Abstract A Sequencing Batch Reactor (SBR) was combined with heterogeneous photocatalysis (TiO2/UV) as a tertiary treatment for a pencil manufacturer's wastewater. The SBR removed almost all Chemical Oxygen Demand (COD) from the wastewater, although color was barely removed. Photocatalysis was optimized using a factorial design. Final COD, Dissolved Organic Carbon (DOC), and color removals were 95%, 80%, and 93%, respectively. Treated wastewater showed no ecotoxicity towards Lactuca sativa. Color removal kinetics (photocatalysis) followed a pseudo-first order model. The SBR + AOP (Advanced Oxidation Process, TiO2/UV) combination was a feasibility choice for removing both COD and color from this wastewater.

Results obtained in a pilot-scale unit designed for COD removal and p-TBC (p-tert-butylcatechol) recovery from a butadiene washing stream (pH 14, 200,000 mg COD L-1, highly toxic) at a petrochemical industry are presented. By adding H3PO4, phase separation is achieved and p-TBC is successfully recovered (88 g L-1 of washing stream). Information (time for phase separation and organic phase characterization) was gathered for designing a future industrial unit. The estimated heat generation rate was 990 kJ min-1 and 15 min were enough to promote phase separation for a liquid column of approximately 1.15 m.

The photocatalytic degradation of phenol in aqueous suspensions of TiO2 under different salt concentrations in an annular reactor has been investigated. In all cases, complete removal of phenol and mineralization degrees above 90% were achieved. The reactor operational parameters were optimized and its hydrodynamics characterized in order to couple mass balance equations with kinetic ones. The photodegradation of the organics followed a Langmuir-Hinshelwood-Hougen-Watson lumped kinetics. From GC/MS analyses, several intermediates formed during oxidation have been identified. The main ones were catechol, hydroquinone, and 3-phenyl-2-propenal, in this order. The formation of negligible concentrations of 4-chlorophenol was observed only in high salinity medium. Acute toxicity was determined by using Artemia sp. as the test organism, which indicated that intermediate products were all less toxic than phenol and a significant abatement of the overall toxicity was accomplished, regardless of the salt concentration.

The photocatalytic activity of bulk and supported TiO2 catalysts were tested using formic acid as a probe molecule. The supported catalysts tested were prepared by impregnation using aluminum oxide (Al2O3) as the support and the bulk catalysts by precipitation, both in sol-gel systems. For purposes of comparison, a photocatalyst supplied by DEGUSSA (P25) was also tested. The photolysis rate was found to be less significant than the photocatalytic rate. The Langmuir-Hinshelwood model was adopted and its constants were estimated and used to compare the various catalysts. The supported catalysts showed no significant activity, in spite of their high specific surface area. The bulk catalysts tested showed the highest photocatalytic rates. The adsorption constants determined experimentally were different from the ones estimated based on the kinetic experiments. The parameter estimation procedures tested were used to clarify this issue.

Photocatalysis has been used as tertiary treatment for petroleum refinery wastewaters to comply with the regulatory discharge limits and to oxidize persistent compounds that had not been oxidized in the biological treatment. The wastewater is generated by the refinery and directly discharged into the Guanabara Bay (Rio de Janeiro). Although BOD removal is high, a residual and persistent COD, besides a somewhat high phenol content remains. Three photocatalysts were tested - TiO2 (Aldrich), ZnO (Aldrich), and TiO2 (P25, Degussa) - the third being the most active. The optimized conditions obtained with an experimental design were 3.0 g L-1 TiO2 and pH 6.3. The use of hydrogen peroxide (H2O2) showed no beneficial effect. Removal of 93% of phenols, 63% of dissolved organic carbon (DOC), and more than 50% of oil and grease (OG) were achieved in the photocatalytic process, improving the quality of the treated wastewater.