吸附

Abstract:

The effect of different hydrophilic/hydrophobic humic acid on the removal of bromide adsorbed on magnetic ion exchange resin was studied. When the pH value of the solution was 7.0, the presence of four humic acid components (very hydrophobicity, slightly hydrophobicity, polar hydrophilicity, neutral hydrophilicity) reduced the removal efficiency of bromide. In contrast, the hydrophobic components of humic acid had the most significant adverse effect on the removal efficiency of bromide. Humic acid weakened the pH dependence of the adsorption process of bromide on resin. The fractions of humic acid can accelerate the adsorption rate of bromide. The adsorption equilibrium was attained quickly. With or without the fractions of humic acid, the kinetic processes of bromide adsorbed on resin agreed with the pseudo-second-order model. Because of the competitive adsorption, the humic acid fractions reduced significantly the equilibrium adsorption capacity of resin for bromide. The adsorption equilibrium can be simulated by Langmuir and Freundlich isotherm model. The existence of HA components can reduce the spontaneity of adsorption system, and the very hydrophobicity component had more significant effect. The results of this investigation were of great significance for the effective control of bromide in water sources.

Key words: magngetic ion exchange resin, humic acid, hydrophilicity, bromide, hydrophobicity, adsorption

中图分类号:

TU991.2

李凌, 丁磊, 薛岗, 贾韫翰, 钟梅英, 张德伟. 不同亲疏水性腐殖酸对磁性离子交换树脂吸附去除水中溴离子的影响[J]. 过程工程学报, 2021, 21(7): 807-816.

LI Ling, Lei DING, Gang XUE, Yunhan JIA, Meiying ZHONG, Dewei ZHANG. Effects of hydrophilicity/hydrophobicity of humic acid components on the removal of bromide adsorbed on magnetic ion exchange resin[J]. The Chinese Journal of Process Engineering, 2021, 21(7): 807-816.

图/表 11

图1 MIEX树脂扫描电镜图

Fig.1 SEM images of MIEX resin

表1 MIEX树脂的性能参数[22]

Table 1 Performance parameters of MIEX resin[22]

Parameter	MIEX
Type	Macroporous
Structure	Polyacrylic
Zero charge point/MW	6.4
Particle size/mm	0.15
Water content/%	65~67.1
Magnetic material content/%	8.52
Total pore volume/(cm³/mL)	0.018
Exchange capacity/(meq/mL)	0.32~0.65
BET specific surface area/(m²/g)	21.47

图2 不同亲/疏水性HA组分对MIEX树脂吸附溴离子的影响

Fig.2 Effect of HA fractions with different hydrophilicity/hydrophobicity on the removal of bromide adsorbed on MIEX resin

图3 不同亲/疏水性HA组分在MIEX树脂上的去除效能

Fig.3 Removal of HA components with different hydrophilic/hydrophobic properties in MIEX resin

表2 四种HA组分的Zeta电位

Table 2 The Zeta potentials of four HA components

Zeta potential/mV	Component of HA
Zeta potential/mV	VHC	SHC	PHC	NHC
pH=7.0	-12.70	-12.60	-9.54	-8.78

图4 不同亲/疏水性HA组分在不同pH值下对MIEX树脂吸附溴离子的影响

Fig.4 Effect of HA fractions with different hydrophilicity/hydrophobicity on the removal of bromide adsorbed on MIEX resin at different pH values

图5 不同亲/疏水性HA组分对溴离子在MIEX树脂上吸附动力学的影响

Fig.5 Effect of HA fractions with different hydrophilicity/hydrophobicity on the kinetics of bromide adsorbed on MIEX resin

表3 吸附动力学模型计算的参数

Table 3 Parameters calculated from adsorption kinetics model

Component of bromide solution	Pseudo-first order kinetic model				Pseudo-second order kinetic model
Component of bromide solution	q_e/ (mg/L)	k₁/min^-1	R²	SE	q_e/ (mg/L)	k₂/min^-1	R²	SE
Br^-	0.34	0.170	0.94	0.008	0.37	0.710	0.99	0.005
Br^-+HA (VHC)	0.05	0.294	0.95	0.001	0.05	10.056	0.98	0.001
Br^-+HA (SHC)	0.03	0.135	0.91	0.001	0.03	6.158	0.96	0.001
Br^-+HA (PHC)	0.07	0.292	0.94	0.002	0.07	7.150	0.97	0.002
Br^-+HA (NHC)	0.09	0.229	0.94	0.003	0.10	3.761	0.98	0.003

图6 不同亲/疏水性HA组分对溴离子在MIEX树脂上吸附平衡的影响

Fig.6 Effect of HA fractions with different hydrophilicity/hydrophobicity on the adsorption equilibrium of bromide adsorbed on MIEX resin

表4 吸附平衡模型计算的参数

Table 4 Parameters calculated from adsorption equilibrium model

Component of bromide solution	Langmuir				Freundlich
Component of bromide solution	q_max/(mg/mL)	k_l/(L/mg)	R²	SE	k_f	1/n	R²	SE
Br^-	13.10	0.001	0.99	0.307	2.50	0.853	0.99	0.020
Br^-+HA (VHC)	1.04	0.304	0.96	0.630	0.27	1.046	0.95	0.186
Br^-+HA (SHC)	1.10	0.578	0.93	0.906	0.47	1.101	0.92	0.259
Br^-+HA (PHC)	1.73	0.052	0.95	0.582	0.91	0.968	0.95	0.171
Br^-+HA (NHC)	1.40	0.913	0.98	0.517	0.78	1.237	0.97	0.152

表5 HA组分存在时Br-在MIEX树脂上的吸附热力学参数

Table 5 Thermodynamic parameters of Br- absorbed on MIEX resin in the presence of HA component

Component	T/K	K_D/(L/mL)	ΔG⁰/ (kJ/mol)	ΔH⁰/ (kJ/mol)	ΔS⁰/(J/mol)
Br^-	288	18.37	-6.77	-92.40	-279.33
	293	7.35	-5.28
	298	5.05	-3.79
Br^-+VHC	288	0.63	1.10	18.45	60.24
	293	0.74	0.80
	298	0.81	0.50
Br^-+SHC	288	1.23	-0.56	2.16	9.44
	293	1.37	-0.61
	298	1.26	-0.65
Br^-+PHC	288	3.04	-2.83	-20.23	-60.40
	293	3.27	-2.53
	298	2.29	-2.23
Br^-+NHC	288	2.89	-2.70	-21.89	-66.61
	293	3.00	-2.37
	298	2.12	-2.04

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不同亲疏水性腐殖酸对磁性离子交换树脂吸附去除水中溴离子的影响

Effects of hydrophilicity/hydrophobicity of humic acid components on the removal of bromide adsorbed on magnetic ion exchange resin

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