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

碱活化蒙脱土负载铁类芬顿体系去除亚甲基蓝

辽宁工业大学　化学与环境工程学院, 辽宁锦州 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
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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: 2022-10-28
- 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, Liaoning, China

Funds: Key Projects of Liaoning Province Education Department of China(No. JZL202015405)；Liaoning Provincial Natural Science Foundation of China(No. 2019-ZD-0699)

摘要

摘要: 尽管高级氧化技术中的芬顿体系具有操作简单和氧化能力强等优点，但其反应条件的苛刻(pH=2.5-3.5)、反应后体系形成大量铁泥、催化剂回收困难等缺陷阻碍了其工业化应用。经过多年研究，发现把铁盐固定到多孔材料上(如活性炭、沸石和粘土)所形成的类芬顿体系可以很好的克服催化剂回收难的问题，并能拓宽反应的pH值。多孔材料具有较大的比表面积，一方面可以起到固定铁的作用，另一方面还可以起到吸附富集有机物、加快反应进行的作用。此外，研究表明一些具有较强酸性的多孔材料，更有利于反应的发生，极大地提高有机污染物的降解效率。因此，对于多相类芬顿催化反应，寻求一种适宜的多孔材料是至关重要的。蒙脱土是由两层硅氧四面体之间夹一层铝氧八面体组成的2：1型层状硅酸盐粘土矿物，在我国储量丰富，价格低廉。其层间阳离子的存在使其具有良好的可交换性。鉴于蒙脱土的结构，本文通过碱活化的方式对其改性，通过控制碱处理的条件实现了对其结构和酸性的有效调控，得到了一系列具有不同结构和酸性的碱活化蒙脱土(Alk-MMT)。以其为载体的负载铁催化剂(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-TPD、XPS、SEM、FT-IR、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。其中以铁负载在100℃碱活化的蒙脱土(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。1Ca-MMT和Alk-MMT的NH₃-TPD图谱图(Ca-MMT (a),Alk-MMT-60 (b), Alk-MMT-80 (c), Alk-MMT-100 (d), Alk-MMT-108 (e))2不同催化剂的类芬顿体系去除MB效果
- 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-TPD, XPS, SEM, FT-IR, 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^oC, 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) (a), Alk-MMT-60 (b), Alk-MMT-80 (c),Alk-MMT-100 (d), Alk-MMT-108 (e)

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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 (a), Fe/Alk-MMT-60 (b), Fe/Alk-MMT-80 (c), Fe/Alk-MMT-100 (d), Fe/Alk-MMT-108 (e)

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图 3 Fe/Alk-MMT的XPS全谱图和Fe 2 p精细谱图

Figure 3. XPS survey image (a) and Fe 2 p spectra of Fe/Ca-MMT (b), Fe/Alk-MMT-60 (c), Fe/Alk-MMT-100 (d)

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图 4 Ca-MMT和Alk-MMT的FT-IR图谱

Figure 4. FT-IR spectra of Ca-MMT (a), Alk-MMT-60 (b), Alk-MMT-80 (c), Alk-MMT-100 (d), Alk-MMT-108 (e)

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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 (a), Alk-MMT-60 (b), Alk-MMT-80 (c), Alk-MMT-100 (d), Alk-MMT-108 (e)

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图 6 Ca-MMT和Alk-MMT的SEM图像

Figure 6. SEM images of Ca-MMT (a), Alk-MMT-60 (b), Alk-MMT-100 (c), Alk-MMT-108 (d)

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图 7 Ca-MMT和Alk-MMT的NH₃-TPD图谱

Figure 7. NH₃-TPD patterns of Ca-MMT (a), Alk-MMT-60 (b), Alk-MMT-80 (c), Alk-MMT-100 (d), Alk-MMT-108 (e)

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图 8 Fe/Ca-MMT和Fe/Alk-MMT催化H₂O₂去除MB效果

Figure 8. Removal efficiency of MB with Fe/Ca-MMT and Fe/Alk-MMT catalyze H₂O₂ ([MB]=50 mg/L, [H₂O₂]=0.85 mmol/L, [catalyst]=0.25 g/L, initial pH=7.0, temperature=50℃, time=300 min)

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图 9 反应温度对类芬顿体系去除MB的影响

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

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图 10 不同H₂O₂浓度对类芬顿体系去除MB的影响

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

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图 11 催化剂用量对类芬顿体系去除MB的影响

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

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图 12 初始pH对类芬顿体系去除MB的影响

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

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图 13 Fe/Alk-MMT-100反应前后的FT-IR图谱

Figure 13. FT-IR spectra of Fe/Alk-MMT-100 (a) before reaction, (b)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

Figure 14. Influence of catalyst cyclic experiment on MB removal rate ([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)

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表 1 Ca-MMT和Alk-MMT的织构特征

Table 1. Textural properties of Alk-MMT determined by N₂ adsorption-desorption

Samples	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

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表 2 碱处理温度对Fe/Alk-MMT催化剂中Fe溶出量的影响

Table 2. 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

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表 3 不同初始pH对Fe/Alk-MMT-100催化剂中Fe溶出量的影响

Table 3. 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	673.0	538.4
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 4 不同催化剂类芬顿体系去除MB的比较

Table 4. Comparison of removal of MB by Fenton-like system composed with different catalyst.

Catalyst	Reaction condition	Removal efficiency	Reference
Fe-MMT	[Cat.] = 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	[Cat.] = 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	[Cat.] = 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	[Cat.] = 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	[Cat.] = 0.33 g·L⁻¹ [H₂O₂] = 4 g L⁻¹ [MB] = 10 mg·L⁻¹ pH = 3.0, t=240 min	98%	[28]
Fe/Alk-MMT	[Cat.] = 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%	本文
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.

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