介孔Fe2O3/SBA-15催化臭氧氧化含酚废水

doi:10.16085/j.issn.1000-6613.2019-0320

摘要/Abstract

摘要：

含酚废水来源广泛自然条件下难以去除，酚类物质毒性大对生态环境和人类生活健康造成了较严重的影响。本文选取了有机废水处理中较为高效的臭氧催化氧化技术，使用臭氧氧源曝气产生大量的含氧自由基，催化氧化降解酚类有机物，同时对活性中心载体进行了优化，选取制备了一类水热稳定性好及机械强度高的多孔材料，使用这些多孔材料对活性中心Fe₂O₃进行了再组装，合成了一系列表面富集Fe₂O₃的SBA-15介孔薄膜材料，由于SBA-15材料较大的比表面积、丰富的孔隙结构、高度分散的活性中心，在臭氧催化氧化含酚废水中取得了较好效果。苯酚溶液初始浓度为100mg/L (COD 238mg/L)、Fe₂O₃(5)/SBA-15催化剂投加量为30g、臭氧气体流量为2mg/min、废水HRT为5min、流量为0.8L/h的条件下，该催化剂能高效连续稳定运行500h不易失活，其COD去除率仍能保持在65%以上，催化剂活性依然保持在83%以上。Fe₂O₃/SBA-15类介孔催化材料在深度处理含酚废水中具有工业化应用潜质。

关键词: 催化, 氧化, 废水, SBA-15, 苯酚

Abstract:

Phenolic compounds have a wide range of sources. It is very difficult to remove phenolic compounds from wastewater under natural conditions. Phenolic compounds are highly toxic and have a serious impact on ecological environment and people's health. In the paper, the efficient ozone catalytic oxidation technology for organic wastewater treatment was selected to degrade and oxidate phenolic organic compounds by oxygen radicals, which produced by ozone aeration. The catalyst carriers were selected and optimized. A kind of porous materials with good hydrothermal stability and high physical strength was prepared. The active sites Fe₂O₃ was modified by these supports, which to synthesize a series of SBA-15 mesoporous materials on whose surface Fe₂O₃ film was enriched. The SBA-15 mesoporous materials had very good effect on catalytic oxidation of phenolic wastewater because of its large specific surface area, abundant porous structure and uniform active sites. The materials could run efficiently and steadily for 500h, with the catalytic activity above 83% under the reaction conditions: initial phenol solution concentration of 100mg/L (COD 238mg/L), hydraulic retention time of phenolic wastewater of 5min, quantity of flow 0.8L/h and ozone aeration rate of 2mg/min and 30g Fe₂O₃(5)/SBA-15 materials. Thus, mesoporous catalytic materials such as Fe₂O₃/SBA-15 have an industrial application potential in advanced treatment of phenolic wastewater.

Key words: catalysis, oxidation, waste water, SBA-15, phenol

中图分类号:

TU991.27

刘俊逸,李倩,李杰,曾国平,吴田,杨昌柱. 介孔Fe₂O₃/SBA-15催化臭氧氧化含酚废水[J]. 化工进展, 2019, 38(11): 5158-5164.

Junyi LIU,Qian LI,Jie LI,Guoping ZENG,Tian WU,Changzhu YANG. Catalytic oxidation of phenolic wastewater by O₃ over mesoporousFe₂O₃/SBA-15[J]. Chemical Industry and Engineering Progress, 2019, 38(11): 5158-5164.

图/表 8

图1 Fe2O3/SBA-15催化臭氧氧化含酚废水设备

图2 Fe2O3/SBA-15类催化剂XRD分析

图3 Fe2O3/SBA-15类催化剂氮吸附和BJH分析

表1 Fe2O3/SBA-15催化臭氧氧化苯酚性能

样品	比表面积 /m²·g^-1	孔容 /cm³·g^-1	苯酚去除率/%	COD去除率/%
无催化剂	—	—	18.8	13.4
SBA-15	780	0.95	51.3	35.8
Fe₂O₃(1)/SBA-15	743	0.90	76.2	61.7
Fe₂O₃(3)/SBA-15	692	0.86	89.3	67.6
Fe₂O₃(5)/SBA-15	656	0.75	99.4	79.5
Fe₂O₃(7)/SBA-15	633	0.71	75.3	60.6
Fe₂O₃(10)/SBA-15	603	0.69	63.2	43.2
反应500h催化剂	483	0.71	85.2	65.3

图4 Fe2O3/SBA-15类催化剂TEM分析

图5 Fe2O3/SBA-15类催化剂FTIR分析

图6 反应时间对Fe2O3/SBA-15类催化剂性能影响

图7 Fe2O3/SBA-15类催化剂500h连续流实验

参考文献 21

1	刘俊逸, 张宇, 张蕾, 等. 含酚工业废水处理技术的研究进展[J]. 工业水处理, 2018, 38(10): 12-16.
	LIUJunyi, ZHANGYu, ZHANGLei, et al. Research progress in the treatment technologies of industrial wastewater containing phenol [J]. Industrial Water Treatment, 2018, 38(10): 12-16.
2	刘俊逸, 黄华, 衷晟, 等. 金属氧化物催化苯酚-甲醇气相C-烷基化的研究进展[J]. 化工进展, 2013, 32(11): 2609-2613.
	LIUJunyi, HUANGHua, ZHONGSheng, et al. Research progress in vapor phase C-alkylation of phenol with methanol over metallic oxides [J]. Chemical Industry and Engineering Progress, 2013, 32(11): 2609-2613.
3	王韬, 李鑫钢, 杜启云. 含酚废水治理技术研究进展[J]. 化工进展, 2008, 27(1): 231-235.
	WANGTao, LIXingang, DUQiyun. Research progress of phenol-containing waste water disposal technique [J]. Chemical Industry and Engineering Progress, 2008, 27(1): 231-235.
4	兰瑞家. 高级氧化法处理水中的有机污染物[D]. 保定: 河北大学, 2013.
	LANRuijia. Degradation of organic pollutants from aqueous solution by advanced oxidation processes [D]. Baoding: Hebei University, 2013.
5	魏令勇, 郭绍辉, 阎光绪. 高级氧化法提高难降解有机污水生物降解性能的研究进展[J]. 水处理技术, 2011, 37(1): 14-19.
	WEILingyong, GUOShaohui, YANGuangxu. Enhancing biodegradability of bio-refractory organic wastewater by advanced oxidation processes: an overview [J]. Technology of Water Treatment, 2011, 37(1): 14-19.
6	李桂菊, 朱丽香, 何迎春. 湿式催化氧化法处理含酚清洗废水的研究[J]. 工业水处理, 2010, 30(5): 38-41.
	LIGuiju, ZHULixiang, HEYingchun. Study on the application of wet catalytic oxidation process to the treatment of phenol-containing cleaning wastewater [J]. Technology of Water Treatment, 2010, 30(5): 38-41.
7	王丽娜, 刘霞, 张垒, 等. PFS混凝组合Ca(ClO)₂氧化深度处理焦化废水实验研究[J]. 工业水处理, 2016, 36(2): 55-58.
	WANGLina, LIUXia, ZHANGLei, et al. Experimental research on the advanced treatment of coking wastewater by polyferric sulfate coagulation combined with calcium hypochlorite oxidation [J]. Chemical Industry and Engineering Progress, 2016, 36(2): 55-58.
8	ZHAOD, CHMELKAB F, STUCKYG D. Triblock copolymer syntheses of mesoporous solica with periodic 50 to 300 Angstrom pores [J]. Science, 1998, 279(5350): 548-552.
9	HUANGHua, LIUJunyi, LIUXianxiang, et al. Microwave-dried α-Fe₂O₃ as a highly efficient catalyst for ortho-methylation of phenol with methanol [J]. Fuel, 2016, 182: 373-381.
10	LIUJunyi, HUANGHua, LIUXianxiang, et al. Preparation of Fe₂O₃ doped SBA-15 for vapor phase ortho-position C-alkylation of phenol with methanol [J]. Catalysis Communications, 2017, 92: 90-94.
11	包木太, 王娜, 陈庆国, 等. Fenton法的氧化机理及在废水处理中的应用进展[J]. 化工进展, 2008, 27(5): 660-665.
	BAOMutai, WANGNa, CHENQingguo, et al. Oxidation mechanism and application progress of Fenton process in wastewater treatment [J]. Chemical Industry and Engineering Progress, 2008, 27(5): 660-665.
12	陈拥军, 窦和瑞, 杨民, 等. 催化湿式氧化法在苯酚废水预处理中的应用研究[J]. 工业水处理, 2002, 6(1): 19-22.
	CHENYongjun, DOUHerui, YANGMin, et al. Study of catalytic wet air oxidation to be used in the pretreatment of phenol wastewater [J]. Chemical Industry and Engineering Progress, 2002, 6(1): 19-22.
13	HUANGRuihuan, YANHuihua, LILaisheng, et al. Catalytic activity of Fe/SBA-15 for ozonation of dimethyl phthalate in aqueous solution [J]. Applied Catalysis B: Environmental, 2011, 106(1): 264-271.
14	PENGChunyun, ZHANGHongjie, YUJiangbo, et al. Synthesis, characterization, and luminescence properties of the ternary europium complex covalently bonded to mesoporous SBA-15 [J]. The Journal of Physical Chemistry B, 2005, 109(32): 15278-15287.
15	MARTÍNEZA, LÓPEZC, MÁRQUEZF, et al. Fischer-Tropsch synthesis of hydrocarbons over mesoporous Co/SBA-15 catalysts: the influence of metal loading, cobalt precursor, and promoters [J]. Journal of Catalysis, 2003, 220(2): 486-499.
16	XINJinni, CUIHongjie, CHENGZhenmin, et al. Bimetallic Ni-Co/SBA-15 catalysts prepared by urea co-precipitation for dry reforming of methane [J]. Applied Catalysis A: General, 2018, 554: 95-104.
17	XUEYujie, YAORuihua, LIJunrui, et al. Efficient Pt-FeO_x/TiO₂@SBA-15 catalysts for selective hydrogenation of cinnamaldehyde to cinnamyl alcohol [J]. Catalysis Science & Technology, 2017, 7(24): 6112-6123.
18	MARTÍNEZF, MELEROJ A, ÁBOTAS J, et al. Treatment of phenolic effluents by catalytic wet hydrogen peroxide oxidation over Fe₂O₃/SBA-15 extruded catalyst in a fixed-bed reactor [J]. Industrial & Engineering Chemistry Research, 2007, 46(13): 4396-4405.
19	BINGJishuai, HUChun, NIEYulun, et al. Mechanism of catalytic ozonation in Fe₂O₃/Al₂O₃@SBA-15 aqueous suspension for destruction of ibuprofen [J]. Environmental Science & Technology, 2015, 49(3): 1690.
20	ZHONGYiwei, WANGZhi, GUOZhancheng, et al. Agglomeration/defluidization in a fluidized bed reduction of Fe₂O₃ particles by CO: Influences of iron precipitation on particle cohesiveness [J]. Powder Technology, 2014, 256(1): 13-19.
21	REYES-CARMONA, ÁLVARO, SORIANOM D, et al. Iron-containing SBA-15 as catalyst for partial oxidation of hydrogen sulfide [J]. Catalysis Today, 2013, 210: 117-123.

[1]	张明焱, 刘燕, 张雪婷, 刘亚科, 李从举, 张秀玲. 非贵金属双功能催化剂在锌空气电池研究进展[J]. 化工进展, 2023, 42(S1): 276-286.
[2]	时永兴, 林刚, 孙晓航, 蒋韦庚, 乔大伟, 颜彬航. 二氧化碳加氢制甲醇过程中铜基催化剂活性位点研究进展[J]. 化工进展, 2023, 42(S1): 287-298.
[3]	谢璐垚, 陈崧哲, 王来军, 张平. 用于SO₂去极化电解制氢的铂基催化剂[J]. 化工进展, 2023, 42(S1): 299-309.
[4]	杨霞珍, 彭伊凡, 刘化章, 霍超. 熔铁催化剂活性相的调控及其费托反应性能[J]. 化工进展, 2023, 42(S1): 310-318.
[5]	郑谦, 官修帅, 靳山彪, 张长明, 张小超. 铈锆固溶体Ce_0.25Zr_0.75O₂光热协同催化CO₂与甲醇合成DMC[J]. 化工进展, 2023, 42(S1): 319-327.
[6]	戴欢涛, 曹苓玉, 游新秀, 徐浩亮, 汪涛, 项玮, 张学杨. 木质素浸渍柚子皮生物炭吸附CO₂特性[J]. 化工进展, 2023, 42(S1): 356-363.
[7]	王正坤, 黎四芳. 双子表面活性剂癸炔二醇的绿色合成[J]. 化工进展, 2023, 42(S1): 400-410.
[8]	高雨飞, 鲁金凤. 非均相催化臭氧氧化作用机理研究进展[J]. 化工进展, 2023, 42(S1): 430-438.
[9]	许春树, 姚庆达, 梁永贤, 周华龙. 共价有机框架材料功能化策略及其对Hg(Ⅱ)和Cr(Ⅵ)的吸附性能研究进展[J]. 化工进展, 2023, 42(S1): 461-478.
[10]	王乐乐, 杨万荣, 姚燕, 刘涛, 何川, 刘逍, 苏胜, 孔凡海, 朱仓海, 向军. SCR脱硝催化剂掺废特性及性能影响[J]. 化工进展, 2023, 42(S1): 489-497.
[11]	顾永正, 张永生. HBr改性飞灰对Hg⁰的动态吸附及动力学模型[J]. 化工进展, 2023, 42(S1): 498-509.
[12]	赵景超, 谭明. 表面活性剂对电渗析减量化工业含盐废水的影响[J]. 化工进展, 2023, 42(S1): 529-535.
[13]	邓丽萍, 时好雨, 刘霄龙, 陈瑶姬, 严晶颖. 非贵金属改性钒钛基催化剂NH₃-SCR脱硝协同控制VOCs[J]. 化工进展, 2023, 42(S1): 542-548.
[14]	孙玉玉, 蔡鑫磊, 汤吉海, 黄晶晶, 黄益平, 刘杰. 反应精馏合成甲基丙烯酸甲酯工艺优化及节能[J]. 化工进展, 2023, 42(S1): 56-63.
[15]	杨寒月, 孔令真, 陈家庆, 孙欢, 宋家恺, 王思诚, 孔标. 微气泡型下向流管式气液接触器脱碳性能[J]. 化工进展, 2023, 42(S1): 197-204.

介孔Fe₂O₃/SBA-15催化臭氧氧化含酚废水

Catalytic oxidation of phenolic wastewater by O₃ over mesoporousFe₂O₃/SBA-15

RichHTML

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

图/表 8

参考文献 21

相关文章 15

编辑推荐

Metrics

本文评价