碱活化蒙脱土负载铁类芬顿体系去除亚甲基蓝

蔡玉福; 周艳军; 路君凤; 张启俭; 王欢; 赵永华

doi:10.13801/j.cnki.fhclxb.20221025.001

碱活化蒙脱土负载铁类芬顿体系去除亚甲基蓝

doi: 10.13801/j.cnki.fhclxb.20221025.001

辽宁工业大学　化学与环境工程学院，锦州 121001

基金项目: 辽宁省教育厅重点攻关项目(JZL202015405)；辽宁省自然科学基金指导计划项目(2019-ZD-0690)

详细信息

通讯作者:
赵永华，博士，教授，硕士生导师，研究方向为多相催化　E-mail: lgdzyh@163.com

中图分类号: O643.32；TB332
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出版历程
- 收稿日期: 2022-08-25
- 修回日期: 2022-09-25
- 录用日期: 2022-10-01
- 网络出版日期: 2022-10-25
- 刊出日期: 2023-08-15

Removal of methylene blue by Fenton-like system with alkali-activated montmorillonite supported iron catalyst

School of Chemistry & Environmental Engineering, Liaoning University of Technology, Jinzhou 121001, China

Funds: Key Projects of Liaoning Province Education Department of China (JZL202015405); Liaoning Provincial Natural Science Foundation of China (2019-ZD-0690)

摘要

摘要: 类芬顿技术是去除水中难降解有机污染物最有应用前景的处理技术之一，构建高效稳定的类芬顿催化剂是其研究的关键。本文采用5 mol/L NaOH溶液在不同温度对Ca-蒙脱土(MMT)进行活化改性，制备了一系列具有不同结构和酸性的碱活化蒙脱土(Alk-MMT)，并将Alk-MMT负载铁催化剂(Fe/Alk-MMT)与H₂O₂组成类芬顿体系用于去除亚甲基蓝(MB)。对所制备的材料进行了XRD、NH₃-程序升温脱附(TPD)、XPS、SEM、FTIR、N₂吸附-脱附等表征分析。结果表明：与Ca-MMT相比，Alk-MMT的结构和酸性均发生了明显的变化，且变化的程度与碱处理温度密切相关。Alk-MMT结构和酸性的变化明显影响类芬顿体系去除MB的性能。其中以Fe/Alk-MMT-100为催化剂的类芬顿体系在反应温度为50℃，催化剂和H₂O₂用量分别为1.25 g/L和0.85 mmol/L，在较宽的pH范围(3.0~9.0)反应300 min后MB的去除效率均可达98.7%以上，且表现出较好的稳定性，重复使用6次后，活性未下降。
- 类芬顿 /
- 碱活化蒙脱土 /
- 亚甲基蓝 /
- 去除率 /
- 稳定性
Abstract: Fenton-like technology is one of the most promising water treatment technologies to remove refractory organic pollutants, and it is the key to construction Fenton-like catalysts with high activity and stability. In this work, a series of alkali-activated montmorillonite (Alk-MMT) with different structure and acidity were prepared via Ca-MMT treated with 5 mol/L NaOH solution at different treatment temperature. Fenton-like system composed with Alk-MMT supported iron catalyst (Fe/Alk-MMT) and H₂O₂ was used to remove methylene blue (MB). The material was systematically characterized by XRD, NH₃-Temperature programmed desorption (TPD), XPS, SEM, FTIR, and N₂ adsorption-desorption at low temperature techniques. The results show that the structure and acidity of Alk-MMT are significantly changed compared with Ca-MMT, which is dependent on the alkali treatment temperature. The structure and acidity of Alk-MMT obviously affect the removal performance of MB in Fenton-like system. The Fenton-like system using Fe/Alk-MMT-100 as catalyst exhibits higher removal efficiency of MB (> 98.7%) under the condition of 50℃, the catalyst dosage of 1.25 g/L, the H₂O₂ concentration of 0.85 mmol/L, and a wide pH (3.0-9.0) range for reacting 300 min. Meanwhile, the activity of the catalyst does not decrease after repeated use for 6 times, which exhibiting a good stability.
- Fenton-like /
- alkali-activated montmorillonite /
- methylene blue /
- removal efficiency /
- stability

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图 1 Ca-蒙脱土(MMT)和Alk-MMT的XRD图谱

Figure 1. XRD patterns of Ca-montmorillonite (MMT) and Alk-MMT

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图 2 Fe/Ca-MMT和Fe/Alk-MMT的XRD图谱

Figure 2. XRD patterns of Fe/Ca-MMT and Fe/Alk-MMT

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图 3 Fe/Ca-MMT、Fe/Alk-MMT的XPS全谱图和Fe2p精细图谱

Figure 3. XPS survey spectra and Fe2p spectra of Fe/Ca-MMT and Fe/Alk-MMT

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图 4 Ca-MMT和Alk-MMT的FTIR图谱

Figure 4. FTIR spectra of Ca-MMT and Alk-MMT

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图 5 Ca-MMT和Alk-MMT的N₂吸附-脱附等温线

Figure 5. N₂ adsorption-desorption isotherms of Ca-MMT and Alk-MMT

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图 6 Ca-MMT和Alk-MMT的SEM图像

Figure 6. SEM images of Ca-MMT and Alk-MMT

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图 7 Ca-MMT和Alk-MMT的NH₃-TPD图谱

TCD—Thermal conductivity detector

Figure 7. NH₃-TPD patterns of Ca-MMT and Alk-MMT

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图 8 Fe/Ca-MMT和Fe/Alk-MMT催化H₂O₂去除亚甲基蓝(MB)效果

[MB]=50 mg/L, [H₂O₂]=0.85 mmol/L, [Catalyst]=0.25 g/L, Initial pH=7.0, Temperature=50℃, Time=300 min

Figure 8. Removal efficiency of methylene blue (MB) with Fe/Ca-MMT and Fe/Alk-MMT catalyze H₂O₂

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图 9 反应温度对类芬顿体系去除MB的影响

[MB]=50 mg/L, [H₂O₂] =0.85 mmol/L, [Fe/Alk-MMT-100]=0.25 g/L, Initial pH=7.0, Temperature=20-60℃, Time=300 min

Figure 9. Influence of reaction temperatures on the removal of MB in Fenton-like system

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图 10 不同H₂O₂浓度对类芬顿体系去除MB的影响

[MB]=50 mg/L, [Fe/Alk-MMT-100]=0.25 g/L, [H₂O₂]=0-1.95 mmol/L, Initial pH=7.0, Temperature=50℃, Time=300 min

Figure 10. Influence of H₂O₂ concentration on the removal of MB in Fenton-like system

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图 11 催化剂用量对类芬顿体系去除MB的影响

[MB]=50 mg/L, [Fe/Alk-MMT-100]=0.15-1.50 g/L, [H₂O₂]=0.85 mmol/L, Initial pH=7.0, Temperature=50℃, Time=300 min

Figure 11. Influence of catalyst dosages on the removal of MB in Fenton-like system

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图 12 初始pH对类芬顿体系去除MB的影响

[MB]=50 mg/L, [Fe/Alk-MMT-100]=1.25 g/L, [H₂O₂]=0.85 mmol/L, Initial pH=3.0-9.0, Temperature=50℃, Time=300 min

Figure 12. Influence of initial pH values on the removal of MB in Fenton-like system

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图 13 Fe/Alk-MMT-100反应前后的FTIR图谱

Figure 13. FTIR spectra of Fe/Alk-MMT-100 before and after reaction

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图 14 催化剂重复使用次数对MB去除的影响

[MB]=50 mg/L, [Fe/Alk-MMT-100]=1.25 g/L, [H₂O₂]=0.85 mmol/L, Initial pH=7.0, Temperature=50℃, Time=300 min

Figure 14. Influence of catalyst recycle times on MB removal rate

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表 1 样品编号说明

Table 1. Sample name description

Sample	Alkali treatment temperature/℃	Content of Fe/wt%
Alk-MMT-60	60	—
Alk-MMT-80	80	—
Alk-MMT-100	100	—
Alk-MMT-108	108	—
Fe/Alk-MMT-60	60	10
Fe/Alk-MMT-80	80	10
Fe/Alk-MMT-100	100	10
Fe/Alk-MMT-108	108	10

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表 2 Ca-MMT和Alk-MMT的织构特征

Table 2. Textural properties of Ca-MMT and Alk-MMT

Sample	BET surface area/(m²·g⁻¹)	Pore volume/(cm³·g⁻¹)	Average pore size/nm
Ca-MMT	49	0.12	9.4
Alk-MMT-60	73	0.11	6.4
Alk-MMT-80	102	0.14	5.6
Alk-MMT-100	130	0.19	6.4
Alk-MMT-108	105	0.17	6.5
Note: BET—Brunauer-Emmett-Teller.

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表 3 碱处理温度对Fe/Alk-MMT催化剂中Fe溶出量的影响

Table 3. Effect of alkali treatment temperature on amount of leaching Fe in Fe/Alk-MMT catalyst

Catalyst	Fe concentration/(μg·L⁻¹)	Fe leaching/(μg·g⁻¹)
Fe/Ca-MMT	33.2	132.8
Fe/Alk-MMT-60	25.6	102.4
Fe/Alk-MMT-80	16.1	64.4
Fe/Alk-MMT-100	12.2	48.8
Fe/Alk-MMT-108	25.5	102.0

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表 4 不同初始pH对Fe/Alk-MMT-100催化剂中Fe溶出量的影响

Table 4. Effect of different initial pH values on amount of leaching Fe in Fe/Alk-MMT-100 catalyst

pH	Fe concentration/(μg·L⁻¹)	Fe leaching/(μg·g⁻¹)
3.0	673.00	538.40
4.0	10.64	8.51
5.0	6.82	5.46
7.0	4.72	3.78
9.0	3.87	3.10

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表 5 不同催化剂类芬顿体系去除MB的比较

Table 5. Comparison of removal of MB by Fenton-like system composed with different catalyst

Catalyst	Reaction condition	Removal efficiency/%	Ref.
Fe-MMT	[Catalyst] = 1.0 g·L⁻¹ [H₂O₂]=10 mmol·L⁻¹ [MB]= 0.2 mmol·L⁻¹ pH=3.0, t=180 min	93.0	[24]
Fe/C	[Catalyst] = 2.0 g·L⁻¹ [H₂O₂] = 4 mL·L⁻¹ [MB] = 10 mg·L⁻¹ pH=3, t=30 min	95	[25]
Ce-doped UiO-67	[Catalyst] = 1.0 g·L⁻¹ [H₂O₂] = 7 mmoL·L⁻¹ [MB] = 500 mg·L⁻¹ pH=3.0, t=30 min	94.1	[26]
Fe₃O₄@PDA-MnO₂	[Catalyst] = 0.2 g·L⁻¹ [H₂O₂] = 200 mL·L⁻¹ [MB] = 40 mg·L⁻¹ pH=3.0, t=240 min	97.36	[27]
HKUST-1/Fe₃O₄ /CMF	[Catalyst] = 0.33 g·L⁻¹ [H₂O₂] = 4 g·L⁻¹ [MB] = 10 mg·L⁻¹ pH=3.0, t=240 min	98.0	[28]
Fe/Alk-MMT	[Catalyst]=1.25 g·L⁻¹ [H₂O₂]=0.85 mmol·L⁻¹ [MB]=50 mg·L⁻¹ pH=3.0-9.0, t=300 min	98.7	This work
Notes: Fe-MMT—Iron-pillared montmorillonitic clay; Fe/C—Iron supported on walnut shell biochar; Ce-doped UiO-67—Cerium instead of a part of zirconium into the UiO-67 skeleton; Fe₃O₄@PDA-MnO₂—Polydopamine (PDA) coating and MnO₂ depositing onto the surface of Fe₃O₄ nanoparticles; HKUST-1/Fe₃O₄/CMF—Cellulose-supported magnetic Fe₃O₄-MOF composites; t—Time.

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