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Frontiers of Environmental Science & Engineering

Front. Environ. Sci. Eng.    2018, Vol. 12 Issue (1) : 6
Significant enhancement in catalytic ozonation efficacy: From granular to super-fine powdered activated carbon
Tianyi Chen1, Wancong Gu1, Gen Li2, Qiuying Wang1, Peng Liang1, Xiaoyuan Zhang1(), Xia Huang1()
1. State Key Joint Laboratory of Environment Simulation and Pollution Control, School of Environment, Tsinghua University, Beijing 100084, China
2. Department of Urban Construction, Wuhan University of Science and Technology, Wuhan 400065, China
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SPAC significantly enhanced the efficacy of catalytic ozonation.

Large external surface reduced the diffusion resistance.

Surface reaction was dominant for SPAC-based catalytic ozonation.

Simple ball milling brought favorable material characteristics for catalysis.

In this study, super-fine powdered activated carbon (SPAC) has been proposed and investigated as a novel catalyst for the catalytic ozonation of oxalate for the first time. SPAC was prepared from commercial granular activated carbon (GAC) by ball milling. SPAC exhibited high external surface area with a far greater member of meso- and macropores (563% increase in volume). The catalytic performances of activated carbons (ACs) of 8 sizes were compared and the rate constant for pseudo first-order total organic carbon removal increased from 0.012 min-1 to 0.568 min-1 (47-fold increase) with the decrease in size of AC from 20 to 40 mesh (863 mm) to SPAC (~1.0 mm). Furthermore, the diffusion resistance of SPAC decreased 17-fold compared with GAC. The ratio of oxalate degradation by surface reaction increased by 57%. The rate of transformation of ozone to radicals by SPAC was 330 times that of GAC. The results suggest that a series of changes stimulated by ball milling, including a larger ratio of external surface area, less diffusion resistance, significant surface reaction and potential oxidized surface all contributed to enhancing catalytic ozonation performance. This study demonstrated that SPAC is a simple and effective catalyst for enhancing catalytic ozonation efficacy.

Keywords Super-fine activated carbon      Catalytic ozonation      External surface area      Surface reaction      Hydroxyl radical     
This article is part of themed collection: Advanced Treatment Technology for Industrial Wastewaters (Responsible Editors: Junfeng Niu & Hongbin Cao)
Corresponding Author(s): Xiaoyuan Zhang,Xia Huang   
Issue Date: 05 January 2018
 Cite this article:   
Tianyi Chen,Wancong Gu,Gen Li, et al. Significant enhancement in catalytic ozonation efficacy: From granular to super-fine powdered activated carbon[J]. Front. Environ. Sci. Eng., 2018, 12(1): 6.
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Tianyi Chen
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Peng Liang
Xiaoyuan Zhang
Xia Huang
Fig.1  (a) TOC removal by the catalyticozonation of oxalate using SPAC and GAC as catalysts over time and(b) pseudo first order rate constants at different SPAC and GAC doses.The dotted lines are kinetic fitting results. The numbers after SPACand GAC are doses with a unit of g/L. Experimental conditions: oxalateconcentration: 100 mg/L, O3 concentration:180–200 mg/L, and flow rate: 1.0 L/min. The pH was not buffered
Fig.2  (a) TOC removal by the catalyticozonation of oxalate using AC catalysts with various sizes and (b)the relationship between pseudo first-order rate constants and carbonradius. The dotted lines in (a) and (b) are kinetics fitting resultsand fitting trend. Experimental conditions: oxalate concentration:100 mg/L, O3 concentration: 180–200 mg/L,flow rate: 1.0 L/min, carbon dose: 2 g/L. The pH was not buffered
Fig.3  (a) Adsorption of oxalateby SPAC and GAC with and without sonication; (b) pseudo second-orderrate constants; (c) initial adsorption rates; (d) adsorbed oxalateat equilibrium. Experimental conditions: oxalate concentration: 100mg/L, carbon dose: 2 g/L. The pH was not buffered
Sample SBET (m2/g) Sa, b)micro
Va, b)micro
GAC 456.9±1.9 208.5 248.4 0.0954 0.0316 0.127
100–160 mesh AC 476.2±2.6 220.7 255.4 0.0948 0.1112 0.206
SPAC 745.3±6.1 24.4 720.9 0.0048 0.2102 0.215
Tab.1  Surface area characterizationsof GAC, 100–160 mesh AC and SPAC
Fig.4  Oxalate removal by ozonealone (green area), ozone+ carbon+ t-butanol (yellow, orange area)and ozone+ carbon (line) in the case of (a) GAC and (b) SPAC. Experimentalconditions: oxalate concentration (OA): 100 mg/L, t-butanol: 1 mM,O3 concentration: 180–200 mg/L, flowrate: 1.0 L/min, carbon dose: 2 g/L. The pH was not buffered
Fig.5  Rct plots for ozone alone, and ozone with GACand SPAC at various carbon doses. The slope of the fitting line representsthe Rct value.Detailed parameters are shown in Table S1. Experimental conditions: pCBA concentration: 2 mM, t-butanol concentration: 320 mM. The pH was not buffered
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