Facile Approach to the Fabrication of Highly Selective CuCl-Impregnated θ-Al2O3 Adsorbent for Enhanced CO Performance.

We have developed a facile and sustainable method to produce a novel θ-Al2O3-supported CuCl adsorbent through impregnation methods using CuCl2 as the precursor. In an easy two-step process, θ-Al2O3 was impregnated with a known concentration of CuCl2 solutions, and the precursor was calcined to prepare CuCl oversupport. The developed novel θ-Al2O3-supported CuCl adsorbent was compared with an adsorbent prepared through the conventional method using CuCl salt. The adsorbents were characterized via X-ray diffraction (XRD), thermal gravimetric analysis (TGA) and temperature-programmed reduction (H2-TPR). Overall, the adsorbent indicates a high CO adsorption capacity, high CO/CO2 and CO/N2 selectivity, and remarkable reusability performance. This process is operated at ambient temperature, which minimizes operation costs in CO separation processes. In addition, these results indicate that the systematic evaluation of alumina-supported CuCl adsorbent can provide significant insight for designing a realistic PSA process for selective CO separation processes.

Simple physical mixing of zeolite prevents sulfur deactivation of vanadia catalysts for NOx removal.

NOx abatement has been an indispensable part of environmental catalysis for decades. Selective catalytic reduction with ammonia using V2O5/TiO2 is an important technology for removing NOx emitted from industrial facilities. However, it has been a huge challenge for the catalyst to operate at low temperatures, because ammonium bisulfate (ABS) forms and causes deactivation by blocking the pores of the catalyst. Here, we report that physically mixed H-Y zeolite effectively protects vanadium active sites by trapping ABS in micropores. The mixed catalysts operate stably at a low temperature of 220 °C, which is below the dew point of ABS. The sulfur resistance of this system is fully maintained during repeated aging/regeneration cycles because the trapped ABS easily decomposes at 350 °C. Further investigations reveal that the pore structure and the amount of framework Al determined the trapping ability of various zeolites.

Hydrogenation of CO to methane over mesoporous nickel-iron-alumina xerogel nano-catalysts.

Mesoporous nickel-iron-alumina xerogel ((40-x)Ni(x)FeAX) nano-catalysts with different iron content (x = 0, 2.5, 5, 7.5, and 10) were prepared by a single-step sol-gel method for use in the methane production from carbon monoxide and hydrogen. The effect of iron content on the catalytic performance of (40-x)Ni(x)FeAX catalysts was investigated. In the methanation reaction, yield for CH4 decreased in the order of 35Ni5FeAX > 32.5Ni7.5FeAX > 30Ni10FeAX > 37.5Ni2.5FeAX > 40Ni0FeAX. This indicated that optimal iron content of mesoporous nickel-iron-alumina xerogel nano-catalyst was required for maximum production of CH4 in the methanation reaction. Experimental results revealed that optimal CO dissociation energy and large H2 adsorption ability of the catalyst were favorable for methane production. Among the catalysts tested, 35Ni5FeAX catalyst, which retained the most optimal CO dissociation energy and the largest H2 adsorption ability, exhibited the best catalytic performance in terms of conversion of CO and yield for CH4 in the methanation reaction. CO dissociation energy and H2 adsorption ability of the catalyst played a key role in determining the catalytic performance of (40-x)Ni(x)FeAX in the methanation reaction.

Polarity effect of pulsed corona discharge for the oxidation of gaseous elemental mercury.

The effect of polarity on the oxidation of Hg(0) was examined in the presence of O(2) via a pulsed corona discharge (PCD). The experimental result showed no difference in the energy yield of Hg(0) oxidation at both positive and negative PCDs (∼8 µg Hg Wh(-1) at following conditions: total flow rate=2 L min(-1) (Hg(0)=50 µg Nm(-3), O(2)=10%, and N(2) balance), temperature=150°C, and specific energy density=5-15 Wh Nm(-3)). This suggests that the positive PCD process used to control gaseous air pollutants may play an essential key role in Hg(0) oxidation because it consumes enough energy (∼15 Wh Nm(-3)) but an electrical precipitator could not because it consumes less energy (∼0.3 Wh Nm(-3)) to oxidize Hg(0).

Removal mechanism of elemental mercury by using non-thermal plasma.

The removal mechanism of elementary mercury (Hg(0)) by non-thermal plasma (NTP) has been investigated, where dielectric barrier discharge and O(3) injection methods as oxidation techniques are employed, together with the analysis of mercury species deposited on the reactor surface using temperature-programmed desorption and dissociation (TPDD) and scanning electron microscopy-energy dispersive spectroscopy. The removal of Hg(0) by NTP is found to be time-dependent and proceed through three domains; the Hg(0) concentration just slightly decreases as soon as NTP is initiated and then becomes constant for several minutes (Region 1), thereafter starts to decrease rapidly for 1h (Region 2) and, after passing fall-off region, very slowly decreases for about 4h (Region 3). The deposited mercury species on the reactor surface were conglomerated like islands, rather than dispersed uniformly, and their ratio of Hg(0) to O composition is observed to be 1:2. Additionally, the new peak in TPDD spectra observed in the region of 260-380°C is proposed as HgO(3). These results lead us to conclude that the deposited mercury species by NTP have extra O atoms to oxidize the adsorbed Hg(0), resulting in the acceleration of removal rate as the oxidation of Hg(0) proceeds.

Insight into the unique oxidation chemistry of elemental mercury by chlorine-containing species: experiment and simulation.

This work investigated the oxidation chemistry of elemental mercury (Hg(0)) by chlorine-containing species produced indirectly through the gas-to-solid phase reaction between NO(x) gases and NaClO(2) powder (NaClO(2)(s)), where both experiment and simulation results were compared to clarify which species are responsible for the oxidation of Hg(0). At first, we introduced 30 ppm of NO(2) into the pack-bed reactor containing NaClO(2)(s) to produce OClO species and then injected NO and Hg(0) (260 microg/Nm(3)) to Mixer, where the concentration of NO was varied up to 180 ppm and the reaction temperature was set to 130 degrees C. We observed for the first time that the degree of Hg(0) oxidation is completely controlled by the introduced concentration of NO: for example, the oxidation efficiency of Hg(0) is drastically increased to become 100% at near 7 ppm NO, but further increasing NO concentration results in the oxidation efficiency of Hg(0) being gradually decreased. The simulation results indicated that such a propensity of Hg(0) oxidation efficiency to NO concentration can be attributed to the NO concentration-dependent Cl, ClO, and Cl(2) formation which plays a critical role in the oxidation of Hg(0).

Reaction pathways of NO oxidation by sodium chlorite powder.

NO oxidation is an important prerequisite step to assist selective catalytic reduction at low temperatures (< 250 degrees C). If sodium chlorite powder (NaClO2(s)) can oxidize NO to NO2, the injection of NaClO2(s) can be simply adapted to NO oxidation. Therefore, we explored the reaction pathways of NO oxidation by NaClO2(s). Known concentrations of NO and NO2 in N2 balance were injected into packed-bed reactor containing NaClO2(s) at 130 degreesC. NaClO2(s) oxidized NO to NO2 which reacts again with NaClO2(s) to produce OClO. Comparison of experimental data with simulation results demonstrates that each NO2 molecule removed by the reaction with NaClO2(s) generated one OClO molecule, which also oxidized NO to NO2 with the production of ClNO and ClNO2. Using these results, we conclude that the oxidation of NO by NaClO2(s) occurred by two pathways. One is through the direct reaction of NO with NaClO(s). The other is through both the reaction of NO with OlCO produced by the reaction of NO2 with NaClO2(s) and the reaction of NO with ClO produced by the reaction of NO with OClO.

Effect of hydrogen generated by dielectric barrier discharge of NH3 on selective non-catalytic reduction process.

Plasma-assisted selective non-catalytic reduction (SNCR) has been investigated to clarify which species generated by the plasma play a crucial role in NO reduction. We find that the presence of O(2) is indispensable and only H(2) is observed to be a stable product by dielectric barrier discharge (DBD) of NH(3). As the extent of NH(3) decomposition by DBD increases, the commencement temperature of SNCR processes is lowered and the working temperature window is widened. This propensity may be attributed to the chemical reaction of H(2) with O(2) to generate OH and H radicals which make it possible to yield NH(2) radicals even at low temperature.

Oxidation of elemental mercury using atmospheric pressure non-thermal plasma.

The oxidation of gas phase elemental mercury (Hg0) by atmospheric pressure non-thermal plasma has been investigated at room temperature, employing both dielectric barrier discharge (DBD) of the gas mixture of Hg0 and injection of ozone (O3) into the gas mixture of Hg0. Results have shown that the oxidative efficiencies of Hg0 by DBD and the injection of O3 are 59% and 93%, respectively, with energy consumption of 23.7 J L(-1). This combined approach has indicated that O3 plays a decisive role in the oxidation of gas phase Hg0. Also the oxidation of Hg0 by injecting O3 into the gas mixture of Hg0 proceeds with better efficiency than DBD of the gas mixture of Hg0. These results have been explained by the incorporation of the competitive reaction pathways between the formation of HgO by O3 and the decomposition of HgO back to Hg0 in the plasma environment.

Influence of HCl on oxidation of gaseous elemental mercury by dielectric barrier discharge process.

The influence of HCl on the oxidation of gaseous elemental mercury (Hg0) has been investigated using a dielectric barrier discharge (DBD) plasma process, where the temperature of the plasma reactor and the composition of gas mixtures of HCl, H2O, NO, and O2 in N2 balance have been varied. We observe that Cl atoms and Cl2 molecules, created by the DBD process, play important roles in the oxidation of Hg0 to HgCl2. The addition of H2O to the gas mixture of HCl in N2 accelerates the oxidation of Hg0, although no appreciable effect of H2O alone on the oxidation of Hg0 has been observed. The increase of the reaction temperature in the presence of HCl results in the reduction of Hg0 oxidation efficiency probably due to the deterioration of the heterogeneous chemical reaction of Hg0 with chlorinated species on the reactor wall. The presence of NO shows an inhibitory effect on the oxidation of Hg0 under DBD of 16% O2 in N2, indicating that NO acts as an O and O3 scavenger. At the composition of Hg0 (280 microg m(-3)), HCl (25 ppm), NO (204 ppm), O2 (16%) and N2 (balance) and temperature 90 degrees C, we obtain the nearly complete oxidation of Hg0 at a specific energy density of 8 J l(-1). These results lead us to suggest that the DBD process can be viable for the treatment of mercury released from coal-fired power plants.

Application of pulsed corona induced plasma chemical process to an industrial incinerator.

Pulsed corona induced plasma chemical process (PPCP) has been investigated for the simultaneous removal of NO(x) (nitrogen oxides) and SO2 (sulfur dioxide) from the flue gas emission. It is one of the world's largest scales of PPCP for treating NO(x) and SO2 simultaneously. A PPCP unit equipped with an average 120 kW modulator has been installed and tested at an industrial incinerator with the gas flow rate of 42 000 m3/h. To improve the removal efficiency of SO2 and NO(x), ammonia (NH3) and propylene (C3H6) were used as chemical additives. It was observed that the pulsed corona induced plasma chemical process made significant NO(x) and SO2 conversion with reasonable electric power consumption. The ammonia injection was very effective in the enhancement of SO2 removal. NO removal efficiency was significantly improved by injecting a C3H6 additive. In the experiments, the removal efficiencies of SO2 and NO(x) were approximately 99 and 70%, respectively. The specific energy consumption during the normal operation was approximately 1.4 Wh/m3, and the nanopulse conversion efficiency of 64.3% was achieved with the pulsed corona induced plasma chemical process.