Kinetic study of the SO2 oxidation reaction over a Pt/Al2O3 diesel oxidation catalyst

Tayebeh Hamzehlouyan1, Chaitanya S. Sampara1 and William S. Epling1* 1 University of Houston, Houston, TX 77204 (United States) *wsepling@central.uh.edu

A reaction mechanism was proposed for the catalytic oxidation of SO2 on Pt/Al2O3 and a kinetic model was developed based on this mechanism and our findings of the reaction orders. Some parameters were identified in the literature, but others had to be fit to match the experimental data. The relative importance of each step in the reaction mechanism was studied using the developed model. Activity recovery through sulfate decomposition and sulfur release was evaluated using temperature programmed desorption and oxidation. The effect of sulfur on NO oxidation over the Pt/Al2O3 catalyst was also studied in a separate set of experiments. Table 1. Reaction orders and activation energy for SO2 oxidation on Pt/Al2O3 O2 Order SO3 Order Ea,app(kJ/mol) Feed condition SO2 Order without SO3 in the feed 1.260.37 -0.250.16 596 with SO3 in the feed 0.880.20 -0.240.13 -0.420.33 9516

ln(Rate)

Introduction Sulfur oxides in diesel engine exhaust interact with the aftertreatment catalysts and deactivate them through sulfur poisoning. In order to understand deactivation behavior of diesel oxidation catalysts (DOCs), as well as the formation of S species that can poison downstream catalyst systems, i.e. selective catalytic reduction (SCR) and lean NOx trap (LNT) catalysts, the SO2 oxidation kinetics and its effect on the oxidation activity of the DOC needs to be understood. A number of studies have been performed focused on sulfur interactions with DOCs and its effect on the NO oxidation activity. SO2 oxidation kinetics on Pt/Al2O3 has also been discussed in a few studies [1-3]. However, no kinetic model has been proposed that accurately describes the SO2 oxidation activity of Pt/Al2O3. In this work, an SO2 oxidation experimental study was performed and a kinetic model was developed and verified with the experimental data in order to properly describe the SO2 oxidation reaction. The effect of sulfur on the NO oxidation activity of this catalyst was also investigated. Materials and Methods A monolith supported Pt/Al2O3 (50 g/ft3 Pt) catalyst was used in the experiments. The sample was inserted into a quartz tube reactor which was placed in a temperature controlled furnace. For temperature measurements, three thermocouples were inserted at different locations inside the reactor. Mass flow controllers were used to meter the gas flow rates to achieve the desired gas concentrations. A separate reactor upstream was used to generate SO3 when SO3 was required in the feed for the kinetic and deactivation studies. For all experiments, the outlet gas concentrations were measured using a MKS MultiGas 2000 FT-IR analyzer. The SO2 oxidation rate dependencies on the SO2, O2 and SO3 concentrations as well as the activation energy were determined experimentally. All of the kinetic experiments were performed in a differential reactor regime to minimize effect of temperature gradients and to avoid mass transfer limitations due to the concentration gradients. Results and Discussion The first set of kinetic experiments was done with no SO3 in the feed. Reaction orders of 1.26 and -0.25 were determined for SO2 and O2, respectively, and an apparent activation energy of 59 kJ/mol was obtained. In order to investigate the effect of SO3, another set of experiments was performed in the presence of SO3 in the feed. Reaction orders of 0.88 and -0.24 were observed for SO2 and O2, respectively, and the SO3 reaction order was found to be -0.45, demonstrating its inhibition effect. An activation energy of 95 kJ/mol was determined in this case. The overall findings are listed in Table 1.

SO2 Dependency 1.0 2.0 -15.7 -16.0 -16.3 -16.6 -16.9 -17.2 -17.5 -17.8

SO3 Dependency 3.0 4.0

O2 Dependency 5.0 6.0

SO3 Order: -0.420.34

O2 Order: -0.240.13 SO2 Order: 0.880.20

ln(Concentration) Figure 1. SO2 oxidation rate dependence on SO2, O2 and SO3 concentrations at 274 C
Significance Sulfur poisoning is one of the major causes of catalyst deactivation in vehicle aftertreatment systems. The kinetics of the SO2 oxidation reaction on a model DOC were determined. The results allow prediction of S species concentrations that will impact downstream catalyst components. References 1. Benzinger W., Wenka A. and Dittmeyer R., Appl. Catal. A: General 397, 209 (2011). 2. Dawody J., Skoglundh, M.and Fridell E., Jour. Molec. Catal. A: Chemical 209, 215 (2004). 3. Xue E., Seshan K.and Ross J.R.H., Appl. Catal. B: Environmental 11, 65 (1996).