Adsorption of n-Butyl Mercaptan on Activated carbon in the absence of oxygen

Vasileios M. Matsis, Helen P. Grigoropoulou Laboratory of Chemical Process Engineering, School of Chemical Engineering, National Technical University of Athens, Zografou Campus, GR-15780 Zografos, Athens, Greece; tel. +30 2107723222, fax: +30 2107723155, e-mail: lenag@chemeng.ntua.gr Drinking water has been found to contain small amounts of a large number of synthetic organic compounds such as phenols, pesticides, nitro compounds and organic sulfur compounds. Additionally freshwater cyanobacteria and algae are responsible for the formation of a wide spectrum of different odorous compounds that are frequently observed in natural waters and are the causes for consumer complaints. Among them, Microcystis flosaquae emits n-butyl mercaptan (C4H9SH) causing off-flavour episodes in water bodies such as lakes which serve for recreation and as an operational water reservoir supplying potable water. Activated carbons, because of their high surface area, highly microporous structure, and a high reactivity of their surface, have been considered to be potential adsorbents for the removal of organic compounds from water. However to propose a single mechanism is not an easy task so that the adsorption of organics from aqueous solutions by activated carbons has been interpreted differently by different workers. In this study n-butyl mercaptan adsorption process onto two brands of commercial activated carbons (granular activated carbon and powder activated carbon) at ambient, anaerobic conditions and neutral pH is investigated. Physical and chemical properties of the as-received and exhausted carbon are evaluated in order to clarify the catalytic effects of transition metals (Fe, Cu present in the material originally or after impregnation) and the contribution of physical adsorption and chemisorption. N-butyl mercaptan in aqueous solution is expected to dissociate to mercaptide ion (C4H9S-) and H+ ions. The pKa for this process is reported to be 10.49 (28oC) which might suggest that at neutral pH solution there is no considerable dissociation of the target compound. The negative result of n-butyl mercaptan low ionization is compensated by the attractive interactions with carbon surface (pH at the point of zero charge is 7.6) and it is likely that even though pH is low for its dissociation, the buffer capacity of carbon keeps mercaptan dissociation at a level favourable for its adsorption in the dissociated form which promotes the whole process. The proposed mechanism which explains the adsorption of n-butyl mercaptan on activated carbon includes: i) the presence of quinone groups which accommodate mercaptan molecules in a physical adsorption process and ii) the reaction of the mercaptide ion with iron and/or copper metals present in the carbon structure via an electron transfer mechanism to give thiyl radicals, dimerization of which leads to disulfide product.

The functional group characterization of granular activated carbon (basic carbon) and powdered activated carbon (balanced acidic and basic groups) supports the experimental findings concerning the availability of surface area to accommodate more mercaptide anions.