铁基改性椰壳生物炭对砷的吸附效果及机制研究

doi:10.16258/j.cnki.1674-5906.2021.07.019

生态环境学报 ›› 2021, Vol. 30 ›› Issue (7): 1503-1512.DOI: 10.16258/j.cnki.1674-5906.2021.07.019

铁基改性椰壳生物炭对砷的吸附效果及机制研究

张苏明¹^,²(), 张建强²^,³, 周凯¹^,^*(), 陈志良²^,³^,^*()

1.河南科技学院园艺园林学院,河南新乡 453000
2.生态环境部华南环境科学研究所,广东广州 510000
3.广东省农田重金属污染土壤治理与修复工程技术研究中心,广东广州 510000

收稿日期:2021-04-19 出版日期:2021-07-18 发布日期:2021-10-09
通讯作者: *周凯（1969年生）,男,副教授,博士,研究方向为城市生态环境治理。E-mail: kzhou89@126.com;陈志良（1976年生）,男,研究员,博士,研究方向为土壤地下水污染防治。E-mail: chenzhiliang@scies.org
作者简介:张苏明（1995年生）,女,硕士研究生,研究方向为景观生态恢复技术研究。E-mail: 861595800 @qq.com
基金资助:
国家重点研发计划项目(2019YFC1805305);广东省基础与应用基础研究基金项目(2019A1515012131);广东省重点研发计划项目(2019B110207001);广东省重点研发计划项目(2020B1111350002);广东省国际合作项目(2021A0505030045);中央级公益性科研院所基本科研业务专项(PM-zx703-202002-035);河南省科技攻关计划项目(172102310755)

Adsorption Effect and Mechanism of Iron-based Modified Coconut Shell Biochar to Arsenic

ZHANG Suming¹^,²(), ZHANG Jianqiang²^,³, ZHOU Kai¹^,^*(), CHEN Zhiliang²^,³^,^*()

1. School of Horticulture and Landscape Architecture, Henan Institute of Science and Technology, Xinxiang 453000, China
2. South China Institute of Environmental Sciences, Central Department of Ecological and Environmental Engineering, Guangzhou 510000, China
3. Research Center for Soil Treatment and Restoration of Heavy Metal Pollution in Guangdong Province, Guangzhou 510000, China

Received:2021-04-19 Online:2021-07-18 Published:2021-10-09

摘要/Abstract

摘要：

目前针对生物炭修复重金属污染的水体、土壤方面的研究虽然很多,但是对其吸附污染物的机制研究却较少。为了提高生物炭对砷的吸附能力,以农业废弃物椰壳为原料,在300 ℃下利用硫酸及硫酸铁制备铁基改性生物炭,采用SEM-EDS、FTIR、XRD及XPS等手段对椰壳生物炭（CSB）、硫酸改性生物炭（SCSB）以及铁基改性生物炭（SFCSB）表面结构与特征进行表征,通过pH值影响实验、等温吸附实验和动力学吸附实验对CSB、SCSB及SFCSB 3种生物炭吸附砷（As）的效果进行比较。结果表明,硫酸及硫酸铁共同改性使生物炭的比表面积增大了1.56倍,表面官能团新增亚甲基（-CH₃）和羧基（-COO）,SFCSB表面的Fe吸附As(Ⅴ)后在Fe2p能级生成了Fe₂O₃和FeOOH,证明铁基改性成功。SFCSB对As(Ⅴ)的吸附符合Elovich动力学模型及Langmiur等温吸附模型,当pH=5时,SFCSB对砷的最大吸附量为14.65 mg∙g^-1,与未改性的CSB相比吸附量提高了238倍。SFCSB对As(Ⅴ)的吸附方式为物理化学吸附,吸附机制包括生物炭表面正电荷与阴离子之间的静电吸引、O-H-As氢键结合、砷氧阴离子与铁氧化物的配位体效应和表面羟基官能团络合等。研究表明,铁基改性椰壳生物炭是一种高效的除砷吸附剂。该研究从农业废弃物利用和环境修复的角度出发,为制备更高效、能深度净化污染的生物炭提供参考,也为吸附机制的探讨提供理论依据。

关键词: 椰壳生物炭, 硫酸, 硫酸铁, 改性, 吸附机制

Abstract:

At present, although there are many researches on biochar remediation of heavy metal polluted water and soil, there are few researches on the mechanism of biochar adsorption of pollutants. In order to improve the adsorption capacity of biochar to arsenic, the agricultural waste coconut shell was used as raw material to prepare iron-based modified biochar using sulfuric acid and ferric sulfate at 300 ℃. The surface structure and characteristics of coconut shell biochar (CSB), sulfuric acid modified biochar (SCSB) and iron-based modified biochar (SFCSB) were characterized by SEM-EDS, FTIR, XRD and XPS. The effect of CSB, SCSB and SFCSB biochar on the adsorption of arsenic (As) was studied and compared by pH influence experiment, isothermal adsorption experiment and kinetic adsorption experiment. The results show that the specific surface area of biochar is increased by 1.56 times by the joint modification of sulfuric acid and ferric sulfate, and the surface functional groups of biochar are increased by methylene (-CH₃) and carboxyl (-COO). After the adsorption of As(Ⅴ) on the surface of SFCSB, Fe₂O₃ and FeOOH are generated at the Fe2p level, which proves that the iron-based modification is successful. The adsorption of As(Ⅴ) by SFCSB was consistent with Elovich kinetic model and Langmiur isothermal adsorption model. When pH=5, the maximum adsorption capacity of SFCSB for arsenic is 14.65 mg∙g^-1, which is 238 times higher than that of the unmodified CSB. The adsorption mode of SFCSB for As(Ⅴ) is physicochemical adsorption, and the adsorption mechanism includes electrostatic attraction between positive charge and anion on the surface of biochar, O-H-As hydrogen bonding, ligand effect between arsenic oxide anion and iron oxide, and complexation of surface hydroxyl functional groups. Studies have shown that iron-based modified coconut shell biochar is an efficient arsenic removal adsorbent. From the perspective of agricultural waste utilization and environmental remediation, this study provides a reference for the preparation of more efficient biochar that can deeply purify pollution, and also provides a theoretical basis for the discussion of adsorption mechanism.

Key words: coconut shell biochar, sulfuric acid, ferric sulfate, modified, adsorption mechanism

中图分类号:

X712

张苏明, 张建强, 周凯, 陈志良. 铁基改性椰壳生物炭对砷的吸附效果及机制研究[J]. 生态环境学报, 2021, 30(7): 1503-1512.

ZHANG Suming, ZHANG Jianqiang, ZHOU Kai, CHEN Zhiliang. Adsorption Effect and Mechanism of Iron-based Modified Coconut Shell Biochar to Arsenic[J]. Ecology and Environment, 2021, 30(7): 1503-1512.

图/表 13

表1 生物炭的基本性质

Table 1 Basic properties of biochar

样品 The sample	pH	比表面积 Specific surface area/(m²∙g^-1)	w_(Fe)/ (mg∙g^-1)
CSB	9.92	247.382	1.78
SCSB	2.16	297.483	1.85
SFCSB-10	1.95	387.224	3.03

图1 生物炭的SEM-EDS图

Fig. 1 SEM-EDS image of biochar A: CSB-SEM, B: SCSB-SEM, C: SFCSB-10-SEM, D: CSB-EDS, E: SCSB-EDS, F: SFCSB-EDS

图2 生物炭的X射线衍射图

Fig. 2 X-ray diffraction pattern of biochar

图3 生物炭的FTIR光谱

Fig. 3 FTIR spectra of biochar

图4 生物炭的XPS（C1s、O1s、Fe2p和S2p）分析图谱

Fig. 4 XPS (C1s, O1s, Fe2P and S2P) analysis patterns of biochar

图5 pH对生物炭吸附As(Ⅴ)的影响

Fig. 5 Effect of pH on the adsorption of As(Ⅴ) by biochar

图6 不同溶液pH下生物炭Zeta电位的变化

Fig. 6 Changes of Biochar’s Zeta Potential under Different Solution pH

图7 生物炭对As(Ⅴ)的吸附动力学曲线（a）准一级动力学模型Quasi first order dynamics,（b）准二级动力学模型Quasi second order dynamics,（c）Elovich动力学模型Elovich model

Fig. 7 Adsorption kinetic curve of As(Ⅴ) on biochar

表2 动力学吸附As(Ⅴ)拟合参数

Table 2 Kinetic adsorption of As(Ⅴ) fitting parameters

样品 The sample	准一级动力学 Quasi first order dynamics				准二级动力学 Quasi second order dynamics		Elovich模型 Elovich model
样品 The sample	q_e/(mg∙g^-1)	k₁/(min^-1)	R²	q_e/(mg∙g^-1)	k₂/(g∙mg^-1∙min^-1)	R²	α/(g∙mg^-1∙min^-1)	Β/(g∙mg^-1)	R²
CSB	0.034	0.161	0.883	0.036	6.408	0.959	0.111	237.665	0.900
SCSB	0.228	0.009	0.993	0.340	0.018	0.992	0.001	2.412	0.975
SFCSB-5	7.331	0.013	0.936	7.798	0.002	0.975	0.418	0.796	0.990
SFCSB-10	5.926	0.063	0.767	8.088	0.003	0.855	1.110	0.747	0.992
SFCSB-15	9.950	0.016	0.882	10.363	0.002	0.950	2.628	0.768	0.988

图8 生物炭对As(Ⅴ)的等温吸附曲线（a）Langmiur模型Langmiur model,（b）Freundlich模型Freundlich model

Fig. 8 Adsorption isotherm of As(Ⅴ) on biochar

表3 改性前后生物炭对As(Ⅴ)吸附等温线模型的拟合参数

Table 3 Fitting parameters of As(Ⅴ)-adsorption isotherm model of biochar before and after modification

样品 The sample	Langmiur模型 Langmiur model			Freundlich模型 Freundlich model
样品 The sample	q_m/ (mg∙g^-1)	K_L/ (L∙mg^-1)	R²	K_F/ (mg^1-ⁿ∙g^-1∙L^-ⁿ)	$\frac{1}{n}/$ (g∙L^-1)	R²
CSB	0.062	3.452	1.000	0.004	0.529	0.465
SCSB	5.209	0.001	0.965	0.003	1.066	0.818
SFCSB-5	9.164	0.393	0.966	3.964	0.177	0.728
SFCSB-10	10.262	0.914	0.954	4.973	0.163	0.979
SFCSB-15	14.297	2.707	0.977	7.320	0.158	0.600

图9 SFCSB-10吸附As(Ⅴ)后的FTIR光谱

Fig. 9 FTIR spectra of SFCSB-10 after adsorption of As(Ⅴ)

图10 SFCSB-10吸附As(Ⅴ)后的XPS（C1s、Fe2p、S2p、O1s、As2p）射线图谱（b）C1s分峰图谱,（c）Fe2p分峰图谱,（d）S2p分峰图谱,（e）O1s分峰图谱,（f）As2p分峰图谱

Fig. 10 XPS (C1s, Fe2p, S2p, O1s, AS2p) spectrum of SFCSB-10 after adsorption of As(Ⅴ) (b) C1s peak segmentation map, (c) Fe2p peak segmentation map, (d) S2p peak segmentation map, (e) O1s peak segmentation map, (f) AS2p peak segmentation map

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铁基改性椰壳生物炭对砷的吸附效果及机制研究

Adsorption Effect and Mechanism of Iron-based Modified Coconut Shell Biochar to Arsenic

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