Ozonation of naphthalenesulphonic acid in the aqueous phase in the presence of basic activated carbons

Abstract

The present study aimed to explore the possibility of increasing the purification efficacy of ozone in the removal of high-toxicity contaminants by using carbons of basic character and to analyze the mechanism involved in this process. These carbons were prepared by treating a commercial activated carbon (Witco, W) with ammonia (W-A), ammonium carbonate (W-C), or urea (W-U), under high pressure and temperature. The ammonia and carbonate treatments slightly increased the mesoporosity and, to a greater degree, the macroporosity of carbon W, whereas the urea treatment produced an increase in the porosity across the whole range of pore sizes. In addition, treatment of the activated carbon with these nitrogenating agents produced a marked change in the chemical nature of its surface. Thus, according to the pH of the point of zero charge (pHPZC) values obtained for each sample, carbon W was neutral (pHPZC = 7.12), but the treated carbons were basic, especially carbon W-U (pHPZC = 8.85). This basicity results from an increased concentration of basic oxygenated and nitrogenated surface functional groups, as confirmed by the results of elemental and XPS analyses. An increase in the degradation of 1,3,6-naphthalenetrisulfonic acid was observed when the activated carbon samples were added to the system. This degradation was especially enhanced in the presence of carbon W-U. The increased NTS degradation rate in the presence of the activated carbon is due to an increased concentration of highly reactive radicals in the system. When the catalytic activity of the activated carbon samples was related to their chemical and textural characteristics, it was found that: (i) The catalytic activity increased with an increase in the surface basicity. Interestingly, in the sample with greatest catalytic activity in NTS ozonation, carbon W-U, most of the nitrogenated surface groups introduced were pyrrol groups. These groups increase the electronic density of the basal plane of the activated carbon, thereby enhancing the reduction of ozone on the surface and the generation of highly reactive radicals in the system. (ii) The greater catalytic activity of carbon W-U may also be partly related to its greater surface area and higher volume of mesopores and macropores; these large pores facilitate access of the ozone to the surface active centers of the carbon, increasing its catalytic activity. The presence of the activated carbon samples during NTS ozonation also favored the removal of total organic carbon present in the solution, due to (a) transformation of organic matter into CO2 through the generation of highly reactive species catalyzed by the presence of the activated carbons (catalytic contribution) and (b) adsorption of NTS oxidation byproducts on the activated carbon (adsorptive contribution). The results obtained show that activated carbons treated with nitrogenating agents are very promising catalysts for application in the ozonation of aromatic compounds.