铝酸钴/蜂窝陶瓷催化剂的制备及其在印染废水处理中的应用
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摘要
为提高污水深度处理的臭氧催化氧化效率,采用涂覆法制备铝酸钴(CoAl_2O_4)/蜂窝陶瓷(CH)催化剂,考察涂覆次数、催化剂投加量、焙烧时间和温度等因素对催化效率的影响,优化催化剂的制备条件;借助X射线衍射仪、场发射扫描电子显微镜和N_2-吸附/脱附等手段分析催化剂的结构,通过对苯二酚的降解效果评价催化剂的催化性能,研究催化剂的使用寿命和催化机制。结果表明:在涂覆6次、700℃焙烧6 h、Co与Al的量比为0.4∶5的条件下,铝酸钴/蜂窝陶瓷(CoAl_2O_4/CH)催化剂的催化活性最高,比表面积和孔容最大(分别达到45.47 m~2/g、0.05 cm~2/g),对苯二酚和化学需氧量(COD)去除率分别达到84.51%和50.60%;制备的CoAl_2O_4/CH催化剂晶相属于尖晶石结构,蜂窝陶瓷涂层为海绵状结构;CoAl_2O_4/CH催化剂使用5次以上,仍保持较高的催化活性和稳定性,应用前景好。
In order to increase the catalytic efficiency of advanced wastewater treatment by catalytic ozonation, cobalt aluminate(CoAl_2O_4)/ceramic honeycomb(CH) catalyst was prepared by a coating method. The influence of coating times, the addition amount of catalyst, calcination time and temperature on the catalytic efficiency was investigated to optimize the preparation conditions. The structure of catalysts were analyzed by X-ray diffractometer, field emission scanning electron microscopy and N_2-adsorption and desorption. The catalytic performance and mechanisms were evaluated by catalytic ozonation of hydroquinone. The results show that the catalytic efficiency of CoAl_2O_4/CH is the highest under the conditions of coating for 6 times, calcination temperature of 700 ℃, calcination time of 6 h and molar ratio of Co to Al of 0.4∶5. The specific surface area and pore volume are the highest and reach 45.47 m~2/g and 0.05 cm~2/g, respectively. Removal rate of hydroquinone is 84.51% and removal rate of COD is 50.60%. The prepared catalysts belong to the spinal structure and the coating has a sponge-like structure. The catalysts maintain high catalytic activity and stability after repeated use for more than 5 times. Therefore, the application is promising.
In order to increase the catalytic efficiency of advanced wastewater treatment by catalytic ozonation, cobalt aluminate(CoAl_2O_4)/ceramic honeycomb(CH) catalyst was prepared by a coating method. The influence of coating times, the addition amount of catalyst, calcination time and temperature on the catalytic efficiency was investigated to optimize the preparation conditions. The structure of catalysts were analyzed by X-ray diffractometer, field emission scanning electron microscopy and N_2-adsorption and desorption. The catalytic performance and mechanisms were evaluated by catalytic ozonation of hydroquinone. The results show that the catalytic efficiency of CoAl_2O_4/CH is the highest under the conditions of coating for 6 times, calcination temperature of 700 ℃, calcination time of 6 h and molar ratio of Co to Al of 0.4∶5. The specific surface area and pore volume are the highest and reach 45.47 m~2/g and 0.05 cm~2/g, respectively. Removal rate of hydroquinone is 84.51% and removal rate of COD is 50.60%. The prepared catalysts belong to the spinal structure and the coating has a sponge-like structure. The catalysts maintain high catalytic activity and stability after repeated use for more than 5 times. Therefore, the application is promising.
引文
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[10] 吴玉琪, 吕功煊, 李树本. CoOx改性TiO2光催化剂的制备、优化及其光催化分解水析氢性能研究[J]. 无机化学学报, 2005, 21(3): 309-314.WU Yuqi, Lü Gongxuan, LI Shuben. The preparation, optimization and photocatalytic properties of CoOx modified TiO2 photocatalysts for hydrogen generation from photocatalytic water splitting[J]. Chinese Journal of Inorganic Chemistry, 2005, 21(3): 309-314.
[11] AGHAMOHAMMADI S, HAGHIGHI M, MALEKI M, et al. Sequential impregnation vs. sol-gel synthesized Ni/Al2O3-CeO2, nanocatalyst for dry reforming of methane: effect of synthesis method and support promotion[J]. Molecular Catalysis, 2017, 431(1): 39-48.
[12] 李冰蕊, 潘家豪, 王挺, 等. 用吸附相反应技术制备弱光响应的铈掺杂TiO2复合光催化剂[J]. 纺织学报, 2018, 39(5): 67-73.LI Bingrui, PAN Jiahao, WANG Ting, et al. Preparation of weak-light-driven TiO2 composite photocatalysts by adsorption phase synthesis[J]. Journal of Textle Research, 2018, 39(5): 67-73.
[13] 郭松林, 肖素萍, 陈林. CuMn/ZrAlTi-堇青石蜂窝陶瓷催化氧化法处理含酚废水[J]. 化工环保, 2012, 32(4): 367-371.GUO Songlin, XIAO Suping, CHEN Lin. Catalytic oxidation treatment of phenol wastewater using CuMn/ZrAlTi-cordierite hneycomb ceramics[J]. Environmental Protection of Chemical Industry, 2012, 32(4): 367-371.
[14] ZHAO L, MA J, SUN Z Z, et al. Catalytic ozonation for the degradation of nitrobenzene in aqueous solution by ceramic honeycomb-supported manganese[J]. Applied Catalysis B Environmental, 2008, 83(3): 256-264.
[15] 陈克强. 乙烯砜型活性染料染色废液的臭氧处理及循环利用[J]. 纺织学报, 1994,15(1): 34-37.CHEN Keqiang. Ozone treatment and recycling of vinyl sulfone reactive dyes waste liquid[J]. Journal of Textle Research, 1994, 15(1): 34-37.
[16] COLINDRES P, MADEIRA Y H, REGUERA E. Removal of reactive black 5 from aqueous solution by ozone for water reuse in textile dyeing processes[J]. Desalination, 2010, 258(4): 154-158.
[17] 李彤, 杨浩, 杨凯文, 等. 铁-锰-碳微电解法处理对苯二酚废水[J]. 化工环保, 2015, 35(2): 127-131.LI Tong, YANG Hao, YANG Kaiwen, et al. Treatment of hydroquinone-containing wastewater by Fe-Mn-C microelectrolysis process[J]. Environmental Protection of Chemical Industry, 2015, 35(2): 127-131.
[18] 郑可, 周少奇, 杨梅梅. 臭氧降解高浓度腐殖酸动力学[J]. 环境科学, 2012, 33(3): 879-884.ZHENG Ke, ZHOU Shaoqi, YANG Meimei. Degradation kinetics of ozone oxidation on high concentration of humic substances[J]. Environmental Science, 2012, 33(3): 879-884.
[19] 张兰河, 高伟围, 陈子成, 等. Mn-Co/蜂窝陶瓷催化剂制备及催化臭氧化对苯二酚性能[J]. 环境科学, 2018, 39(7): 3194-3202.ZHANG Lanhe, GAO Weiwei, CHEN Zicheng, et al. Preparation of Mn-Co/ceramic honeycomb catalyst and its performance on catalytic ozonation of hydro-quinone[J]. Environmental Science, 2018, 39(7): 3194-3202.
[20] 唐祝兴, 薛君. Fe3O4@Vc磁性纳米材料的合成及其对水中Cu(Ⅱ)的吸附性能研究[J]. 沈阳理工大学学报, 2013, 32(6): 82-87.TANG Zhuxing, XUE Jun. A method to produce magnetic ascorbic acid-coated Fe3O4 nanoparticles and the study of removal of Cu (Ⅱ) ions from aqueous solution[J]. Journal of Shenyang Ligong University, 2013, 32(6):82-87.
[21] 刘鸿健, 钱杰生. 差示-双波长分光光度法及其应用[J]. 东南大学学报(自然科学版), 1997, 27(4): 97-100.LIU Hongjian, QIAN Jiesheng. Differential-dual wavelength spectrophotometry and its application[J]. Journal of Southeast University (Natural Sicence Edition), 1997, 27(4): 97-100.
[22] POZNYAK T. Microorganisms inactivation by ozone dissolved in aqueous solution: a kinetic study based on bacterial culture lipids unsaturation[J]. Ozone Science and Engineering, 2015, 37(2): 119-126.
[23] 潘璐阳, 王树涛, 张兰河, 等. 掺杂型纳米MnO2/Al2O3催化剂的制备及催化臭氧化处理驱油污水二级出水[J]. 硅酸盐通报, 2015, 34(8): 2260-2266.PAN Luyang, WANG Shutao, ZHANG Lanhe, et al. Preparation of doped nano-MnO2/Al2O3 catalyst and catalytic ozonation of secondary effluent of oil extraction wastewater for advanced treatment[J]. Bulletin of the Chinese Ceramic Society, 2015, 34(8): 2260-2266.
[24] 雷利荣, 李友明. 臭氧及催化臭氧氧化法处理制浆废水的研究进展[J]. 中国造纸, 2013, 32(5): 55-61.LEI Lirong, LI Youming. Research progress of pulp mill effluent treatment with ozonation and catalytic ozonation technology[J]. China Pulp Paper, 2013, 32(5): 55-61.
[25] LI X, LIN J, LIN J, et al. Protective effects of dihydromyricetin against ·OH induced mesenchymal stem cells damage and mechanistic chemistry[J]. Molecules, 2016, 21(5): 604-610.
[26] LIU S, SONG H, WEI S, et al. Effect of direct electrical stimulation on decolorization and degradation of azo dye reactive brilliant red X-3B in biofilm-electrode reactors[J]. Biochemical Engineering Journal, 2015, 93(2): 294-302.
[27] GLAZE W H, KANG J W. Advanced oxidation process, description of a kinetic model for the oxidation of hazardous materials in aqueous media with ozone and hydrogen peroxide[J]. Industrial Engineering Chemistry Research, 1989, 28(11): 134-142.
[28] LANGLARIS B, RECKHOW D A, BRINK D R. Ozone in water treatment: application and engineering, cooperative research report[J]. Journal of Environmental Quality, 1991, 20(34): 881-882.
[29] 张兰河, 高伟围, 陈子成, 等. CoAl2O4/蜂窝陶瓷催化剂的制备及其催化臭氧化性能[J]. 无机化学学报, 2017, 33(6): 985-992.ZHANG Lanhe, GAO Weiwei, CHEN Zicheng, et al. CoAl2O4/ceramic honeycomb catalyst: preparation and performance on catalytic ozonation in wastewater treatment[J]. Chinese Journal of Inorganic Chemistry, 2017, 33(6): 985-992.
[30] KAN J, DENG L, LI B, et al. Performance of Co-doped Mn-Ce catalysts supported on cordierite for low concentration chlorobenzene oxidation[J]. Applied Catalysis A General, 2016, 530(1): 21-29.
[2] 董殿波. 印染废水处理技术研究进展[J]. 染料与染色, 2015, 52(4): 56-63.DONG Dianbo. Review on treatment of dyes waste-water[J]. Dyestuffs and Coloration, 2015, 52(4): 56-63.
[3] BELTRAN F J, RIVAS F J, MONTERODEESPINOSA R. Ozone-enhanced oxidation of oxalic acid in water with cobalt catalysts: 1. homogeneous catalytic ozon-ation[J]. Industrial and Engineering Chemistry Research, 2003, 42(14): 3210-3217.
[4] 贾艳萍, 姜成, 郭泽辉, 等. 印染废水深度处理及回用研究进展[J]. 纺织学报, 2017, 38(8): 172-180.JIA Yanping, JIANG Cheng, GUO Zehui, et al. Research progress on deep treatment and recycling of dye wastewater[J]. Journal of Textle Research, 2017, 38(8): 172-180.
[5] 李凯歌. 负载型杂多化合物和多组分金属氧化物催化剂的制备及选择氧化性能研究[D]. 长春: 吉林大学, 2014:1-20.LI Kaige. Preparation of supported polyoxometalates and multi-component metal oxides catalysts for selective oxidation[D]. Changchun: Jilin University, 2014:1-20.
[6] 李旭凯, 谢桂红, 郭转弟, 等. 活性炭及其负载活性组分催化臭氧氧化机理[J]. 广东化工, 2012, 39(5): 334-335.LI Xukai, XIE Guihong, GUO Zhuandi, et al.Mechanism of catalytic ozonation by activated carbon and supported active component catalyst[J]. Guangdong Chemical, 2012, 39(5): 334-335.
[7] YOSHIDA H, TAKAGI S. Effects of seed roasting temperature and time on the quality characteristics of sesame (Sesamum indicum) oil[J]. Journal of the Science of Food Agriculture, 2015, 75(1): 19-26.
[8] 雷利荣, 李友明. 臭氧及催化臭氧氧化法处理制浆废水的研究进展[J]. 中国造纸, 2013, 32(5): 55-61.LEI Liring, LI Youming. Research progress of pulp mill effluent treatment with ozonation and catalytic ozonation technology[J]. China Pulp Paper, 2013, 32(5): 55-61.
[9] 张耀辉, 涂勇, 唐敏, 等. Fe2O3-TiO2-MnO2/Al2O3催化臭氧化催化剂的制备及表征[J]. 中国环境科学, 2016, 36(10): 3003-3009.ZHANG Yaohui, TU Yong, TANG Min, et al. Preparation and characterization of Fe2O3-TiO2-MnO2/Al2O3 catalysts[J]. China Environmental Science, 2016, 36(10): 3003-3009.
[10] 吴玉琪, 吕功煊, 李树本. CoOx改性TiO2光催化剂的制备、优化及其光催化分解水析氢性能研究[J]. 无机化学学报, 2005, 21(3): 309-314.WU Yuqi, Lü Gongxuan, LI Shuben. The preparation, optimization and photocatalytic properties of CoOx modified TiO2 photocatalysts for hydrogen generation from photocatalytic water splitting[J]. Chinese Journal of Inorganic Chemistry, 2005, 21(3): 309-314.
[11] AGHAMOHAMMADI S, HAGHIGHI M, MALEKI M, et al. Sequential impregnation vs. sol-gel synthesized Ni/Al2O3-CeO2, nanocatalyst for dry reforming of methane: effect of synthesis method and support promotion[J]. Molecular Catalysis, 2017, 431(1): 39-48.
[12] 李冰蕊, 潘家豪, 王挺, 等. 用吸附相反应技术制备弱光响应的铈掺杂TiO2复合光催化剂[J]. 纺织学报, 2018, 39(5): 67-73.LI Bingrui, PAN Jiahao, WANG Ting, et al. Preparation of weak-light-driven TiO2 composite photocatalysts by adsorption phase synthesis[J]. Journal of Textle Research, 2018, 39(5): 67-73.
[13] 郭松林, 肖素萍, 陈林. CuMn/ZrAlTi-堇青石蜂窝陶瓷催化氧化法处理含酚废水[J]. 化工环保, 2012, 32(4): 367-371.GUO Songlin, XIAO Suping, CHEN Lin. Catalytic oxidation treatment of phenol wastewater using CuMn/ZrAlTi-cordierite hneycomb ceramics[J]. Environmental Protection of Chemical Industry, 2012, 32(4): 367-371.
[14] ZHAO L, MA J, SUN Z Z, et al. Catalytic ozonation for the degradation of nitrobenzene in aqueous solution by ceramic honeycomb-supported manganese[J]. Applied Catalysis B Environmental, 2008, 83(3): 256-264.
[15] 陈克强. 乙烯砜型活性染料染色废液的臭氧处理及循环利用[J]. 纺织学报, 1994,15(1): 34-37.CHEN Keqiang. Ozone treatment and recycling of vinyl sulfone reactive dyes waste liquid[J]. Journal of Textle Research, 1994, 15(1): 34-37.
[16] COLINDRES P, MADEIRA Y H, REGUERA E. Removal of reactive black 5 from aqueous solution by ozone for water reuse in textile dyeing processes[J]. Desalination, 2010, 258(4): 154-158.
[17] 李彤, 杨浩, 杨凯文, 等. 铁-锰-碳微电解法处理对苯二酚废水[J]. 化工环保, 2015, 35(2): 127-131.LI Tong, YANG Hao, YANG Kaiwen, et al. Treatment of hydroquinone-containing wastewater by Fe-Mn-C microelectrolysis process[J]. Environmental Protection of Chemical Industry, 2015, 35(2): 127-131.
[18] 郑可, 周少奇, 杨梅梅. 臭氧降解高浓度腐殖酸动力学[J]. 环境科学, 2012, 33(3): 879-884.ZHENG Ke, ZHOU Shaoqi, YANG Meimei. Degradation kinetics of ozone oxidation on high concentration of humic substances[J]. Environmental Science, 2012, 33(3): 879-884.
[19] 张兰河, 高伟围, 陈子成, 等. Mn-Co/蜂窝陶瓷催化剂制备及催化臭氧化对苯二酚性能[J]. 环境科学, 2018, 39(7): 3194-3202.ZHANG Lanhe, GAO Weiwei, CHEN Zicheng, et al. Preparation of Mn-Co/ceramic honeycomb catalyst and its performance on catalytic ozonation of hydro-quinone[J]. Environmental Science, 2018, 39(7): 3194-3202.
[20] 唐祝兴, 薛君. Fe3O4@Vc磁性纳米材料的合成及其对水中Cu(Ⅱ)的吸附性能研究[J]. 沈阳理工大学学报, 2013, 32(6): 82-87.TANG Zhuxing, XUE Jun. A method to produce magnetic ascorbic acid-coated Fe3O4 nanoparticles and the study of removal of Cu (Ⅱ) ions from aqueous solution[J]. Journal of Shenyang Ligong University, 2013, 32(6):82-87.
[21] 刘鸿健, 钱杰生. 差示-双波长分光光度法及其应用[J]. 东南大学学报(自然科学版), 1997, 27(4): 97-100.LIU Hongjian, QIAN Jiesheng. Differential-dual wavelength spectrophotometry and its application[J]. Journal of Southeast University (Natural Sicence Edition), 1997, 27(4): 97-100.
[22] POZNYAK T. Microorganisms inactivation by ozone dissolved in aqueous solution: a kinetic study based on bacterial culture lipids unsaturation[J]. Ozone Science and Engineering, 2015, 37(2): 119-126.
[23] 潘璐阳, 王树涛, 张兰河, 等. 掺杂型纳米MnO2/Al2O3催化剂的制备及催化臭氧化处理驱油污水二级出水[J]. 硅酸盐通报, 2015, 34(8): 2260-2266.PAN Luyang, WANG Shutao, ZHANG Lanhe, et al. Preparation of doped nano-MnO2/Al2O3 catalyst and catalytic ozonation of secondary effluent of oil extraction wastewater for advanced treatment[J]. Bulletin of the Chinese Ceramic Society, 2015, 34(8): 2260-2266.
[24] 雷利荣, 李友明. 臭氧及催化臭氧氧化法处理制浆废水的研究进展[J]. 中国造纸, 2013, 32(5): 55-61.LEI Lirong, LI Youming. Research progress of pulp mill effluent treatment with ozonation and catalytic ozonation technology[J]. China Pulp Paper, 2013, 32(5): 55-61.
[25] LI X, LIN J, LIN J, et al. Protective effects of dihydromyricetin against ·OH induced mesenchymal stem cells damage and mechanistic chemistry[J]. Molecules, 2016, 21(5): 604-610.
[26] LIU S, SONG H, WEI S, et al. Effect of direct electrical stimulation on decolorization and degradation of azo dye reactive brilliant red X-3B in biofilm-electrode reactors[J]. Biochemical Engineering Journal, 2015, 93(2): 294-302.
[27] GLAZE W H, KANG J W. Advanced oxidation process, description of a kinetic model for the oxidation of hazardous materials in aqueous media with ozone and hydrogen peroxide[J]. Industrial Engineering Chemistry Research, 1989, 28(11): 134-142.
[28] LANGLARIS B, RECKHOW D A, BRINK D R. Ozone in water treatment: application and engineering, cooperative research report[J]. Journal of Environmental Quality, 1991, 20(34): 881-882.
[29] 张兰河, 高伟围, 陈子成, 等. CoAl2O4/蜂窝陶瓷催化剂的制备及其催化臭氧化性能[J]. 无机化学学报, 2017, 33(6): 985-992.ZHANG Lanhe, GAO Weiwei, CHEN Zicheng, et al. CoAl2O4/ceramic honeycomb catalyst: preparation and performance on catalytic ozonation in wastewater treatment[J]. Chinese Journal of Inorganic Chemistry, 2017, 33(6): 985-992.
[30] KAN J, DENG L, LI B, et al. Performance of Co-doped Mn-Ce catalysts supported on cordierite for low concentration chlorobenzene oxidation[J]. Applied Catalysis A General, 2016, 530(1): 21-29.