MnO x /ZrO2 催化剂制备及催化臭氧氧化降解甲基橙

doi:10.11949/j.issn.0438-1157.20181346

摘要/Abstract

摘要：

以商品化ZrO₂为载体，采用等体积浸渍法制备MnO _x /ZrO₂催化剂，对目标污染物甲基橙溶液进行催化臭氧降解效果研究。比较不同焙烧温度（350、400、500和550℃）、不同MnO _x 负载量（5%、10%、15%和18%）等制备条件对催化剂活性的影响，结果表明：在400℃，MnO _x 负载量为15%时，催化剂对催化臭氧降解甲基橙溶液表现出最好的活性。反应进行60 min后，甲基橙溶液的脱色率达92.8%，较单独臭氧氧化提高了36.1%。催化剂15%MnO _x /ZrO₂（400℃）的酸碱使用范围（pH为2.7、6.5、8.7、10.8）实验表明：甲基橙溶液不同初始pH条件同样会影响催化剂的活性，且pH=2.7时表现出最好的催化效果，甲基橙脱色率可达95%。循环实验表明，15%MnO _x /ZrO₂（400℃）具有较好的稳定性，催化剂循环使用三次后，甲基橙溶液脱色率仍保持在85%以上，且活性组分的流失是降低催化剂活性的一个重要原因。

关键词: 等体积浸渍法, 催化剂, 甲基橙, 催化臭氧氧化, 脱色反应

Abstract:

The MnO _x /ZrO₂ catalyst was prepared by the equal volume impregnation method with commercial ZrO₂ as carrier, and the catalytic ozone degradation effect of the target pollutant methyl orange solution was studied. The factors of calcination temperature and MnO _x loading content were studied to determine the optimal catalyst preparation condition. It turned out that, the catalyst would get the best catalytic activity with 15% MnO _x loading and being calcined at 400℃, and the decolorization efficiency of methyl orange was 92.8% over the catalyst of 15%MnO _x /ZrO₂ (400℃), which increased by 36.1% compared with that in the ozonation without catalyst after 60 min of reaction. Also, the initial pH of methyl orange solution (pH =2.7,6.5,8.7,10.8) was investigated during the catalytic ozonation process. The 15%MnO _x /ZrO₂ (400℃) catalyst performed a higher catalytic efficiency of 95% at pH=2.7 than that value of 6.5 without adjustment by acid or alkali. The catalyst cycle test showed a better stability for 15%MnO _x /ZrO₂ (400℃), and the decolorization rate of methyl orange slightly drop down to about 85% after three times reuse. Moreover，the loss of MnO _x was an important reason for the descent of catalyst activity by characterization experiments.

Key words: incipient wetness impregnation method, catalyst, methyl orange, catalytic ozonation, decolorization reaction

中图分类号:

TQ 028.8

于海斌, 刘强, 周立坤, 陈赞, 罗超, 张贯艳, 乔利娜, 王建杰. MnO _x /ZrO₂ 催化剂制备及催化臭氧氧化降解甲基橙[J]. 化工学报, 2019, 70(4): 1436-1445.

Haibin YU, Qiang LIU, Likun ZHOU, Zan CHEN, Chao LUO, Guanyan ZHANG, Jianjie QIAO Lina WANG. Preparation of MnO _x /ZrO₂ catalyst and catalytic ozonation degradation of methylorange[J]. CIESC Journal, 2019, 70(4): 1436-1445.

图/表 15

图1 实验装置

Fig.1 Schematic diagram of experimental apparatus

图2 载体与催化剂的N2吸脱附等温曲线

Fig.2 N2 adsorption-desorption isotherms of ZrO2 support, fresh and used 15%MnO x /ZrO2 (400℃) catalysts

表1 载体与催化剂的物理吸附结果

Table 1 BET information of ZrO2 support, fresh and used 15%MnO x /ZrO2 (400℃) catalysts

Sample	S _BET/(m²/g)	D _p/nm	V _micro/(m³/g)
ZrO₂ support	13.22	20.64	0.068
fresh 15%MnO _x /ZrO₂ (400℃)	12.90	26.23	0.084
used 15%MnO _x /ZrO₂ (400℃)	13.20	20.54	0.068

图3 不同焙烧温度下15%MnO x /ZrO2催化剂的XRD谱图

Fig.3 XRD patterns of 15%MnO x /ZrO2 catalysts at different calcination temperature

图4 不同负载量催化剂MnO x /ZrO2 (400℃)的XRD谱图

Fig.4 XRD patterns of MnO x /ZrO2 (400℃) catalysts in different loadings of MnO x

图5 ZrO2载体和15%MnO x /ZrO2（400℃）催化剂的SEM、TEM及EDS mapping照片

Fig.5 SEM, TEM or EDS mapping photos of ZrO2 support and 15%MnO x /ZrO2 (400℃) catalysts

图6 焙烧温度对15%MnO x /ZrO2催化剂活性的影响

Fig.6 Effect of calcination temperature on catalytic activity of 15%MnO x /ZrO2 in ozonation(catalyst dosage=1.0 g/L, pH=6.5±0.05, ozone flow=0.6 mg/min, MO concentration=100 mg/L, temperature=25℃±1℃, volume=500 ml)

图7 MnO x 负载量对MnO x /ZrO2（400℃）催化剂活性的影响

Fig.7 Effect of MnO x load on catalytic activity of MnO x /ZrO2 (calcination at 400℃) in ozonation (catalyst dosage=1.0 g/L, pH=6.5±0.05, ozone flow=0.6 mg/min, MO concentration=100 mg/L, temperature=25℃±1℃, volume=500 ml)

图8 溶液初始pH对15%MnO x /ZrO2（400℃）催化降解甲基橙的影响

Fig.8 Effect of initial solution pH on decolorization of methyl orange in catalytic ozonation with 15%MnO x /ZrO2 (400℃) catalyst(catalyst dosage=1.0 g/L, ozone flow=0.6 mg/min, MO concentration=100 mg/L, temperature=25℃±1℃, volume=500 ml)

表2 不同pH条件下15%MnO x /ZrO2 （400℃）催化臭氧氧化降解甲基橙一级反应速率常数及相关系数

Table 2 Rate constant and correlation coefficients of methyl orange decolorization in different pH over 15%MnO x /ZrO2 (400℃) catalyst

pH	Rate constant k/min^-1	R ²
2.7	0.053	0.94
6.5	0.043	0.99
8.7	0.023	0.93
10.8	0.015	0.98

图9 15%MnO x /ZrO2（400℃）作用下不同pH条件下甲基橙脱色一级反应动力学

Fig.9 First kinetic graph of methyl orange decolorization at different pH over 15%MnO x /ZrO2 (400℃) catalyst

图10 甲基橙溶液起始pH=2.7时不同体系下甲基橙脱色过程的一级反应动力学

Fig.10 First kinetic graph of methyl orange decolorization process in different systems at pH=2.7

表3 甲基橙溶液起始pH=2.7时反应60 min后不同体系下甲基橙脱色过程的一级反应速率常数及相关系数

Table 3 Rate constant and correlation coefficients of methyl orange decolorization process in different systems after 60 min reaction at pH=2.7

System	Rate constant k/ min^-1	R ²
15% MnO _x /ZrO₂ (400℃) adsorption	0.006	0.93
O₃ alone	0.026	0.97
ZrO₂+O₃	0.029	0.93
15% MnO _x /ZrO₂ (400℃)+O₃	0.046	0.96

图11 15%MnOx/ZrO2（400℃）催化剂稳定性考察

Fig.11 Stability of 15%MnO x /ZrO2 (400℃) catalyst(catalyst dosage=1.0 g/L, pH=2.7, ozone flow=0.6 mg/min, MO concentration=100 mg/L, temperature=25℃±1℃, volume=500 ml)

表4 15% MnOx/ZrO2 （400℃）催化剂循环使用1次和3次后溶液中Mn、Zr元素的含量表征结果

Table 4 Loss of Mn and Zr element contents in reaction solution after 1st and 3rd runs over 15%MnO x /ZrO2 (400℃) catalyst

Run times	Element content/(mg/L)
Run times	Mn	Zr
1	2.60	0.29
3	0.76	7.67

参考文献 40

1	李丽华, 马明明, 任庆军, 等 . CeO₂/三维石墨烯催化臭氧化降解刚果红[J]. 化工环保，2017, 37(3): 294-299.
	Li L H , Ma M M , Ren Q J , et al . Degradation of congo red by catalytic ozonation on CeO₂/3D graphene[J]. Environ. Pro. Chem. Ind., 2017, 37(3): 294-299.
2	任南琪, 周显娇, 郭婉茜, 等 . 染料废水处理技术研究进展[J]. 化工学报, 2013, 64(1): 84-94.
	Ren N Q , Zhou X J , Guo W Q , et al . A review on treatment methods of dye wastewater[J]. CIESC Journal, 2013, 64(1): 84-94.
3	Habiba U , Siddique T A , Lee J J L , et al . Adsorption of methyl orange by chitosan/polyvinyl alcohol/zeolite electrospun composite nanofibrous membrane[J]. Carbohydr. Polym., 2018, 191: 79-85.
4	张轶, 从燕青, 孙培德 . 电絮凝处理甲基橙废水的实验及动力学模型[J]. 化工学报, 2009, 60(9): 2339-2345.
	Zhang Y , Cong Y Q , Sun P D . Experiment and kinetic model for methyl orange wastewater removal by electroagulation[J]. CIESC Journal, 2009, 60(9): 2339-2345.
5	Li P , Liu Z P , Wang X G , et al . Enhanced decolorization of methyl orange in aqueous solution using ironecarbon micro-electrolysis activation of sodium persulfate[J]. Chemosphere, 2017, 180: 100-107.
6	张婷 . 高级氧化技术的研究进展[J]. 广州化工, 2011, 39(14): 36-39.
	Zhang T . Research progress of advanced oxidation technologies[J]. Guangzhou Chemical Industry, 2011, 39(14): 36-39.
7	刘爱萍 . 高级氧化技术在水处理中的研究与展望[J]. 科技致富向导, 2011, (3): 187-204.
	Liu A P . Research and development of advanced oxidation processes in water treatment[J]. Guide of Sci-tech Magazine, 2011, (3): 187-204.
8	任百祥, 范晶莹, 杨春维 . 磁性活性炭催化氧化降解水中甲基橙[J]. 化工环保, 2015, 35(4): 409-413.
	Ren B X , Fan J Y , Yang C W . Degradation of methyl orange in water by catalytic ozone oxidation with magnetic activated carbon[J]. Environ. Pro. Chem. Ind., 2015, 35(4): 409-413.
9	Tang Y M , Pan Z Q , Li L S . pH-insusceptible cobalt-manganese immobilizing mesoporous siliceous MCM-41 catalyst for ozonation of dimethyl phthalate[J]. J. Colloid Interface Sci., 2017, 508: 196-202.
10	Tong S P , Shi R , Zhang H , et al . Catalytic performance of Fe₃O₄-CoO/Al₂O₃ catalyst in ozonation of 2-(2, 4-dichlorophenoxy) propionic acid, nitrobenzene and oxalic acid in water[J]. J. Environ. Sci., 2010, 22(10): 1623-1628.
11	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氧化处理驱油污水二级出水[J]. 硅酸盐通报, 2015, 34(8): 2260-2266.
	Pan L Y , Wang S T , Zhang L H , et al . Preparation of dope nano-MnO₂/Al₂O₃ catalyst and catalytic ozonation of secondary effluent of oil extraction wastewater for advanced treatment[J]. Bull. Chin. Ceramic Soc., 2015, 34(8): 2260-2266.
12	Asma A , Monia G , Javier R T F , et al . Nitrobenzene degradation in aqueous solution using ozone/cobalt supported activated carbon coupling process: a kinetic approach[J]. Sep. Purif. Technol., 2017, 184: 308-318.
13	Zhang J H , Zhang Q , Shao X Z , et al . Properties of magnetic carbon nanomaterials and application in removal organic dyes[J]. Chemosphere, 2018, 207: 377-384.
14	何志桥, 姜哲, 姜理英, 等 . 多壁碳纳米管的氨表面改性及其臭氧催化降解草酸[J]. 化工学报, 2012, 63(8): 2551-2556.
	He Z Q , Jiang Z , Jiang L Y , et al . Surface modification of multi-walled carbon nanotubes by ammonia and catalytic degradation of oxalic by ozonation[J]. CIESC Journal, 2012, 63(8): 2551-2556.
15	Liu X M , Lu G Q , Yan Z F . Synthesis and stabilization of nanocrystalline zirconia with MSU mesostructure[J]. J. Phys. Chem. B, 2004, 108: 15523-15528.
16	Su C L , Li J R , He D H , et al . Synthesis of isobutene from synthesis gas over nanosize zirconia catalysts [J]. Appl. Catal., A, 2000, 202(1): 81-89.
17	Michael W , David M , Antonelli J , et al . Synthesis and characterization of phosphated mesoporous zirconium oxide[J]. Nanostruct. Mater., 1997, 9(16): 165-168.
18	Song Y Q , Liu H M , He D H . Effects of hydrothermal conditions of ZrO₂ on catalyst properties and catalytic performances of Ni/ZrO₂ in the partial oxidation of methane[J]. Energy Fuels, 2010, 24(5): 2817-2824.
19	Benito M , Padilla R , Rodríguez L , et al . Zirconia supported catalysts for bioethanol steam reforming: effect of active phase and zirconia structure[J]. J. Power Sources, 2007, 169(1): 167-176.
20	贡湘君, 叶飞, 刘荣, 等 . 四方相氧化锆基MnO _x -CeO₂负载型催化剂在低温NH₃-SCR中的应用[J]. 功能材料, 2015, 10(46): 10090-10094.
	Gong X J , Ye F , Liu R , et al . Low-temperature selective catalytic reduction with NH₃ over MnO_x-CeO₂ catalysts supported on nano tetragonal-phase zirconia[J]. Journal of Functional Materials, 2015, 10(46): 10090-10094.
21	彭爱国, 贺周初, 肖伟, 等 . 化学二氧化锰的研究进展[J].无机盐工业, 2011, 43(3): 8-11.
	Peng A G , He Z C , Xiao W , et al . Research progress of chemical manganese dioxide[J]. Inorganic Chemicals Industry, 2011, 43(3): 8-11.
22	袁建梅, 杨德敏 . 非均相催化臭氧氧化深度处理钻井废水的效能研究[J]. 工业水处理, 2014, 34(8): 36-40.
	Yuan J M , Yang D M . Efficiency research on the advanced treatment of drilling wastewater by heterogeneous catalytic ozonation[J]. Industrial Water Treatment, 2014, 34(8): 36-40.
23	郭春芳 . 催化臭氧氧化工艺深度处理印染废水[J]. 工业水处理, 2013, 33(7): 43-46.
	Guo C F . Study on the advanced treatment of printing & dyeing wastewater by catalysis ozone oxidation process[J]. Industrial Water Treatment, 2013, 33(7): 43-46.
24	Andreozzi R , Insola A , Caprio V , et al . The use of manganese dioxide as a heterogeneous catalyst for oxalic acid ozonation in aqueous solution[J]. Appl. Catal., A, 1996, 138(1): 75-81.
25	Tong S P , Liu W P , Leng W H , et al . Characteristics of MnO₂ catalytic ozonation of sulfosalicylic acid and propionic acid in water[J]. Chemosphere, 2003, 50(10): 1359-1364.
26	Mullet M , Fievet P , Szymczyk A , et al . A simple and accurate determination of the point of zero charge of ceramic membranes[J]. Desalination, 1999, 121: 41-48.
27	Gayle N , Rob H , Mary D . Granular activated carbon: importance of surface properties in the adsorption of naturally occurring organics[J]. Colloids Surf., A, 1993, 78: 65-71.
28	张永利, 韦朝海, 史册, 等 . Cu-Fe-Ru-La/γ-Al₂O₃湿式氧化催化剂的制备、表征及机理[J]. 人工晶体学报, 2013, 42(7): 1457-1469.
	Zhang Y L , Wei C H , Shi C , et al . Preparation, characterization and mechanism of Cu-Fe-Ru-La/γ-Al₂O₃ catalysts for wastewater wet oxidation[J]. J. Synthetic Cryst., 2013, 42(7): 1457-1469.
29	刘昳 . 钛催化剂光催化降冰片二烯异构研究[D]. 天津: 天津大学, 2009.
	Liu Y . Study on photocatalytic isomerization of norbornadiene with titanium catalyst[D]. Tianjin: Tianjin University, 2009.
30	赵基钢, 沈本贤, 肖卫国 . 薄片状TS-1分子筛催化剂及其在丙烯环氧化反应中的催化性能[J]. 石化技术与应用, 2010, 28(1): 1-4.
	Zhao J G , Shen B X , Xiao W G . Research of lamellar TS-1 molecular sieve catalyst and their catalytic performance in propylene oxidation[J]. Petrochemical Technology & Application, 2010, 28(1): 1-4.
31	Huang H B , Ye X G , Huang W J , et al . Ozone-catalyticoxidation of gaseous benzene over MnO₂/ZSM-5 at ambient temperature: catalytic deactivationand its suppression[J]. Chem. Eng. J., 2015, 264: 24-31.
32	Shahzad A , Quan X , Chen S , et al . Synthesis of manganese incorporated hierarchical mesoporous silica nanosphere with fibrous morphology by facile one-pot approach for efficient catalytic ozonation[J]. J. Hazard. Mater., 2016, 318: 308-318.
33	柯武, 张永丽, 张静, 等 . Fe-MnO _x 催化臭氧氧化甲基橙[J]. 四川大学学报, 2016, 48(1): 221-226.
	Ke W , Zhang Y L , Zhang J , et al . Ozonation of methyl orange catalyzed by Fe-MnO _x [J]. J. Sichuan Univ., 2016, 48(1): 221-226.
34	王伟平, 陈凌燕, 杨水金 . H₃PW₍₁₂₎O₍₄₀₎/ZrO₂催化合成环己酮乙二醇缩酮[J]. 湖北师范大学学报(自然科学版), 2011, 31(1): 84-88.
	Wang W P , Chen L Y , Yang S J . Synthesis of cyclohexanone glycol ketal catalyzed by H₃PW₍₁₂₎O₍₄₀₎/ZrO₂ [J]. Journal of Hubei Normal Univerity(Nature Science), 2011, 31(1): 84-88.
35	Abidin A Z , Bakar N H H A , Ng E P , et al . Rapid degradation of methyl orange by Ag doped zeolite X in the presence of borohydride[J]. Journal of Taibah University for Science, 2017, 11: 1070-1079.
36	Gholamreza M , Maryam M . Degradation and biodegradability improvement of the reactive red 198 azo dye using catalytic ozonation with MgO nanocrystals[J]. Chem. Eng. J., 2009, 152: 1-7.
37	Nidhi G , Bonamail P . Core-shell structure of metal loaded CdS-SiO₂ hybrid nanocomposites for complete photomineralization of methyl orange by visible light[J]. J. Mol. Catal. A: Chem., 2014, 391: 158-167.
38	Xing S T , Hu C , Qu J H , et al . Characterization and reactivity of MnO _x supported on mesoporous zirconia for herbicide 2, 4-D mineralization with ozone[J]. Environ. Sci. Technol., 2008, 42: 3363-3368.
39	Sui M H , Xing S C , Sheng L , et al . Heterogeneous catalytic ozonation of ciprofloxacin in water with carbon nanotube supported manganese oxides as catalyst[J]. J. Hazard. Mater., 2012, 227/228: 227-236.
40	Faheem N , Cao H B , Xie Y B , et al . Selection of active phase of MnO₂ for catalytic ozonation of 4-nitrophenol[J]. Chemosphere, 2017, 168: 1457-1466.

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MnO _x /ZrO₂ 催化剂制备及催化臭氧氧化降解甲基橙

Preparation of MnO _x /ZrO₂ catalyst and catalytic ozonation degradation of methylorange

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