膨润土基类芬顿复合材料的制备及其吸附去除废水中污染物的性能

郑宇; 于洁; 李平; 王趁义; 徐园园; 田啸; 汤唯唯

doi:10.13801/j.cnki.fhclxb.20210922.002

膨润土基类芬顿复合材料的制备及其吸附去除废水中污染物的性能

doi: 10.13801/j.cnki.fhclxb.20210922.002

郑宇^1,,
于洁²,
李平¹,
王趁义^1, ,,
徐园园^1,,
田啸¹,
汤唯唯¹

1.
浙江万里学院　生物与环境学院，宁波 315100
2.
宁波晟乾环境技术开发有限公司，宁波 315100

基金项目: 国家自然科学基金(21207036)；浙江省基础公益研究计划(LGF21E080014)；浙江省一流学科“生物工程”开放基金(KF2021008)；浙江省有机废弃物转化及过程强化技术重点实验室项目(2020E10018)；浙江万里学院乡村环保产业技术推广科技特派团队项目

详细信息

通讯作者:
王趁义，博士，教授，硕士生导师，研究方向为污染环境的生态修复与治理　E-mail：wcyxz@163.com

中图分类号: X705
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出版历程
- 收稿日期: 2021-06-04
- 修回日期: 2021-09-13
- 录用日期: 2021-09-13
- 网络出版日期: 2021-09-23
- 刊出日期: 2022-06-01

Preparation of bentonite-based Fenton composite material and its adsorption and removal of pollutants in wastewater

ZHENG Yu^1
,,
YU Jie²,
LI Ping¹,
WANG Chenyi^{1
, ,},
XU Yuanyuan^1
,,
TIAN Xiao¹,
TANG Weiwei¹

1.
College of Biology and Environment, University of Zhejiang Wanli, Ningbo 315100, China
2.
Ningbo Shengqian Environmental Technology Development CO. LTD., Ningbo 315100, China

摘要

摘要: 为实现废弃物资源化及去除废水中污染物，将粉煤灰、干化污泥、牡蛎壳等3种原料按照一定比例混合为基础原料(FDO)，掺入2种膨润土基无机矿物材料，制得具有去除氨氮(NH₄⁺-N)和高锰酸盐指数(I_Mn)双重功能的2种新型类芬顿复合材料(SFM)，分别记作活性白土型(ATC/FDO)、膨润土型(BT/FDO)。使用SEM和BET对SFM的表面形貌、孔径结构进行了表征，对比研究了2种SFM在类芬顿体系下对废水中的I_Mn和NH₄⁺-N的吸附去除效果，并采用动力学和吸附等温模型分析其吸附特性。结果表明，ATC/FDO对I_Mn和NH₄⁺-N的去除效果优于BT/FDO，处理5天后，相应的去除率分别高达95.76%和99.65%；ATC/FDO最优制备条件是：FDO∶ATC的质量比为5∶5，煅烧温度400℃，煅烧时间120 min；最佳使用条件是：20℃、pH=6.5，ATC/FDO∶H₂O₂用量比为5 g/L∶1 mL/L。2种SFM对NH₄⁺-N的吸附过程均符合准二级动力学，且符合Freundlich吸附等温方程。研究结果能为废弃物的资源化利用和水处理领域提供新技术和新材料。
- 类芬顿复合材料 /
- 最优制备条件 /
- 处理条件优化 /
- NH₄⁺-N去除率 /
- I_Mn去除率
Abstract: In order to realize waste recycling and remove pollutants from wastewater, two new Fenton-like compo-sites (SFM) with dual functions of removing ammonia nitrogen (NH₄⁺-N) and permanganate index (I_Mn) were prepared. The two SFMs are made by mixing fly ash, dried sludge and oyster shell as basic raw materials (FDO) in a certain proportion and adding two bentonite based inorganic mineral materials, which are respectively recorded as activated clay type (ATC/FDO) and bentonite type (BT/FDO). The surface morphology and pore structure of SFM were characterized by SEM and BET. The adsorption and removal effects of I_Mn and NH₄⁺-N in wastewater under the Fenton-like system of two kinds of SFM were comparatively studied, and the adsorption characteristics were analyzed by kinetics and adsorption isotherm models. The results show that the removal effect of ATC/FDO on I_Mn and NH₄⁺-N is better than that of BT/FDO. After 5 days of treatment, the corresponding removal rate of ATC/FDO on I_Mn and NH₄⁺-N is as high as 95.76% and 99.65% respectively. The optimum preparation conditions of ATC/FDO are as follows: the mass ratio of activated clay as basic raw material is 5∶5, calcination temperature is 400℃, calcination time is 120 min. The optimum conditions are 20℃, pH=6.5, and the dosage ratio of ATC/FDO to H₂O₂ is 5 g/L∶1 ml/L. The adsorption process of NH₄⁺-N on the two SFMs conforms to the quasi-second-order kinetics and the Freundlich adsorption isotherm equation. The research results can provide new technologies and new materials for waste resource utilization and water treatment.
- Fenton-like composites /
- optimal preparation conditions /
- optimized processing conditions /
- NH₄⁺-N removal rate /
- I_Mn removal rate

HTML全文

图 1 基础原料(FDO)与活性白土(ATC)膨润土(BT)的质量比 (a)、新型类芬顿复合材料(SFM)的煅烧时间 (b) 和煅烧温度 (c)对污染物去除率的影响

Figure 1. Influences of mass ratio of basic raw material (FDO) to activated clay (ATC) bentonite (BT) (a), calcination time (b) and calcination temperature (c) of new Fenton like composite (SFM) on pollutant removal rate

I_Mn—Permanganate index

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图 2 活性白土型(ATC/FDO) (a) 和膨润土型(BT/FDO) (b)新型类芬顿复合材料放大倍数为50.0 K的SEM图像

Figure 2. SEM images of activated clay type (ATC/FDO) (a) and bentonite type (BT/FDO) (b) new Fenton like composites at 50.0 K magnification

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图 3 SFM的初始pH (a)、投加浓度值 (b)、H₂O₂投加浓度值 (c)、处理温度 (d) 和处理时间 (e) 对污染物去除率的影响

Figure 3. Influence of SFM's initial pH (a), dosing concentration value (b), H₂O₂ dosing concentration value (c), treatment temperature (d) and treatment time (e) on the removal rate of pollutants

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图 4 SFM的准一级 (a)、准二级 (b)NH₄⁺-N吸附曲线及反应动力学线性拟合曲线 (c)

Figure 4. Quasi first order (a), quasi second order (b) adsorption curves of NH₄⁺-N and reaction kinetics linear fitting curves (c) of SFM

q_e—Equilibrium adsorption capacity; q_t—Adsorption capacity at time t

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图 5 SFM的NH₄⁺-N吸附量曲线 (a) 、Langmuir (b) 及Freundlich (c) 吸附等温方程拟合曲线

Figure 5. NH₄⁺-N adsorption curves (a), Langmuir (b) and Freundlich (c) adsorption isotherm equation fitting curves of SFM

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表 1 试验材料及主要成分

Table 1. Main components of test materials

Material/wt%	SiO₂	Al₂O₃	Fe₂O₃	MgO	CaO	Na₂O	K₂O	Ignition loss
Dried sludge	47.65	13.84	14.14	4.22	3.12	1.92	0.94	3.44
Fly ash	45.32	24.29	7.39	2.46	2.69	1.38	0.75	2.42
Bentonite	69.80	14.26	1.86	2.78	1.78	1.48	1.61	3.16
Activated clay	63.44	15.69	2.37	1.36	0.58	0.69	0.84	3.94
Oyster shell	7.89	0.68	0.45	1.98	86.34	0.64	0.86	4.89

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表 2 SFM的NH₄⁺-N吸附动力学参数

Table 2. Kinetic parameters of NH₄⁺-N adsorption of SFM

Model	Parameters and equations	ATC/FDO	BT/FDO
First order kinetics	Equation	y=−0.0396x−0.1756	y=−0.0440x+0.5594
	R²	0.9203	0.8457
	q_e/(mg·g⁻¹)	1.1	1.014
	q_max/(mg·g⁻¹)	1.093	1.005
Second order kinetics	Equation	y=0.8365x+ 9.5827	y=0.7547x+ 27.5633
	R²	0.9986	0.9853
	q_e/(mg·g⁻¹)	1.091	1.016
Notes: R²—Correlation coefficient; q_max—Maximum adsorption capacity.

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表 3 SFM的NH₄⁺-N等温线参数

Table 3. Isotherm parameters NH₄⁺-N adsorption of SFM

Model	Parameters and equations	ATC/FDO	BT/FDO
Langmuir	Equation	y=0.0316x+26.0459	y=0.1833x+31.1318
	R²	0.8738	0.8583
	q_e/(mg·g⁻¹)	3.1614	2.215
	K_L	0.0012	0.0059
Freundlich	Equation	y=0.9389x−2.6443	y=0.8022x−2.9694
	R²	0.9993	0.9966
	K_f	0.0711	0.0513
	1/n	0.9389	0.8022
Notes: K_L—Parameters of Langmuir; K_f—Parameters of Freundlich; 1/n—Parameters of Freundlich.

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