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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- 被引次数: 0
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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参考文献(25)

[1]	ZHOU W, ZHAO H, GAO J, et al. Influence of a reagents addition strategy on the Fenton oxidation of rhodamine B: Control of the competitive reaction of OH[J]. Rsc Advances,2016,6(110):108791-108800. doi: 10.1039/C6RA20242J
[2]	闫云涛, 张柯, 毛岩鹏, 等. Fe₂O₃@SCe多相芬顿催化剂的制备及其降解放热性能[J]. 中国环境科学, 2020, 40(8):3375-3384. doi: 10.3969/j.issn.1000-6923.2020.08.015 YAN Y T, ZHANG K, MAO Y P, et al. Fe₂O₃@SCe Preparation of heterogeneous Fenton catalyst and its degradation exothermic performance[J]. China Environmental Science,2020,40(8):3375-3384(in Chinese). doi: 10.3969/j.issn.1000-6923.2020.08.015
[3]	SHU J, CHEN M, WU H, et al. An innovative method for synergistic stabilization/solidification of Mn²⁺, NH₄⁺-N, PO₄^3- and F^- in electrolytic manganese residue and phosphogypsum[J]. Journal of Hazardous Materials,2019,376:212-222. doi: 10.1016/j.jhazmat.2019.05.017
[4]	杨昕达, 郝林林, 常达, 等. 膨润土对垃圾渗滤液絮凝预处理的强化效果[J]. 环境工程学报, 2021(5):1549-1557. doi: 10.12030/j.cjee.202010110 YANG X D, HAO L L, CHANG D, et al. Strengthening effect of bentonite on flocculation pretreatment of landfill leachate[J]. Journal of Environmental Engineering,2021(5):1549-1557(in Chinese). doi: 10.12030/j.cjee.202010110
[5]	LIU T, TIAN X F, ZHAO Y, et al. Swelling of K⁺, Na⁺ and Ca²⁺-montmorillonites and hydration of interlayer cations: A molecular dynamics simulation[J]. Chinese Physics B,2010,19(10):656-662.
[6]	YIP C K, LAM L Y, HU X. A novel heterogeneous acid-activated clay supported copper catalyst for the photobleaching and degradation of textile organic pollutant using photo-Fenton-like reaction[J]. Chemical Communications,2005,41(25):3218-3220.
[7]	陈宁, 王海滨, 刘树信. 空心粉煤灰对铁氧体-炭黑/水泥基复合材料吸波性能的影响[J]. 复合材料学报, 2017, 34(6):1381-1387. CHENG N, WANG H B, LIU S X. Effect of hollow fly ash on the wave absorption properties of Ferrite-carbon black/cement-based composites[J]. Acta Materiae Compositae Sinica,2017,34(6):1381-1387(in Chinese).
[8]	BOULOS R A, HAMAGEA C, DUAN X, et al. Unzipping oyster shell[J]. Rsc Advances,2013,3(10):3284-3290. doi: 10.1039/c2ra21763e
[9]	张天永, 王智超, 姜爽, 等. 煤渣在水处理方面的应用研究进展[J]. 现代化工, 2018, 38(3):32-36. ZHANG T Y, WANG Z C, JIANG S. et. al. Research progress in the application of coal slag in water treatment[J]. Modern Chemical Industry,2018,38(3):32-36(in Chinese).
[10]	王晶, 高娜, 刘双元, 等. 活性污泥微生物解壳聚糖松江菌中菌胶团形成相关大型基因簇的鉴定和分析[J]. 微生物学通报, 2019, 46(8):1946-1953. WANG J, GAO N, LIU S Y, et al. Identification and analysis of large-scale gene clusters related to the formation of micelles in the activated sludge microbial chitosan solution of Songjiang bacteria[J]. Microbiology Bulletin,2019,46(8):1946-1953(in Chinese).
[11]	刘文, 李天华, 张滕军, 等. 牡蛎壳中钙的改性及吸附特性的研究[J]. 材料导报, 2012, 26(18):88-92. doi: 10.3969/j.issn.1005-023X.2012.18.024 LIU W, LI T H, ZHANG T J, et al. Study on the modification of calcium in oyster shell and its adsorption characteristics[J]. Material Guide,2012,26(18):88-92(in Chinese). doi: 10.3969/j.issn.1005-023X.2012.18.024
[12]	生态环境部. 水质高锰酸盐指数的测定: GB/T 11892—1989[S]. 北京: 北京环保监测中心, 1989. Ministry of Ecology and Environment. The water quality Determination of permanganate index: GB/T 11892—1989[S]. Beijing: Beijing Environmental Monitoring Center, 1989(in Chinese).
[13]	生态环境部. 水质铵的测定水杨酸分光光度法: GB/T7481—1987[S]. 赣州: 赣州环境监测站, 1987. Ministry of Ecology and Environment. The water quality The determination of ammonium Salicylic acid spectrophotometry: GB/T7481—1987[S]. Ganzhou: Ganzhou Environmental Monitoring Station, 1987(in Chinese).
[14]	陈凤霞, 马家海. Fe₃O₄@PCDP纳米复合材料的制备及其在类芬顿体系中的应用(英文)[J]. 中国科学院大学学报, 2020, 37(5):593-598. doi: 10.7523/j.issn.2095-6134.2020.05.003 CHEN F X, MA J H. Preparation of Fe₃O₄@PCDP nanocomposite and its application in Fenton-like system (English)[J]. Journal of University of Chinese Academy of Sciences,2020,37(5):593-598(in Chinese). doi: 10.7523/j.issn.2095-6134.2020.05.003
[15]	魏光涛, 周萍, 韦藤幼, 等. H₃PMo₁₂O₄₀/活性白土UV-H₂O₂催化氧化降解甲基橙[J]. 化工环保, 2011, 31(3):210-213. doi: 10.3969/j.issn.1006-1878.2011.03.005 WEI G T, ZHOU P, WEI T Y, et al. Catalytic oxidative degradation of methyl orange by H₃PMo₁₂O₄₀/activated clay UV- H₂O₂[J]. Chemical Environmental Protection,2011,31(3):210-213(in Chinese). doi: 10.3969/j.issn.1006-1878.2011.03.005
[16]	MAHATA B K, CHUNG K L, CHANG S M. Removal of ammonium nitrogen (NH₄⁺-N) by Cu-loaded amino-functionalized adsorbents[J]. Chemical Engineering Journal,2021,411(7):128-139.
[17]	郭欢. 硅藻土-钨渣基多孔陶粒的制备与性能研究[D]. 赣州: 江西理工大学, 2017. GUO H. Study on the preparation and properties of diatomite-tungsten slag-based porous ceramsite[D]. Ganzhou: Jiangxi University of Science and Technology, 2017(in Chinese).
[18]	魏建平, 戴俊, 王政锦, 等. Fenton试剂氧化降解甲烷的动力学规律[J]. 煤炭学报, 2013, 38(9):1597-1603. WEI J P, DAI J, WANG Z J, et al. Kinetic law of Fenton reagent oxidative degradation of methane[J]. Journal of China Coal Society,2013,38(9):1597-1603(in Chinese).
[19]	GERMÁN S M , GABRIEL R M, EDUARDO M D C, et al. Electro-Fenton and Electro-Fenton-like with in situ electrogeneration of H₂O₂ and catalyst applied to 4-chlorophenol mineralization[J]. Electrochimica Acta,2016,195:246-256. doi: 10.1016/j.electacta.2016.02.093
[20]	赵雅娴, 武帅, 康宸, 等. H₂O₂改性对聚丙烯腈原丝化学结构的影响[J]. 复合材料学报, 2019, 36(1):85-95. ZHAO Y X, WU S, KANG C. et al. Effect of H₂O₂ modification on the chemical structure of polyacrylonitrile precursor[J]. Acta Materiae Compositae Sinica,2019,36(1):85-95(in Chinese).
[21]	CHEN C Y, TANG C, WANG H F, et al. Oxygen reduction reaction on graphene in an Electro-Fenton system: in situ generation of H₂O₂ for the oxidation of organic compounds[J]. Chemsuschem,2016,9(10):1194-1199. doi: 10.1002/cssc.201600030
[22]	赵海谦, 高杏存, 王忠华, 等. Fe²⁺/H₂O₂体系O₂生成路径[J]. 化工学报, 2016, 67(6):237-245. ZHAO H Q, GAO X C, WANG Z H, et al. O₂ generation path in Fe²⁺/H₂O₂ system[J]. Journal of Chemical Industry,2016,67(6):237-245(in Chinese).
[23]	陈仕稳, 聂锦旭, 谢伟楠, 等. 改性膨润土颗粒对微污染水中有机物和氨氮的吸附[J]. 环境工程学报, 2015, 9(6):2739-2744. doi: 10.12030/j.cjee.20150632 CHEN S W, NIE J X, XIE W N, et al. Adsorption of organic matter and ammonia nitrogen in micro-polluted water by modified bentonite particles[J]. Journal of Environmental Engineering,2015,9(6):2739-2744(in Chinese). doi: 10.12030/j.cjee.20150632
[24]	王趁义, 黄添浩, 滕丽华, 等. 绿沸石对废水中氨氮的吸附效果研究[J]. 非金属矿, 2019, 42(1):21-24. doi: 10.3969/j.issn.1000-8098.2019.01.007 WANG C Y, HUANG T H, TENG L H, et al. Study on the adsorption effect of Green Zeolite on ammonia nitrogen in wastewater[J]. Non-Metallic Minerals,2019,42(1):21-24(in Chinese). doi: 10.3969/j.issn.1000-8098.2019.01.007
[25]	魏世勇, 杨小洪. 针铁矿-高岭石复合体的表面性质和吸附氟的特性[J]. 环境科学, 2010, 31(9):2134-2142. WEI S Y, YANG X H. Surface properties and fluorine adsorption characteristics of goethite-kaolinite complex[J]. Environmental Science,2010,31(9):2134-2142(in Chinese).