黏土负载型类Fenton催化剂的研究进展

doi:10.16085/j.issn.1000-6613.2017-2060

摘要/Abstract

摘要： 黏土负载型类Fenton催化剂是将活性金属固定在黏土上，用以催化活化H₂O₂产生羟基自由基去除难降解有机污染物，克服了均相Fenton氧化适用pH范围窄、易产生铁泥沉淀等缺点。本文从黏土的类型和结构特点出发，简述了层状与非层状黏土负载活性金属的特点及其催化性能；分析了柱撑、浸渍、沉积-沉淀等活性金属负载方法和黏土的改性手段；阐述了负载活性金属类型及其对催化性能的影响。针对黏土负载型类Fenton催化剂的特点和现阶段存在的问题，从黏土负载型催化剂的活性金属负载形式、负载方法和高效稳定催化性能的需求等角度指出了今后的研究方向。

关键词: 催化剂, 载体, 污染, 类Fenton, 黏土, 双氧水

Abstract: Clay-supported Fenton-like catalyst is prepared by immobilizing active metals on clays for the catalytic activation of H₂O₂ to create hydroxyl radicals to remove the refractory organic pollutants. It could overcome the disadvantages of homogeneous Fenton reactions such as narrow suitable pH range and production of iron sludge. This paper briefly introduced the catalytic performance of the layered and non-layered clay supporting active metals according to their types and structural characteristics. The synthetic and modification methods such as pillaring, impregnation and deposition precipitation were systematically analyzed, and the types of supported active metals and their effects on the catalytic performance were elaborated. With an eye towards the technical features and current challenges, we proposed several possible topics for the future studies including the form of supported active metals, the loading methods, and the requirements for the efficent and stable catalytic performance.

Key words: catalyst, support, pollution, Fenton-like, clay, hydrogen peroxide

中图分类号:

X703

廖丰, 龙明策. 黏土负载型类Fenton催化剂的研究进展[J]. 化工进展, 2018, 37(09): 3401-3409.

LIAO Feng, LONG Mingce. Recent progress on the clay supported Fenton-like catalyst[J]. Chemical Industry and Engineering Progress, 2018, 37(09): 3401-3409.

参考文献

[1] LUO Mingliang, BOWDEN D, BRIMBLECOMBE P. Catalytic property of Fe-Al pillared clay for Fenton oxidation of phenol by H₂O₂[J]. Applied Catalysis B:Environmental, 2009, 85(3):201-206.
[2] 徐小妹, 潘顺龙, 李健生, 等. 多孔载体负载型Fenton催化剂降解酚类污染物的研究进展[J]. 化工进展, 2014, 33(6):1465-1474. XU Xiaomei, PAN Shunlong, LI Jiansheng, et al. Research progress of phenols degradation with Fenton catalyst supported on porous materials[J]. Chemical Industry and Engineering Progress, 2014, 33(6):1465-1474.
[3] KHANKHASAEVA S T, DAMBUEVA D V, DASHINAMZHILOVA E T, et al. Fenton degradation of sulfanilamide in the presence of Al, Fe-pillared clay:catalytic behavior and identification of the intermediates[J]. Journal of Hazardous Materials, 2015, 293:21-29.
[4] CHEN H H, THIRUMAVALAVAN M, LIN F Y, et al. A facile approach for achieving an effective dual sorption ability of Si/SH/S grafted sodium montmorillonite[J]. RSC Advances, 2015, 5(71):57792-57803.
[5] MUKHERJEE S. The science of clays[M]. Berlin:Springer Netherlands, 2013:318.
[6] 王春风, 顾华志, 周飞. 无机柱化蛭石的制备研究[J]. 稀有金属材料与工程, 2011, 40(22):73-76. WANG Chunfeng, GU Huazhi, ZHOU Fei. Research on the preparation of inorganic-intercalated vermiculite[J]. Rare Metal Materials & Engineering, 2011, 40(22):73-76.
[7] CHEN Qiuqiang, WU Pingxiao, DANG Zhi, et al. Iron pillared vermiculite as a heterogeneous photo-Fenton catalyst for photocatalytic degradation of azo dye reactive brilliant Orange X-GN[J]. Separation & Purification Technology, 2010, 71(3):315-323.
[8] RAMIREZ J H, COSTA C A, MADEIRA L M, et al. Fenton-like oxidation of Orange Ⅱ solutions using heterogeneous catalysts based on saponite clay[J]. Applied Catalysis B:Environmental, 2006, 71(1):44-56.
[9] SUM O S N, FENG Jiyun, HUB Xijun, et al. Photo-assisted Fenton mineralization of an azo-dye acid BlackⅠusing a modified laponite clay-based Fe nanocomposite as a heterogeneous catalyst[J]. Topics in Catalysis, 2005, 33(1/4):233-242.
[10] FENG Jiyun, HU Xijun, YUE Po Lock, et al. A novel laponite clay-based Fe nanocomposite and its photo-catalytic activity in photo-assisted degradation of Orange Ⅱ[J]. Chemical Engineering Science, 2003, 58(3):679-685.
[11] 王万军.高岭石有机插层复合物的制备、表征及应用探讨[D]. 长沙:中南大学, 2005. WANG Wanjun. Preparation, characterization and application of kaolinite-organics intercalation compounds[D]. Changsha:Central South University, 2005.
[12] GUO Sheng, ZHANG Gaoke, WANG Jiquan. Photo-Fenton degradation of Rhodamine B using Fe₂O₃-kaolin as heterogeneous catalyst:characterization, process optimization and mechanism[J]. Journal of Colloid & Interface Science, 2014, 433(11):1-8.
[13] ZHANG Gaoke, GAO Yuanyuan, ZHANG Yalei, et al. Fe₂O₃-pillared rectorite as an efficient and stable Fenton-like heterogeneous catalyst for photodegradation of organic contaminants[J]. Environmental Science & Technology, 2010, 44(16):6384-9.
[14] SU Chengyuan, LI Weiguang, LIU Xingzhe, et al. Fe-Mn-sepiolite as an effective heterogeneous Fenton-like catalyst for the decolorization of reactive brilliant blue[J]. Frontiers of Environmental Science & Engineering, 2016, 10(1):37-45.
[15] XI Yunfei, SUN Zhiming, HREID T, et al. Bisphenol a degradation enhanced by air bubbles via advanced oxidation using in situ generated ferrous ions from nano zero-valent iron/palygorskite composite materials[J]. Chemical Engineering Journal, 2014, 247(7):66-74.
[16] GARRIDO-RAMIREZ E G, SIVAIAH M V, BARRAULT J, et al. Catalytic wet peroxide oxidation of phenol over iron or copper oxide-supported allophane clay materials:influence of catalyst SiO₂/Al₂O₃ ratio[J]. Microporous & Mesoporous Materials, 2012, 162(162):189-198.
[17] 邵鸿飞.铝柱撑蒙脱石负载Au(或Pt)催化剂的制备及其催化氧化CO性质的研究[D]. 济南:山东大学, 2013. SHAO Hongfei. Preparation of supported gold (platinum) catalysts on Al-pillared montmorillonite and study of catalytic oxidation of carbon monoxide[D]. Jinan:Shandong University, 2013.
[18] 陈秋强.异相photo-Fenton催化剂——铁柱撑粘土光催化降解活性艳橙X-GN研究[D]. 广州:华南理工大学, 2010. CHEN Qiuqiang. Study on iron pillared clay as a heterogeneous photo-Fenton catalyst for photocatalytic degradation of azo dye reactive brilliant Orange X-GN[D]. Guangzhou:South China University of Technology, 2010.
[19] HUANG Zhujian, WU Pingxiao, GONG Beini, et al. Preservation of glutamic acid-iron chelate into montmorillonite to efficiently degrade Reactive Blue 19 in a Fenton system under sunlight irradiation at neutral pH[J]. Applied Surface Science, 2016, 370:209-217.
[20] WANG Guanghua, LU Yunzhou, LI Wenbing, et al. Synthesis and catalytic performance of Al-pillared clays supported Fe₃O₄ nanoparticles[J]. Advanced Materials Research, 2012, 581/582(1):292-296.
[21] PIZARRO A H, MOLINA C B, MUNOZ M, et al. Combining HDC and CWPO for the removal of p-chloro-m-cresol from water under ambient-like conditions[J]. Applied Catalysis B:Environmental, 2017, 216:20-29.
[22] GUZ L, CURUTCHET G, TORRES S R M, et al. Adsorption of crystal violet on montmorillonite(or iron modified montmorillonite) followed by degradation through Fenton or photo-Fenton type reactions[J]. Journal of Environmental Chemical Engineering, 2014, 2(4):2344-2351.
[23] KOMLÓSI A, KUZMANN E, NAGY N M, et al. Incorporation of Fe in the interlayer of Na-bentonite via treatment with FeCl₃ in acetone[J]. Clays & Clay Minerals, 2007, 55(1):89-95.
[24] 牛露, 赵彬侠, 叶维, 等. Fe-Zn-Al-柱撑蒙脱石催化剂的制备及其降解酸性橙Ⅱ性能[J].硅酸盐学报, 2016, 44(10):1501-1508. NIU Lu, ZHAO Binxia, YE Wei, et al. Fe-Zn-Al pillared montmorillonite for catalytic wet peroxide oxidation degradation of Orange AcidⅡ:preparation methods and properties[J]. Journal of the Chinese Ceraminc Society, 2016, 44(10):1501-1508.
[25] 丛兴顺, 王力, 张明伟. Fe/Cr柱撑蒙脱石的水热法制备与表征[J]. 工业催化, 2006, 14(5):61-64. CONG Xingshun, WANG Li, ZHANG Mingwei. Preparation of Fe/Cr-pillared montmorillonite by hydrothermal method and its characterization[J]. Industrial Catalysis, 2006, 14(5):61-64.
[26] YUAN Linhu. Magnetically recoverable Fe₃O₄-modified bentonite as a heterogeneous catalyst of H₂O₂ activation for efficient degradation of methyl Orange[J]. Polish Journal of Environmental Studies, 2017, 26(5):2355-2361.
[27] YIP C K, LAM L Y, HU Xijun. Chemical-vapor-deposited copper on acid-activated bentonite clay as an applicable heterogeneous catalyst for the photo-Fenton-like oxidation of textile organic pollutants[J]. Industrial & Engineering Chemistry Research, 2008, 44(21):7983-7990.
[28] ZHOU Shiwei, ZHANG Changbo, HU Xuefeng, et al. Catalytic wet peroxide oxidation of 4-chlorophenol over Al-Fe-, Al-Cu-, and Al-Fe-Cu-pillared clays:sensitivity, kinetics and mechanism[J]. Applied Clay Science, 2014, 95(3):275-283.
[29] KERKEZ D V, TOMASEVIC D D, KOZMA G, et al. Three different clay-supported nanoscale zero-valent iron materials for industrial azo dye degradation:a comparative study[J]. Journal of the Taiwan Institute of Chemical Engineers, 2014, 45(5):2451-2461.
[30] HONG Ran, GUO Zupei, GAO Juan, et al. Rapid degradation of atrazine by hydroxyl radical induced from montmorillonite templated subnano-sized zero-valent copper[J]. Chemosphere, 2017, 180:335-342.
[31] CHENG Mingming, SONG Wenjing, MA Wanhong, et al. Catalytic activity of iron species in layered clays for photodegradation of organic dyes under visible irradiation[J]. Applied Catalysis B:Environmental, 2008, 77(3/4):355-363.
[32] FENG Jiyun, HU Xijun, YUE P L. Discoloration and mineralization of OrangeⅡusing different heterogeneous catalysts containing Fe:a comparative study[J]. Environmental Science & Technology, 2004, 38(21):5773-5778.
[33] CAUDO S, CENTI G, GENOVESE C, et al. Copper-and iron-pillared clay catalysts for the WHPCO of model and real wastewater streams from olive oil milling production[J]. Applied Catalysis B:Environmental, 2007, 70(1):437-446.
[34] MOLINA C B, CASAS J A, ZAZO J A, et al. A comparison of Al-Fe and Zr-Fe pillared clays for catalytic wet peroxide oxidation[J]. Chemical Engineering Journal, 2006, 118(1):29-35.
[35] 徐睿, 周世伟, 张华, 等.铁铜柱撑黏土催化4-氯酚氧化降解研究[J].工业水处理, 2015, 35(4):20-24. XU Rui, ZHOU Shiwei, ZHANG Hua, et al. Research on Fe-Cu pillared clay for catalyzing 4-chlorophenol oxidation degradation[J]. Industrial Water Treatment, 2015, 35(4):20-24.
[36] HADJLTAIEF H B, ZINA M B, GALVEZ M E, et al. Photo-Fenton oxidation of phenol over a Cu-doped Fe-pillared clay[J]. Comptes Rendus Chimie, 2015, 18(10):1161-1169.
[37] GARRIDO-RAMIREZ E G, MARCO J F, ESCALONA N, et al. Preparation and characterization of bimetallic Fe-Cu allophane nanoclays and their activity in the phenol oxidation by heterogeneous electro-Fenton reaction[J]. Microporous & Mesoporous Materials, 2016, 225(4):303-311.
[38] LEE H V, JUAN J C, TAUFIQYAP Y H. Preparation and application of binary acid-base CaO-La₂O₃ catalyst for biodiesel production[J]. Renewable Energy, 2015, 74:124-132.
[39] FIDA H, ZHANG Gaoke, GUO Sheng, et al. Heterogeneous Fenton degradation of organic dyes in batch and fixed bed using La-Fe montmorillonite as catalyst[J]. Journal of Colloid & Interface Science, 2017, 490:859-868.
[40] KHANKHASAEVA S T, DASHINAMZHILOVA E T, DAMBUEVA D V. Oxidative degradation of sulfanilamide catalyzed by Fe/Cu/Al-pillared clays[J]. Applied Clay Science, 2017, 146:92-99.
[41] TIMOFEEVA M N, KHANKHASAEVA S T, TALSI E P, et al. The effect of Fe/Cu ratio in the synthesis of mixed Fe, Cu, Al-clays used as catalysts in phenol peroxide oxidation[J]. Applied Catalysis B:Environmental, 2009, 90(3/4):618-627.
[42] HUANG Zhujian, WU Pingxiao, LI Hailing, et al. Synthesis and catalytic properties of La or Ce doped hydroxy-FeAl intercalated montmorillonite used as heterogeneous photo Fenton catalysts under sunlight irradiation[J]. RSC Advances, 2014, 4(13):6500-6507.
[43] GAO Han, ZHAO Binxia, LUO Jinchao, et al. Fe-Ni-Al pillared montmorillonite as a heterogeneous catalyst for the catalytic wet peroxide oxidation degradation of Orange Acid Ⅱ:preparation condition and properties study[J]. Microporous & Mesoporous Materials, 2014, 196:208-215.
[44] WEI Xipeng, WU Honghai, SUN Feng. Magnetite/FeAl-montmorillonite as a Fenton catalyst with efficient degradation of phenol[J]. Journal of Colloid & Interface Science, 2017, 504:611-619.
[45] LI Wenbing, WAN Dong, WANG Guanghua, et al. Heterogeneous Fenton degradation of orange Ⅱ by immobilization of Fe₃ O₄ nanoparticles onto Al-Fe pillared bentonite[J]. Korean Journal of Chemical Engineering, 2016, 33(5):1557-1564.
[46] WAN Dong, WANG Guanghua, LI Wenbing, et al. Investigation into the morphology and structure of magnetic bentonite nanocomposites with their catalytic activity[J]. Applied Surface Science, 2017, 413:398-407.
[47] JIN Mingjie, LONG Mingce, SU Hanrui, et al. Magnetically separable maghemite/montmorillonite composite as an efficient heterogeneous Fenton-like catalyst for phenol degradation[J]. Environmental Science & Pollution Research, 2017, 24(2):1926-1937.