Excellent activity and selectivity of Pd/ZSM-5 catalyst in the selective catalytic reduction of NOx by H2.

Superior de-NOx activity and N2 selectivity of the Pd/ZSM-5 catalyst was observed at low temperature (<200 °C) for the selective catalytic reduction of NOx by H2 (H2-SCR). Various Pd/ZSM-5 catalysts were prepared by calcinating at different temperatures (e.g., 500 °C, 650 °C, 750 °C, and 850 °C) and treated at reductive conditions before the H2-SCR reaction was performed. Among the prepared catalysts, the one prepared at the calcination temperature at 750 °C resulted in 96.7% NOx conversion and 96.8% N2 selectivity at 150 °C. Based on the H2-O2 reaction, the higher activity of the Pd/ZSM-5 catalyst calcined at 750 °C was attributed to its superior H2 activation ability for the H2-SCR reaction. The combined X-ray diffraction (XRD), temperature-programmed hydride decomposition (TPHD), and transmission electron microscopy (TEM) results revealed that highly dispersed Pd particles were generated on the catalyst calcined at 750 °C, while large Pd agglomerates were formed on the one calcined at 500 °C. It can be concluded that the catalytic activity of Pd/ZSM-5 improves by optimizing the calcination temperature, resulting in high Pd dispersion. Moreover, the Pd catalyst calcined at 750 °C showed high resistance to CO, maintaining >94% NOx conversion at 175 °C under 1000 ppm CO in the feed gas. Therefore, the catalyst calcined at 750 °C can be potentially used for industrial applications because of its simple preparation method and high resistance to CO.

Effects of thermal aging on the electronic and structural properties of Pt-Pd and toluene oxidation activity.

Catalytic oxidation is a feasible method for remediating volatile organic compounds (VOCs), due to its lower energy consumption and mineralization of VOCs into H2O and CO2. Noble metal-based catalysts are preferred for the catalytic oxidation of VOCs because of their superior activity, but they are usually deactivated by thermal aging which sinters the metal particles. Here, we report that Pt-Pd/Al2O3 thermally aged at 700-900 °C in air showed enhanced catalytic activity for toluene oxidation in humid conditions. There were electronic and structural changes in the thermally aged Pt-Pd/Al2O3, as confirmed by numerous analyses. Both Pt and Pd existed in a metallic rather than oxidized state without additional reduction steps. The noble metal particles were assembled to form Pt-Pd alloy, in the form of isolated Pd atoms surrounded by Pt atoms. This specific alloy structure was found to be crucial to the observed enhancement in catalytic toluene oxidation at low temperature.

High-Throughput NOx Removal by Two-Stage Plasma Honeycomb Monolith Catalyst.

A two-stage plasma catalyst system for high-throughput NOx removal was investigated. Herein, the plasma stage involved the large-volume plasma discharge of humidified gas and was carried out in a sandwich-type honeycomb monolith reactor consisting of a commercial honeycomb catalyst (50 mm high; 93 mm in diameter) located between two parallel perforated disks that formed the electrodes. The results demonstrated that, in the plasma stage, the reduction of NOx did not occur at room temperature; instead, NO was only oxidized to NO2 and n-heptane to oxygenated hydrocarbons. The oxidation of NO and n-heptane in the honeycomb plasma discharge state was largely affected by the humidity of the feed gas. Furthermore, the oxidation of NO to NO2 occurs preferably to that of n-heptane with a tendency of the NO oxidation to decrease with increasing feed gas humidity. The reason is that the generation of O3 decreases as the amount of water vapor in the feed gas increases. Compared to the catalyst alone, the two-stage plasma catalyst system increased NOx removal by 29% at a temperature of 200 °C and an energy density of 25 J/L.

Effective practical removal of acetaldehyde by a sandwich-type plasma-in-honeycomb reactor under surrounding ambient conditions.

The effective removal of acetaldehyde by humidified air plasma was investigated with a high throughput of contaminated gas in a sandwiched honeycomb catalyst reactor at surrounding ambient temperature. Here, acetaldehyde at the level of a few ppm was successfully oxidized by the honeycomb plasma discharge despite the harsh condition of large water content in the feed gas. The conversion rate of acetaldehyde increased significantly with the presence of catalysts coating on the surface channels. The increased conversion rate was also obtained with a high specific energy input (SEI) and total flow rate. Interestingly, the conversion changed negligibly under the acetaldehyde concentration range from 5 to 20 ppm. However, the conversion rate decreased toward increased water amount in the feed gas. Notably, about 60% of acetaldehyde in the feed was oxidized under SEI of 40 J/L at water amounts ≤ 2.5%, approximately 0.5 g/kWh for acetaldehyde removal. Also, the plasma-catalyst reaction was superior to the thermal reactive catalyst for acetaldehyde removal in airborne pollutants. In comparison with other plasma-catalyst sources for acetaldehyde removal, the energy efficiency under the condition is comparable. Moreover, the honeycomb plasma discharge features high throughput, avoiding pressure drop, and straightforward reactor configuration, suggesting potential practical applications.

Dependence of humidified air plasma discharge performance in commercial honeycomb monoliths on the configuration and key parameters of the reactor.

The effect of the reactor configuration and several key parameters such as the gas temperature, humidity, and flow rate on the corona discharge plasma in honeycomb monoliths was investigated. The AC corona discharge-based plasma reactor consisted of two parallel electrodes (perforated disk/wire-mesh) placed at both ends of the honeycomb monolith. Although the wire-mesh electrode offers increased sharpness, the perforated disk electrode, where the corona discharge started at the sharp edges of the holes, produced more discharge power because of the larger effective electrode area. Loading a small amount of metal onto the monolith was found to increase the discharge power significantly. Coating the monolith with a zeolite such as ZSM-5 (Si/Al: 23.9) led to a decrease in the discharge power because of its hydrophobic nature and large surface area. The result also revealed that the operating temperature, the humidity of the feed gas, and the gas velocity were key factors affecting the discharge performance. The discharge power was inversely proportional to the temperature. On the other hand, the use of a high-velocity feed gas with high water vapor content was found to be particularly advantageous for obtaining high discharge power.

Nonthermal plasma in practical-scale honeycomb catalysts for the removal of toluene.

Nonthermal plasma combined with a practical-scale honeycomb catalyst of 5.0 cm in height and 9.3 cm in diameter was investigated for the removal of toluene. The creation of plasma in the honeycomb catalyst greatly depended on the humidity of the feed gas and the presence of metals on the honeycomb surface. Compared to the bare ceramic honeycomb, the metal-loaded one gave higher toluene removal efficiency because the decomposition of toluene by the plasma-generated reactive species occurred not only homogeneously in the gas phase but also heterogeneously on the catalyst surface. The present plasma-catalytic reactor was able to successfully remove about 80% of dilute toluene (15 ppm in air) at a large flow rate of 60 L/min with a specific energy input of 58 J/L. The honeycomb-based plasma-catalytic reactor system is promising for practical applications since it can overcome such problems as high-pressure drop and difficulty in scale-up encountered in packed-bed reactors.

Urealess NOx Reduction by Carbon Monoxide in Simulated Lean-Burn Exhausts.

The lean NOx aftertreatment is one of the major barriers to the widespread adoption of advanced combustion powertrains for the reduction of both greenhouse gases and toxic exhausts. Urea/SCR, selective catalytic reduction of NOx by NH3 generated through urea decomposition, is commonly regarded as the best way to reduce NOx in low temperature lean exhaust. However, the urea/SCR system has inherent drawbacks, i.e., periodic refill of the aqueous urea solution and a complicated hardware system. Here, we demonstrated a state-of-the-art catalyst that is extremely selective and efficient for reducing NOx, primarily with the most abundant reductant, CO, particularly in the presence of O2 (>5%) at low temperature. Under temperatures lower than 250 °C, IrRu/Al2O3 catalysts achieved higher NOx conversion by CO only than a commercial Cu-based urea/SCR catalyst employing NH3 as a primary reductant. Furthermore, the IrRu catalyst revealed high thermal stability and SO2 tolerance, which are very important factors for real world applications.

Combination of photocatalysis and HC/SCR for improved activity and durability of DeNOx catalysts.

A photocatalytic HC/SCR system has been developed and its high deNOx performance (54.0-98.6% NOx conversion) at low temperatures (150-250 °C) demonstrated by using a representative diesel fuel hydrocarbon (dodecane) as the reductant over a hybrid SCR system of a photocatalytic reactor (PCR) and a dual-bed HC/SCR reactor. The PCR generates highly active oxidants such as O3 and NO2 from O2 and NO in the feed stream, followed by the subsequent formation of highly efficient reductants such as oxygenated hydrocarbon (OHC), NH3, and organo-nitrogen compounds. These reductants are the key components for enhancing the low temperature deNOx performance of the dual-bed HC/SCR system containing Ag/Al2O3 and CuCoY in the front and rear bed of the reactor, respectively. The OHCs are particularly effective for both NOx reduction and NH3 formation over the Ag/Al2O3 catalyst, while NH3 and organo-nitrogen compounds are effective for NOx reduction over the CuCoY catalyst. The hybrid HC/SCR system assisted by photocatalysis has shown an overall deNOx performance comparable to that of the NH3/SCR, demonstrating its potential as a promising alternative to the current urea/SCR and LNT technologies. Superior durability of HC/SCR catalysts against coking by HCs has also been demonstrated by a PCR-assisted regeneration scheme for deactivating catalysts.