Catalytic ozonation based on carbon materials for removing dissolved organic compounds from water:A review

doi:10.16085/j.issn.1000-6613.2015.06.041

Abstract

Abstract: Catalytic ozonation based on carbon materials labeled as CMs/O₃ was well characterized by superior organics removal, high ozone utilization and without metal leaching; however, most of them were still at the stage of laboratory research, since a stable catalytic property of CMs could not be expected after a long running. In this paper, the main reaction mechanisms in CMs/O₃ system for removing dissolved organics from water, both surface catalytic oxidation and hydroxyl radicals(HO·)oxidation in bulk solution were discussed and the influences of critical factors in heterogeneous reaction pathways and organics removal efficiency were elaborated. It was pointed out that the consumption of basic active sites and the accumulation of acid oxygen-containing groups on the surface were considered to cause a partial deactivation of CMs in cyclic experiments. In addition, using mesoporous catalyst, optimizing pH and normalized ozone dosage, could help in reducing internal mass transfer resistances, thus enhance target organics removal. This paper reviewed the recent advances of CMs/O₃ applied in model organic pollutants removal and industrial wastewater treatment. Multi-walled carbon nanotube(MWCNT)and the innovative loading technology could improve CMs/O₃ performances in deep purification of micro-polluted water body. Coupling mature treatment methods and CMs/O₃ in an efficient and low-cost process was proposed as the important direction of further study.

Key words: carbon materials, ozonation, catalysis, organic compounds, surface, hydroxyl radicals

摘要： 碳质材料催化臭氧氧化(CMs/O₃)体系具有除污性能强、臭氧利用率高和无金属溶出的特点, 但受制于CMs催化性能的易失性, 该方法目前仍处于实验室研发阶段。本文系统阐述了CMs/O₃体系的反应原理, 并认为表面催化氧化与均相羟自由基(HO·)反应是去除水中溶解性有机物的主要途径;详细分析了影响非均相反应机理与体系处理效能的关键因素, 并指出在反应过程中, 碳表面碱性活性点位的消耗与酸性含氧基团的累积可导致其催化性能的降低, 而选择以中孔结构为主的碳质材料, 优化溶液pH值和臭氧相对投加量等操作参数, 将有利于降低CMs内部的传质阻力, 显著提高对目标污染物的去除率。基于新近发表的文献, 本文综述了CMs/O₃对多种有机污染物和实际废水的处理效能, 并认为多壁碳纳米管(MWCNT)的引入与新型固着、负载技术的使用, 有望提升CMs/O₃在微污染水体深度净化领域的实用化水平。同时, 努力将CMs/O₃与现有技术相耦合, 建立经济、高效的组合工艺也是当前应用研究的重要方向。

关键词: 碳质材料, 臭氧氧化, 催化作用, 有机化合物, 表面, 羟自由基

CLC Number:

X703

QIAN Feiyue, WANG Fanfan, LIU Xiaopeng, LI Yuehan, WANG Jianfang. Catalytic ozonation based on carbon materials for removing dissolved organic compounds from water:A review[J]. Chemical Industry and Engineering Progree, 2015, 34(06): 1755-1761.

钱飞跃, 王翻翻, 刘小朋, 李月寒, 王建芳. 碳质材料催化臭氧氧化去除水中溶解性有机物的研究进展[J]. 化工进展, 2015, 34(06): 1755-1761.

References

[1] Kasprzyk-Hordern B, Ziolek M, Nawrocki J. Catalytic ozonation and methods of enhancing molecular ozone reactions in water treatment[J]. Applied Catalysis B, 2003, 46(4):639-669.
[2] Nawrocki J, Kasprzyk-Hordern B. The efficiency and mechanisms of catalytic ozonation[J]. Applied Catalysis B, 2010, 99(1-2):27-42.
[3] Rivera-Utrilla J, Sanchez-Polo M. Ozonation of naphthalenesulphonic acid in the aqueous phase in the presence of basic activated carbons[J]. Langmuir, 2004, 20(21):9217-9222.
[4] Beltran F J, Acedo B, Rivas F J, et al. Pyruvic acid removal from water by the simultaneous action of ozone and activated carbon[J]. Ozone:Science & Engineering, 2005, 27(2):159-169.
[5] Rivera-Utrilla J, Mendez-Diaz J, Sanchez Polo M, et al. Removal of the surfactant sodium dodecylbenzenesulphonate from water by simultaneous use of ozone and powdered activated carbon:Comparison with systems based on O₃ and O₃/H₂O₂[J]. Water Research, 2006, 40(8):1717-1725.
[6] Faria P C C, Orfao J J M, Pereira M F R. Activated carbon and ceria catalysts applied to the catalytic ozonation of dyes and textile effluents[J]. Applied Catalysis B, 2009, 88(3-4):341-350.
[7] Beltran F J, Pocostales J P, Alvarez P M, et al. Diclofenac removal from water with ozone and activated carbon[J]. Journal of Hazardous Materials, 2009, 163(2-3):768-776.
[8] Qu X F, Zheng J T, Zhang Y Z. Catalytic ozonation of phenolic wastewater with activated carbon fiber in a fluid bed reactor[J]. Journal of Colloid and Interface Science, 2007, 309(2):429-434.
[9] Liu Z Q, Ma J, Cui Y H, et al. Effect of ozonation pretreatment on the surface properties and catalytic activity of multi-walled carbon nanotube[J]. Applied Catalysis B, 2009, 92(3-4):301-306.
[10] Goncalves A G, Figueiredo J L, Orfao J J M, et al. Influence of the surface chemistry of multi-walled carbon nanotubes on their activity as ozonation catalysts[J]. Carbon, 2010, 48(15):4369-4381.
[11] Liu Z Q, Ma J, Cui Y H, et al. Factors affecting the catalytic activity of multi-walled carbon nanotube for ozonation of oxalic acid[J]. Separation and Purification Technology, 2011, 78(2):147-153.
[12] Rodriguez Reinoso F. The role of carbon materials in heterogeneous catalysis[J]. Carbon, 1998, 36(3):159-175.
[13] Lin S H, Lai C L. Kinetic characteristics of textile wastewater ozonation in fluidized and fixed activated carbon beds[J]. Water Research, 2000, 34(3):763-772.
[14] Faria P C C, Orfao J J M, Pereira M F R. Mineralisation of coloured aqueous solutions by ozonation in the presence of activated carbon[J]. Water Research, 2005, 39(8):1461-1470.
[15] Serp P, Corrias M, Kalck P. Carbon nanotubes and nanofibers in catalysis[J]. Applied Catalysis A, 2003, 25(2):337-358.
[16] Goncalves A G, Orfao J J M, Pereira M F R. Catalytic ozonation of sulphamethoxazole in the presence of carbon materials:Catalytic performance and reaction pathways[J]. Journal of Hazardous Materials, 2012, 239-240(15):167-174.
[17] 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]. Journal of Hazardous Materials, 2012, 227-228:227-236.
[18] Faria P C C, Orfao J J M, Pereira M F R. Adsorption of anionic and cationic dyes on activated carbons with different surface chemistries[J]. Water Research, 2004, 38(8):2043-2052.
[19] Alvarez P M, Garcia-Araya J F, Beltran F J. The influence of various factors on aqueous ozone decomposition by granular activated carbons and the development of a mechanistic approach[J]. Carbon, 2006(44):3102-3112.
[20] Zhang Y Z, Sun B Y, Deng S H, et al. Methyl orange degradation by pulsed discharge in the presence of activated carbon fibers[J]. Chemical Engineering Journal, 2010, 159(1-3):47-52.
[21] Beltran F J, Pocostales J P, Alvarez P M, et al. Mechanism and kinetic considerations of TOC removal from the powdered activated carbon ozonation of diclofenac aqueous solutions[J]. Journal of Hazardous Materials, 2009, 169(1-3):532-538.
[22] Rivera-Utrilla J, Sanchez-Polo M, Mendez-Diaz J D, et al. Behavior of two different constituents of natural organic matter in the removal of sodium dodecylbenzenesulfonate by O₃ and O₃-based advanced oxidation processes[J]. Journal of Colloid and Interface Science, 2008, 325(2):432-439.
[23] Beltran F J, Garcia-Araya J F, Giraldez I. Gallic acid water ozonation using activated carbon[J]. Applied Catalysis B:Environmental, 2006, 63(3-4):249-259.
[24] Dehouli H, Chedeville O, Cagnon B, et al. Influences of pH temperature and activated carbon properties on the interaction ozone activated carbon for a wastewater treatment process[J]. Desalination, 2010, 254(1-3):12-16.
[25] de Oliveria T F, Chedeville O, Cagnon B, et al. Degradation of kinetics of DEP in water by ozone/activated carbon process:Influence of pH[J]. Desalination, 2011, 269(1-3):271-275.
[26] Xing L L, Xie Y B, Cao H B, et al. Activated carbon-enhanced ozonation of oxalate attributed to HO· oxidation in bulk solution and surface oxidation:Effects of the type and number of basic sites[J]. Chemical Engineering Journal, 2014, 245:71-79.
[27] Zhuang H F, Han H J, Hou B L, et al. Heterogeneous catalytic ozonation of biologically pretreated Lurgi coal gasification wastewater using sewage sludge based activated carbon supported manganese and ferric oxides as catalysts[J]. Bioresource Technology, 2014, 166:178-185.
[28] Gu L, Zhang X W, Lei L C. Degradation of aqueous p-Nitrophenol by ozonation integrated with activated carbon[J]. Industrial and Engineering Chemistry Research, 2008, 47(18):6809-6815.
[29] Gu L, Zhang X W, Lei L C, et al. Enhanced degradation of nitrophenol in ozonation integrated plasma modified activated carbon[J]. Microporous and Mesoporous Materials, 2009, 119(1-3):237-244.
[30] Liu Z Q, Ma J, Cui Y H, et al. Influence of different heat treatments on the surface properties and catalytic performance of carbon nanotube in ozonation[J]. Applied Catalysis B, 2010, 101(1-2):74-80.
[31] 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.
[32] 李璐, 封莉, 张立秋. 污泥基活性炭表面官能团对其催化臭氧氧化活性的影响[J]. 环境化学, 2014, 33(6):937-942.
[33] Nawrocki J. Catalytic ozonation in water:Controversies and questions[J]. Applied Catalysis B, 2013, 142-143:465-471.
[34] 王佳裕, 戴启洲, 鱼杰, 等. 活性炭催化臭氧氧化扑热息痛的机制研究[J]. 环境科学, 2014, 34(4):1402-1410.
[35] 曹永海, 李博, 余皓, 等. 纳米碳材料催化液相选择性氧化的研究进展[J]. 化工学报, 2014, 65(7):2645-2656.
[36] Beltran F J, Pocostales P, Alvarez P M, et al. Catalysts to improve the abatement of sulfamethoxazole and the resulting organic carbon in water during ozonation[J]. Applied Catalysis B, 2009, 92(3-4):262-270.
[37] Goncalves A, Orfao J J M, Pereira M F R. Ozonation of bezafibrate promoted by carbon materials[J]. Applied Catalysis B, 2013, 140-141:82-91.
[38] Chaichanawong J, Yamamoto T, Ohmori T. Enhancement effect of carbon adsorbent on ozonation of aqueous phenol[J]. Journal of Hazardous Materials, 2010, 175(1-3):673-679.
[39] Zhang S, Wang D, Quan X, et al. Multi-walled carbon nanotubes immobilized on zero-valent iron plates (Fe⁰-CNTs) for catalytic ozonation of methylene blue as model compound in a bubbling reactor[J]. Separation and Purification Technology, 2013, 116:351-359.
[40] 钱飞跃, 孙贤波, 刘勇弟, 等. 活性炭/臭氧氧化法连续处理印染废水生化出水的性能研究[J]. 水处理技术, 2014, 40(2):92-95.
[41] Restivo J, Orfao J J M, Pereira M F R, et al. Catalytic ozonation of organic micropollutants using carbon nanofibers supported on monoliths[J]. Chemical Engineering Journal, 2013, 230:115-123.
[42] Sui M H, Sheng L, Lu K X, et al. FeOOH catalytic ozonation of oxalic acid and the effect of phosphate binding on its catalytic activity[J]. Applied Catalysis B, 2010, 96(1-2):94-110.
[43] Fan X L, Restivo J, Orfao J J M, et al. The role of multiwalled carbon nanotubes (MWCNTs) in the catalytic ozonation of atrazine[J]. Chemical Engineering Journal, 2014, 241:66-76.
[44] Restivo J, Orfao J J M, Armenise S, et al. Catalytic ozonation of metolachlor under continuous operation using nanocarbon materials on a ceramic monoliths[J]. Journal of Hazardous Materials, 2012, 239-240:249-256.
[45] Alvarez P M, Pocostales J P, Beltran F J. Granular activated carbon promoted ozonation of a food-processing secondary effluent[J]. Journal of Hazardous Materials, 2011, 185(2-3):776-783.
[46] Alvarez P M, Beltran F J, Masa F J, et al. A comparison between catalytic ozonation and activated carbon adsorption/ozone- regeneration processes for wastewater treatment[J]. Applied Catalysis B, 2009, 92(3-4):393-400.
[47] Nawrocki J, Fijolek L. Catalytic ozonation——Effect of carbon contaminants on the process of ozone decomposition[J]. Applied Catalysis B, 2013, 142-143:307-314.
[48] Nawrocki J, Orfao J J M, Pereira M F R, et al. Catalytic ozonation of oxalic acid using carbon nanofibres on macrostructured supports[J]. Water Science & Technology, 2012, 65(10):1854-1862.
[49] Li L S, Zhu W P, Zhang P Y, et al. Comparison of AC/O₃-BAC and O₃-BAC processes for removing organic pollutants in secondary effluent[J]. Chemosphere, 2006, 62(9):1514-1522.
[50] Qian F Y, Sun X B, Liu Y D. Removal characteristics of organics in biotreated textile wastewater reclamation by a stepwise coagulation and intermediate GAC/O₃ oxidation process[J]. Chemical Engineering Journal, 2013, 214(2):112-118.
[51] Qian F Y, Sun X B, Liu Y D, et al. Removal and transformation of effluent organic matter (EfOM) in biotreated textile wastewater by GAC/O₃ pre-oxidation and enhanced coagulation[J]. Environmental Technology, 2013, 34(12):1513-1520.
[52] Corneal L M, Baumann M, Masten S J, et al. Mn oxide coated catalytic membranes for a hybrid ozonation-membrane filtration:Membrane microstructural characterization[J]. Jorunal of Membrane Science, 2011, 369(1-2):182-187.
[53] Fan X J, Wang L Y, Zhang X H, et al. Performance of an integrated process combining ozonation with ceramic membrane ultra-filtration for advanced treatment of drinking water[J]. Desalination, 2014, 335(1):47-54.