腐殖酸和吐温-80对微米镍铁/多氯联苯体系的传质调控研究

doi:10.16258/j.cnki.1674-5906.2022.07.019

生态环境学报 ›› 2022, Vol. 31 ›› Issue (7): 1456-1464.DOI: 10.16258/j.cnki.1674-5906.2022.07.019

腐殖酸和吐温-80对微米镍铁/多氯联苯体系的传质调控研究

吕贵方¹^,²(), 吴颖欣², 董长勋¹^,^*(), 卢阳², 周玥², 曾文军¹^,², 吴文成²^,^*()

1.南京农业大学理学院,江苏南京 210095
2.生态环境部华南环境科学研究所,广东广州 510655

收稿日期:2021-12-12 出版日期:2022-07-18 发布日期:2022-08-31
通讯作者: 吴文成,E-mail: wuwencheng@scies.org
^*董长勋,E-mail: dongcx@njau.edu.cn;
作者简介:吕贵方（1997年生）,男,硕士研究生,研究方向为环境污染物控制。E-mail: 1362447284@qq.com
基金资助:
国家自然科学基金项目(41907115);广州市科技计划项目(202102021025)

Study on the Mass Transfer Regulation in Micro-scale Ni-Fe/PCBs System by Humic Acid and Tween-80

LÜ Guifang¹^,²(), WU Yingxin², DONG Changxun¹^,^*(), LU Yang², ZHOU Yue², ZENG Wenjun¹^,², WU Wencheng²^,^*()

1. College of Sciences, Nanjing Agricultural University, Nanjing 210095, P. R. China
2. South China Institute of Environment Sciences, Ministry of Ecology and Environment, Guangzhou 510655, P. R. China

Received:2021-12-12 Online:2022-07-18 Published:2022-08-31

摘要/Abstract

摘要：

多氯联苯（PCBs）向铁基材料表面传输的过程（即传质过程）是铁基材料降解PCBs的关键途径。腐殖酸（HA）和表面活性剂吐温-80（Tween-80）能够通过改变传质过程来影响PCBs的降解而被广泛关注,但关于两者改变传质过程差异性及其机制的报道较少。通过制备微米镍铁（Ni/Fe）颗粒,探究不同质量浓度HA（10、50、100 mg∙L^-1）和Tween-80[1、25、500倍临界胶束浓度 (CMC)]对Ni/Fe降解水溶液中2, 2′, 4′, 4′, 5-五氯联苯（PCB-99）的影响,通过体系中PCB-99、HA和Tween-80的固液分配来解析两者改变传质过程的机制与差异。结果表明,HA和Tween-80均抑制Ni/Fe降解PCB-99,降解过程符合准二级动力学模型,HA或Tween-80的质量浓度越高,抑制作用越显著,PCB-99的降解率越低。其中,HA吸附在Ni/Fe表面形成HA层,覆盖反应位点,阻碍PCB-99和水与Ni/Fe接触,导致留在固相上而未被降解的PCB-99占初始加入量的49.48%。相反,Tween-80主要通过增流和增溶作用影响传质过程,Tween-80吸附在Ni/Fe表面,能够降低界面张力,增加PCB-99的流动性,导致传质效率下降;当液相中的Tween-80质量浓度超过CMC时,PCB-99被困在胶束形成的疏水核中,占PCB-99初始加入量的56.01%,难以接触Ni/Fe。该研究可为持久性有机卤代烃的降解提供科学依据。

关键词: 镍铁颗粒, 多氯联苯, 表面活性剂, 腐殖酸, 传质过程

Abstract:

The transfer process of polychlorinated biphenyls (PCBs) to the surface of iron-based materials (i.e., mass transfer process) is a key step in the degradation of PCBs by iron-based materials. Humic acid (HA) and surfactant Tween-80 have been widely concerned for their ability to affect the degradation of PCBs by changing the mass transfer process, while there are few reports on the differential mechanisms of these two factors. In this study, the micro-scale Ni-Fe particles were employed to explore the effects of HA (10, 50 and 100 mg∙L^-1) and Tween-80 [1, 25 and 500 critical micelle concentration (CMC)] on the degradation of 2, 2′, 4, 4′, 5-pentachlorobiphenyl (PCB-99) by Ni/Fe in aqueous solution. The solid-liquid distributions of HA, Tween-80 and PCB-99 were analyzed to understand the differential mechanisms regulating the mass transfer process. The results showed that both HA and Tween-80 inhibited the degradation of PCB-99 by Ni/Fe, and both of the degradation processes conformed to the pseudo-second-order kinetic model. The higher concentration of HA or Tween-80 resulted in more significant inhibition and lower degradation rate of PCB-99. The HA layer on the Ni/Fe surface covered the reactive sites and prevented the contact of PCB-99 with Ni/Fe, resulting in 49.48% of PCB-99 remaining on the solid phase without being degraded. Tween-80 mainly affected the mass transfer process via enhancing the mobility and solubilization of PCB-99. The Tween-80 adsorbed on the Ni/Fe surface reduced the interfacial tension, increased the mobility of PCB-99, and led to a decrease in mass transfer efficiency. When the concentration of Tween-80 in the liquid phase exceeds the CMC value, the formed micelles trapped 56.01% of PCB-99 in the hydrophobic core, making it difficult to contact with Ni/Fe. This study provides a scientific basis for the degradation of persistent organohalogenated hydrocarbons.

Key words: nickel-iron particles (Ni/Fe), polychlorinated biphenyls (PCBs), surfactant (Tween-80), humic acid (HA), mass transfer process

中图分类号:

吕贵方, 吴颖欣, 董长勋, 卢阳, 周玥, 曾文军, 吴文成. 腐殖酸和吐温-80对微米镍铁/多氯联苯体系的传质调控研究[J]. 生态环境学报, 2022, 31(7): 1456-1464.

LÜ Guifang, WU Yingxin, DONG Changxun, LU Yang, ZHOU Yue, ZENG Wenjun, WU Wencheng. Study on the Mass Transfer Regulation in Micro-scale Ni-Fe/PCBs System by Humic Acid and Tween-80[J]. Ecology and Environment, 2022, 31(7): 1456-1464.

图/表 6

图1 ZVI（a）和Ni/Fe（b）的SEM图像以及Ni/Fe的EDS图谱（c）

Figure 1 SEM images of ZVI (a), Ni/Fe (b) and EDS spectrum of Ni/Fe (c)

图2 不同质量浓度的HA（a）和Tween-80（b）影响下Ni/Fe降解PCB-99的动力学曲线及平衡降解率（c）图中的误差线为标准差（n=3）,下同;不同的字母表示不同处理间差异极显著（P<0.001）,下同

Figure 2 Kinetic curves of the degradation of PCB-99 by Ni/Fe with different concentrations of HA (a) and Tween-(b), and the degradation rates of PCB-99 (c) The error bars in the figure are standard deviations (n=3), the same below; different letters indicate extremely significant differences among different treatments (P<0.001), the same below

表1 HA和Tween-80影响下Ni/Fe降解PCB-99的动力学拟合结果

Table 1 Kinetic fitting results of Ni/Fe degradation of PCB-99 under the influence of HA and Tween-80

因素 Factor	质量浓度 C_(Factor)	准一级降解动力学 Pseudo-first-order degradation kinetics		准二级降解动力学 Pseudo-second-order degradation kinetics
因素 Factor	质量浓度 C_(Factor)	k₁/h^-1	r₁²	k₂/[(mg∙L^-1)^-1∙h^-1]	r₂²
HA	0	0.01389	0.81	0.03395	0.90
	10 mg∙L^-1	0.00949	0.90	0.01446	0.92
	50 mg∙L^-1	0.00762	0.89	0.01039	0.90
	100 mg∙L^-1	0.00533	0.90	0.00638	0.92
Tween-80	1 CMC	0.01042	0.99	0.01413	0.99
	25 CMC	0.00900	0.75	0.01154	0.80
	500 CMC	0.00691	0.75	0.00830	0.79

图3 不同质量浓度HA和Tween-80影响下PCB-99在固液两相中的分配

Figure 3 The partition of PCB-99 in solid and liquid phases under the influence of HA and Tween-80 at different concentrations

图4 不同质量浓度的HA（a）和Tween-80（b）在Ni/Fe降解PCB-99体系中的吸附动力学曲线

Figure 4 The adsorption kinetics curves of HA (a) and Tween-80 (b) at different concentrations in Ni/Fe degradation system

表2 Ni/Fe吸附HA和Tween-80的动力学拟合结果

Table 2 Kinetic fitting results of HA and Tween-80 adsorption on Ni/Fe

因素 Factor	质量浓度 µ_(factor)	q_e/ (mg∙g^-1)	准一级吸附动力学 Pseudo-First-Order Adsorption Kinetics			准二级吸附动力学 Pseudo-second-order adsorption kinetics
因素 Factor	质量浓度 µ_(factor)	q_e/ (mg∙g^-1)	q_c/(mg∙g^-1)	K₁/h^-1	r₁²	q_c/(mg∙g^-1)	K₂/(g∙mg^-1∙h^-1)	r₂²
HA	10 mg∙L^-1	0.50	0.49	1.86497	0.96	0.50	12.87341	0.99
	50 mg∙L^-1	1.23	1.23	2.64982	0.86	1.27	6.77221	0.99
	100 mg∙L^-1	2.27	2.20	0.84679	0.70	2.37	0.30022	0.99
Tween-80	1 CMC	0.49	0.36	0.36033	0.85	0.49	3.58238	0.99
	25 CMC	10.37	8.03	0.05684	0.92	10.71	0.01875	0.99
	500 CMC	210.83	198.34	0.02222	0.96	250	0.000176	0.95

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腐殖酸和吐温-80对微米镍铁/多氯联苯体系的传质调控研究

Study on the Mass Transfer Regulation in Micro-scale Ni-Fe/PCBs System by Humic Acid and Tween-80

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