天然含铁锰矿对砷的高效去除性能与机制研究

田周炀; 郑倩; 杜晓丽; 陈成; 李传维; 涂书新

doi:10.12153/j.issn.1674-991X.20230058

天然含铁锰矿对砷的高效去除性能与机制研究

doi: 10.12153/j.issn.1674-991X.20230058

1.
华中农业大学资源与环境学院
2.
武汉芳笛环保股份有限公司
3.
北京建工环境修复股份有限公司

基金项目: 国家自然科学基金项目(42277392)；国家重点研发计划项目(2018YFC1800305)

详细信息

作者简介:
田周炀(1999—)，女，硕士研究生，研究方向为重金属污染修复，tianzy@webmail.hzau.edu.cn

通讯作者:
涂书新(1962—)，男，教授，主要从事环境污染与修复，stu@mail.hzau.edu.cn

中图分类号: X52
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- 文章访问数: 123
- HTML全文浏览量: 63
- PDF下载量: 32
- 被引次数: 0
出版历程
- 收稿日期: 2023-01-29
- 录用日期: 2023-07-04
- 修回日期: 2023-07-04
- 网络出版日期: 2023-11-24

Study on efficient arsenic removal performance and mechanism of natural ferromanganese ore

1.
College of Resources and Environment, Huazhong Agricultural University
2.
Wuhan Fangdi Environmental Protection Co., Ltd.
3.
Beijing Construction Engineering Group Environmental Remediation Co., Ltd.

摘要

摘要:
为开发高效、廉价的水体As(Ⅲ)去除材料，采用天然铁锰矿(NFM)作为吸附剂，通过动力学、热力学、等温吸附以及吸附/解吸试验评估其对As(Ⅲ)的吸附性能，结合傅里叶变换红外光谱、扫描电镜以及X射线光电子能谱（XPS）等表征手段进行机理分析，并与铁锰二元氧化物(FMO)、水钠锰矿(Bir)和针铁矿(Goe)的吸附特性进行对比。结果表明：NFM主要由锰氧化物和铁氧化物组成，铁锰摩尔比为6∶1，比表面积为280.4 m²/g，对As(Ⅲ)的饱和吸附容量为48.3 mg/g。Freundlich模型和准二级动力学模型能较好地拟合NFM的吸附过程。XPS等分析表明，NFM的吸附和氧化的协同作用是去除As(Ⅲ)的关键因素。其中，锰氧化物展示出优异的氧化As(Ⅲ)的能力，而铁氧化物具有强的吸附作用。
- As(Ⅲ) /
- 天然含铁锰矿 /
- 锰氧化物 /
- 铁氧化物 /
- 吸附 /
- 氧化
Abstract:
In order to develop an efficient and inexpensive material for As(Ⅲ) removal from water, natural ferromanganese ore (NFM) was used as adsorbent. Kinetic, thermodynamic, isothermal adsorption and adsorption/desorption experiments were conducted to evaluate the adsorption performance of As(Ⅲ). The mechanism was analyzed by Fourier transform infrared spectroscopy, scanning electron microscopy, X-ray photoelectron spectroscopy, and the adsorption characteristics were compared with those of iron-manganese binary oxide (FMO), birnessite (Bir), and goethite (Goe). The results showed that NFM was mainly composed of manganese oxide and iron oxide, with a Fe-Mn molar ratio of 6∶1, the specific surface area of 280.4 m²/g, and a saturation adsorption capacity of 48.3 mg/g for As(Ⅲ). The Freundlich model and the pseudo-second order kinetic model could better fit the adsorption process of NFM. XPS and other characterization analyses indicated that the synergistic effect of adsorption and oxidation of NFM was the key factor for As(Ⅲ) removal. Among them, manganese oxides exhibited excellent oxidation of As(Ⅲ), while iron oxides had strong adsorption.
- As(Ⅲ) /
- natural ferromanganese ore /
- manganese oxide /
- iron oxide /
- adsorption /
- oxidation

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图 1 吸附剂的XRD与FTIR图谱

Figure 1. XRD spectrum and FTIR spectra of original absorbents

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图 2 吸附剂对As(Ⅲ)的吸附等温线

Figure 2. Adsorption isotherm plot of As(Ⅲ) on adsorbents

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图 3 ln K_c与1/T×10⁻³的拟合线

Figure 3. Fitting plot of ln K_c versus 1/T×10⁻³

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图 4 吸附剂对As(Ⅲ)的吸附动力学

Figure 4. Adsorption kinetics of As(Ⅲ) on adsorbents

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图 5 pH对吸附剂吸附As(Ⅲ)的影响

Figure 5. Effect of pH on the adsorption of As(Ⅲ) on adsorbents

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图 6 吸附剂对As(Ⅲ)的吸附和解吸

Figure 6. Adsorption and desorption of As(Ⅲ) on adsorbents

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图 7 吸附剂吸附As(Ⅲ)前后的XRD图谱

Figure 7. XRD spectrum of absorbents before and after absorption of As(Ⅲ)

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图 8 吸附剂吸附As(Ⅲ)前后的FTIR光谱

Figure 8. FTIR spectra of absorbents before and after absorption of As(Ⅲ)

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图 9 吸附剂吸附砷前后的SEM图谱

Figure 9. SEM micrographs of absorbents before and after absorption of As(Ⅲ)

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图 10 NFM吸附As(Ⅲ)前后的XPS图谱

Figure 10. XPS spectra of NFM before and after adsorption of As(Ⅲ)

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表 1 NFM元素含量分析

Table 1. Percentage content of each element of NFM %　

元素	含量	元素	含量
Fe	72.32	P	0.76
Mn	11.78	Zn	0.09
Ca	0.33	Ni	0.04
Si	3.46	As	0.01
Al	2.52	Pb	0.02
Mg	0.27	Cr	0.01
注：仅显示含量大于0.01%的元素。

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表 2 吸附剂的Fe、Mn含量和比表面积

Table 2. Fe, Mn content and specific surface area of the adsorbent

吸附剂	元素含量/%		铁锰比	比表面积/(m²/g)
吸附剂	Fe	Mn	铁锰比	比表面积/(m²/g)
NFM	72.3	11.8	1∶6.12	280.4
FMO	46.9	13.5	3.47∶1	268.8
Bir		52.3		102.9
Goe	67.4			95.8

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表 3 吸附剂对As(Ⅲ)的吸附的Langmuir和Freundlich模型参数

Table 3. Langmuir and Freundlich model parameters for adsorption of As(Ⅲ) on adsorbents

吸附剂	Langmuir模型			Freundlich模型
吸附剂	q_m	b	R²	K_f	n	R²
NFM	48.3	0.0649	0.962	8.07	3.36	0.998
FMO	70.9	0.350 0	0.973	17.4	3.09	0.957
Bir	33.2	0.006 0	0.662	0.86	1.91	0.977
Goe	44.3	0.038 0	0.905	5.81	3.04	0.984

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表 4 不同温度下As(Ⅲ)在吸附剂上吸附的热力学参数

Table 4. Thermodynamic parameters of As(Ⅲ) adsorption on adsorbents at different temperatures

吸附剂	ΔG₀/(kJ/mol)			ΔH₀ / (kJ/mol)	ΔS₀ / 〔J/(K·mol)〕	R²
吸附剂	278 K	298 K	308 K	ΔH₀ / (kJ/mol)	ΔS₀ / 〔J/(K·mol)〕	R²
NFM	−41.0	−44.0	−45.4	27.7	0.0148	0.9999
FMO	−16.6	−20.9	−23.1	44.2	0.218 0	0.8714
Bir	−8.71	−9.42	−9.77	1.18	0.0356	0.9899
Goe	−12.4	−13.6	−14.2	4.55	0.061 0	0.8936

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表 5 准一级动力学模型和准二级动力学模型拟合参数

Table 5. Fitting parameters of pseudo-first-order and pseudo-second-order kinetic models

吸附剂	准一级动力学模型			准二级动力学模型
吸附剂	q_e1	K₁	R²	q_e2	K₂	h₀	R²
NFM	8.22	0.124	0.983	21.9	0.0563	27.0	0.998 6
FMO	5.68	0.196	0.966	23.9	0.153	87.4	0.999 9
Bir	1.14	0.068 9	0.205	7.07	0.559	27.9	0.998 5
Goe	4.23	0.187	0.955	17.6	0.175	54.2	0.999 7

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表 6 吸附剂中不同价态Mn、Fe、 As的原子占比

Table 6. Atomic percentages of the different valence of Mn, Fe, As in absorbents %　

吸附剂	Mn(Ⅱ)	Mn(Ⅲ)	Mn(Ⅳ)	Fe(Ⅱ)	Fe(Ⅲ)	As(Ⅲ)	As(Ⅴ)
NFM	19.64	59.53	20.83	36.07	63.93	0	0
NFM-As(Ⅲ)	62.89	21.39	15.72	53.27	46.73	47.78	52.22
FMO	11.48	24.64	63.88	63.03	36.97	0	0
FMO-As(Ⅲ)	60.28	19.44	20.28	62.42	37.58	29.39	70.61
Bir	54.38	20.84	24.78	0	0	0	0.00
Bir-As(Ⅲ)	62.22	13.42	24.36	0	0	35.50	64.50
Goe	0	0	0	63.38	36.62	0	0
Goe-As(Ⅲ)	0	0	0	49.13	50.87	56.54	43.46

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