Preparation of Fe2O3/modified natural zeolite catalyst and mechanism study on catalytic ozonation of 4-chlorophenol

doi:10.16085/j.issn.1000-6613.2019-1735

Abstract

Abstract:

In order to improve the efficiency of heterogeneous catalytic ozonation of refractory organic wastewater, Fe₂O₃/modified natural zeolite (MNZ) catalyst was prepared by impregnation method, in which the hexadecyl trimethyl ammonium bromide (CTMAB) modified natural zeolite and Fe(NO₃)₃·9H₂O solution were used as the carrier and a precursor of active components, respectively. The structure and constituent of the catalyst were analyzed and the catalytic ozonation performance of 4-chlorophenol (4CP) as well as the catalytic mechanisms were studied by using energy dispersive spectrometer (EDS), scanning electron microscope (SEM), Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and N₂ adsorption/desorption, respectively. The results showed that the Fe₂O₃/MNZ catalyst maintained the surface structure of natural zeolite and Fe₂O₃ was uniformly deposited on the surface of zeolite, which confirmed the catalyst had typical molecular sieve structure. The special surface area, pore volume and pore size of the catalyst were 12.776m²/g, 0.042cm³/g and 3.932nm, respectively. The removal efficiencies of 4CP and COD were 87.26% and 48.83% when the initial concentration of 4CP, O₃ concentration, temperature and pH were 100mg/L, 2.6mg/L, 25℃ and 7.0±0.2, respectively. MNZ and Fe₂O₃ synthetically promoted the decomposition of ozone into hydroxyl radical(·OH) with high oxidation capacity and thus improved the removal efficiency of 4CP. So, the reaction followed the mechanism of hydroxyl radical.

Key words: zeolite, catalytic ozonation, radical, 4-chlorophenol

摘要：

为了提高非均相催化臭氧氧化体系处理难降解有机废水的效率，分别以十六烷基三甲基溴化铵（CTMAB）改性的天然沸石和Fe(NO₃)₃·9H₂O溶液作为载体和活性组分前体，采用浸渍法制备Fe₂O₃/改性天然沸石催化剂（MNZ），利用能谱仪（EDS）、扫描电镜（SEM）、傅里叶变换红外光谱仪（FTIR）、X射线衍射仪（XRD）、X射线光电子能谱仪（XPS）、N₂-吸附/脱附等方法分析催化剂的结构和组成，研究其催化臭氧氧化对氯苯酚的效果和催化机制。结果表明：Fe₂O₃/MNZ催化剂保持了天然沸石的表面结构。Fe₂O₃均匀负载在沸石表面，属于典型的分子筛结构，比表面积、孔容和孔径分别为12.776m²/g、0.042cm³/g和3.932nm。在对氯苯酚初始浓度为100mg/L、臭氧浓度为2.6mg/L、温度为25℃、pH为7.0±0.2的条件下，对氯苯酚和化学需氧量（COD）去除率分别为87.26%和48.83%。天然沸石与Fe₂O₃共同促进臭氧分解生成强氧化能力的羟基自由基（·OH），提高了对氯苯酚的去除率，反应体系遵循羟基自由基作用机理。

关键词: 沸石, 催化臭氧氧化, 自由基, 对氯苯酚

CLC Number:

X703

Lanhe ZHANG, Lin GUO, Jianing LI, Zicheng CHEN, Yanping JIA, Zheng LI, Xiaohui GUAN. Preparation of Fe₂O₃/modified natural zeolite catalyst and mechanism study on catalytic ozonation of 4-chlorophenol[J]. Chemical Industry and Engineering Progress, 2020, 39(8): 3086-3094.

张兰河, 郭琳, 李佳宁, 陈子成, 贾艳萍, 李正, 关晓辉. Fe₂O₃/改性沸石催化剂的制备及其催化臭氧氧化对氯苯酚[J]. 化工进展, 2020, 39(8): 3086-3094.

References

1	AHMADI M, KAKAWANDI B, JAAFARZADEH N, et al. Catalytic ozonation of high saline petrochemical wastewater using PAC@FeIIFe₂IIIO₄: optimization, mechanisms and biodegradability studies[J]. Separation and Purification Technology, 2017, 177: 293-303.
2	刘俊逸, 李倩, 李杰, 等. 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.
2	LIU J Y, LI Q, LI J, et al. Catalytic oxidation of phenolic wastewater by O₃ over mesoporous Fe₂O₃/SBA-15[J]. Chemical Industry and Engineering Progress, 2019, 38(11): 5158-5164.
3	WU J J, MURUGANANDHAM M, CHANG L T, et al. Catalytic ozonation of oxalic acid using SrTiO₃ catalyst[J]. Ozone: Science and Engineering, 2011, 33(1): 74-79.
4	亓丽丽. 非均相臭氧催化氧化对氯苯酚机理研究及其工艺应用[D]. 哈尔滨: 哈尔滨工业大学, 2013.
4	QI L L. Mechanism research and application process of catalytic ozonation for degradation of 4-chlorophenol[D]. Harbin: Harbin Institute of Technology, 2013.
5	CHEN C, YAN X, YOZA B A, et al. Efficiencies and mechanisms of ZSM5 zeolites loaded with cerium, iron, or manganese oxides for catalytic ozonation of nitrobenzene in water[J]. Science of the Total Environment, 2018, 612: 1424-1432.
6	AYTEN A. The modification of aluminium content of natural zeolites with different composition[J]. Powder Technology, 2018, 344: 199-207.
7	GUMUS D, AKBAL F. A comparative study of oaonation, iron coated zeolite catalyzed ozonation and granular activated carbon catalyzed ozonation of humic acid[J]. Chemosphere, 2017, 174(5): 218-231.
8	ALVER E, AYSEGUL U M. Anionic dye removal from aqueous solutions using modified zeolite: adsorption kinetics and isotherm studies[J]. Chemical Engineering Journal, 2012, 200-202: 59-67.
9	王琳琳, 张智明, 丁阿强, 等. 沸石材料的改性及其对水体污染物的吸附性能[J]. 化工进展, 2018, 37(6): 2269-2281.
9	WANG L L, ZHANG Z M, DING A Q, et al. Modification of zeolite material and their adsorption for the pollutants in aqueous solution[J]. Chemical Industry and Engineering Progress, 2018, 37(6): 2269-2281.
10	董玉明, 蒋平平，张爱民. 介孔结构的α-FeOOH对苯酚的催化臭氧化降解[J]. 无机化学学报, 2009, 25(9): 1595-1600.
10	DONG Y M, JIANG P P, ZHANG A M. Catalytic ozonation degradation of phenol in water by mesoporous α-FeOOH[J]. Chinese Journal of Inorganic Chemistry, 2009, 25(9): 1595-1600.
11	杜珮雯, 党宏钰, 张永祥. 改性沸石和铁粉的复合材料处理水中六价铬的研究[J]. 中国环境科学, 2015, 35(5): 1384-1390.
11	DU P W, DANG H Y, ZHANG Y X. Kinetic study for removal of soluble Cr(Ⅳ) by prepared surfactant-modified zeolites supported zero-valent iron composite[J]. China Environmental Science, 2015, 35(5): 1384-1390.
12	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.
12	ZHANG Y H, TU Y, TANG M, et al. Preparation and characterization of Fe₂O₃-TiO₂-MnO₂/Al₂O₃ catalysts[J]. China Environmental Science, 2016, 36(10): 3003-3009.
13	FERNANDO J, BELTRAN, FRANCISCO J, et al. Iron type catalysts for the ozonation of oxalic acid in water[J]. Water Research,2005,39(15): 3553-3564.
14	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.
14	ZHANG L H, GAO W W, CHEN Z C, 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.
15	谢德龙, 万隆, 刘志环, 等. 共沉淀法制备Fe-Cu基预合金粉的低温热压烧结[J]. 粉末冶金材料科学与工程, 2015, 20(1): 93-98.
15	XIE D L, WAN L, LIU Z H, et al. Low-temperature hot press sintering of Fe-Cu based pre-alloyed powder manufactured by co-precipitation method[J]. Materials Science and Engineering of Powder Metallurgy, 2015, 20(1): 93-98.
16	LIOTTA L F, GRUTTADAURIA M, CARLO G D, et al. Heterogeneous catalytic degradation of phenolic substrates: catalysts activity[J]. Journal of Hazardous Materials, 2009, 162(2/3): 588-606.
17	莫立焕, 王聪聪, 何帅明, 等. 人造沸石催化臭氧处理对氯苯酚废水的研究[J]. 纸和造纸, 2014, 33(11): 62-66.
17	MO L H, WANG C C, HE S M, et al. Treatment of p-chlorophenol wastewater by artificial zeolite catalytic ozonation[J]. Paper and Paper Making, 2014, 33(11): 62-66.
18	ELAIOPOULOS K, PERRAKI T, GRIGOROPOULOU E. Mineralogical study and porosimetry measurements of zeolites from scaloma area, thrace, greece[J]. Microporous & Mesoporous Materials, 2008, 112(1-3): 441-449.
19	张涛, 马军, 陈忠林, 等. 有机酸在金属氧化物上的吸附对催化臭氧氧化的影响[J]. 环境科学, 2005, 26(5): 85-88.
19	ZHANG T, MA J, CHEN Z L, et al. Effect of organic acids adsorption on catalytic ozonation with metal oxides[J]. Environmental Science, 2005, 26(5): 85-88.
20	ELAIOPOULOS K, PERRAKI T, GRIGOROPOULOU E. Monitoring the effect of hydrothermal treatments on the structure of a natural zeolite through a combined XRD, FTIR, XRF, SEM and N₂-porosimetry analysis[J]. Microporous & Mesoporous Materials, 2010, 134(1-3): 29-43.
21	范钧朝, 陈爱因, 陈诗, 等. 过渡金属Fe、Co、Ni介孔分子筛MCM-41催化剂的制备及其氧化性能[J]. 环境化学, 2016, 35(6): 1116-1124.
21	FAN J Z, CHEN A Y, CHEN S, et al. Synthesis of Fe, Co, Ni loaded MCM-41 mesoporous molecular sieves and their catalytic oxidation performance[J]. Environmental Chemistry, 2016, 35(6): 1116-1124.
22	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.
23	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.
23	LEI L R, LI Y M. Research progress of pulp mill effluent treatment with ozonation and catalytic ozonation technology[J]. China Pulp & Paper, 2013, 32(5): 55-61.
24	张兰河, 周靖, 郭映辉, 等. CeO₂/Al₂O₃催化剂的制备表征及在污水处理中的应用[J]. 农业工程学报, 2017, 33(1): 219-224.
24	ZHANG L H, ZHOU J, GUO Y H, et al. Preparation and characterization of CeO₂/Al₂O₃ and its application on advanced treatment of wastewater[J]. Transactions of the Chinese Society of Agricultural Engineering, 2017, 33(1): 219-224.
25	白小霞, 杨庆, 丁昀, 等. 催化臭氧氧化处理难降解石化废水技术的研究进展[J]. 化工进展, 2016, 35(1): 263-268.
25	BAI X X, YANG Q, DING Y, et al. Research progress of catalytic ozonation process to treat refractory petrochemical wastewater[J]. Chemical Industry and Engineering Progress, 2016, 35(1): 263-268.
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: 294-302.
27	戴慧旺, 陈建新, 苗笑增, 等. 醇类对UV-Fenton体系羟基自由基淬灭效率的影响[J]. 中国环境科学, 2018, 38(1): 202-209.
27	DAI H W, CHEN J X, MIAO X Z, et al. Effecct of alcohols on scavenging efficiencies to hydroxyl radical in UV-Fenton system[J]. China Environmental Science, 2018, 38(1): 202-209.
28	DING L, SUN C Z, TANG C J, et al. Investigations of surface VO_xspecies and their contributions to activities of VO_x/Ti_0.5Sn_0.5O₂ catalysts toward selective catalytic reduction of NO by NH₃[J]. Applied Catalysis A: General, 2012, 431/432(29): 126-136.
29	ERNST M, LUROT F, SCHROTTER J C. Catalytic ozonation of refractory organic model compounds in aqueous solution by aluminum oxide[J]. Applied Catalysis B: Environmental, 2004, 47(1): 15-25.
30	吕杭杰, 贾建洪, 金赞芳, 等. Fe-Mn负载凹凸棒催化剂的制备及协同臭氧化处理甲基橙模拟废水的应用[J].高校化学工程学报, 2017, 31(5): 1217-1224.
30	LYU H J, JIA J H, JIN Z F, et al. Preparation of Fe-Mn palygorskite catalysts and their cooperation with ozonation in simulated methyl orange wastewater treatment[J]. Journal of Chemical Engineering of Chinese Universities, 2017, 31(5): 1217-1224.
31	MARTINS R C, QUINTA-FERREIRA R M. Phenolic wastewaters depuration and biodegradability enhancement by ozone over active catalysts[J]. Desalination, 2011, 270(1/2/3): 90-97.
32	XU Z Z, CHEN Z L, CYNTHIA J, et al. Catalytic efficiency and stability of cobalt hydroxide for decomposition of ozone and p-chloronitrobenzene in water[J]. Catalysis Communications, 2009, 10(8): 1221-1225.
33	邵琴, 金腊华, 刘玉兵, 等.沸石载体催化剂研制及其催化臭氧氧化染料废水的研究[J].环境污染与防治, 2010, 32(12): 59-62, 66.
33	SHAO Q, JIN L H, LIU Y B, et al. Preparation of zeolite catalysts for ozone catalytic oxidation of dye wastewater[J]. Environmental Pollution & Control, 2010, 32(12): 59-62, 66.

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Preparation of Fe₂O₃/modified natural zeolite catalyst and mechanism study on catalytic ozonation of 4-chlorophenol

Fe₂O₃/改性沸石催化剂的制备及其催化臭氧氧化对氯苯酚

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