Numerical Investigation on the Intraphase and Interphase Mass Transfer Limitations for NH3-SCR over Cu-ZSM-5

A systematic modeling approach was scrutinized to develop a kinetic model and a novel monolith channel geometry was designed for NH3 selective catalytic reduction (NH3-SCR) over Cu-ZSM-5. The redox characteristic of Cu-based catalysts and the variations of NH3, NOx concentration, and NOx conversion along the axis in porous media channels were studied. The relative pressure drop in different channels, the variations of NH3 and NOx conversion efficiency were analyzed. The model mainly considers NH3 adsorption and desorption, NH3 oxidation, NO oxidation, and NOx reduction. The results showed that the model could accurately predict the NH3-SCR reaction. In addition, it was found that the Cu-based zeolite catalyst had poor low-temperature catalytic performance and good high-temperature activity. Moreover, the catalytic reaction of NH3-SCR was mainly concentrated in the upper part of the reactor. In addition, the hexagonal channel could effectively improve the diffusion rate of gas reactants to the catalyst wall, reduce the pressure drop and improve the catalytic conversion efficiencies of NH3 and NOx.

The Study of C3H6 Impact on Selective Catalytic Reduction by Ammonia (NH3-SCR) Performance over Cu-SAPO-34 Catalysts

In present work, the catalytic performance of Cu-SAPO-34 catalysts with or without propylene during the NH3-SCR process was conducted, and it was found that the de-NOx activity decreased during low temperature ranges (<350 °C), but obviously improved within the range of high temperatures (>350 °C) in the presence of propylene. The XRD, BET, TG, NH3-TPD, NOx-TPD, in situ DRIFTS and gas-switch experiments were performed to explore the propylene effect on the structure and performance of Cu-SAPO-34 catalysts. The bulk characterization and TG results revealed that neither coke deposition nor the variation of structure and physical properties of catalysts were observed after C3H6 treatment. Generally speaking, at the low temperatures (<350 °C), active Cu2+ species could be occupied by propylene, which inhibited the adsorption and oxidation of NOx species, confining the SCR reaction rate and causing the deactivation of Cu-SAPO-34 catalysts. However, with the increase of reaction temperatures, the occupied Cu2+ sites would be recovered and sequentially participate into the NH3-SCR reaction. Additionally, C3H6-SCR reaction also showed the synergetic contribution to the improvement of NOx conversion at high temperature (>350 °C).

Numerical analysis on a novel CGPFs for improve NOx conversion efficiency and particulate combustion efficiency to reduce exhaust pollutant emission

Improving the NOx conversion efficiency and particulate combustion efficiency under cold start conditions (low temperature conditions) is still the main challenge faced by catalytic gasoline particulate filter system (CGPFs). In this study, the physical and mathematical models of novel CGPFs are proposed based on the computational fluid dynamics software. Then, the models are validated based on experiments, and the performances of conventional and novel CGPFs are analyzed comparatively. The comparison conclusions indicate that the NOx conversion efficiency of the novel CGPFs increases by 3.2% and the particulate combustion efficiency increases by 2.7% under the same operating condition. Finally, the effects of exhaust flow vf, exhaust oxygen concentration Co, exhaust NO concentration CNO and electric heating power Pe on the NOx conversion efficiency and particulate combustion efficiency are investigated. The weights of each influencing parameter on the NOx conversion efficiency and particulate combustion efficiency are explored by orthogonal tests. The conclusions show that the NOx conversion efficiency is increased by 3.6% and the particulate combustion efficiency is increased by 16.7% compared to the initial condition. This study has an important reference value for improving the purification efficiency of vehicle emission under cold start conditions.

Effect of Ion-Exchange Sequences on Catalytic Performance of Cerium-Modified Cu-SSZ-13 Catalysts for NH3-SCR

Cerium-modified Cu-SSZ-13 catalysts were prepared by an aqueous ion-exchange method, and Ce and Cu were incorporated through different ion-exchange sequences. The results of NH3-SCR activity evaluations displayed that Cu1(CeCu)2 catalyst presented excellent catalytic activity, and over 90% NOx conversion was obtained across the temperature range of 200–500 °C. The characterization results showed that the ion-exchange sequence of Cu and Ce species influenced the crystallinity of the zeolites and the coordination of Al. A small amount of Ce could participate in the reduction process and change the location and coordination environment of copper ions. Furthermore, Ce-modified Cu-SSZ-13 catalysts possessed more acidic sites due to their containing replacement of Ce and movement of Cu in the preparation process. The cooperation of strong redox abilities and NH3 storage capacity led to the increase of active adsorbed species adsorption and resulted in better activity of Cu1(CeCu)2.

Effect of Mn On The Performance and Mechanism of Catalysts For The Synthesis of (Ce,La)CO3F

In accordance with the cerium-lanthanum ratio of fluorocerium ores in the mineralogy of the Baiyun Ebo process, pure substances such as Ce(NO3)3·6H2O, La(NO3)3·6H2O were used to synthesize (Ce,La)CO3F grains to simulate bastnaesite minerals by hydrothermal method, and used as NH3-SCR denitrification catalysts. After being roasted at a series of different temperatures, the catalyst surface produced a well-crystallised Ce7O12 species as the active component for denitrification. The activity results showed that the synthetic (Ce,La)CO3F was roasted at 500°C, and the NOx conversion was 27% at 200°C. The NH3-SCR catalytic activity of the synthesised (Ce,La)CO3F was improved by loaded transition metal Mn. The best catalyst was found to be produced by impregnating (Ce,La)CO3F with 1 mol/L manganese nitrate solution, with a NOx conversion of 80% at 250°C. The physicochemical properties were analysed using XRD, BET, H2-TPR, NH3-TPD and XPS. The loading of Mn resulted in the appearance of numerous well-dispersed MnOx species on the catalyst surface, the dispersion of Ce7O12 species was also greatly enhanced, and the reduction in grain size indicated that Mnn+ entered into the (Ce,La)CO3F lattice causing lattice shrinkage. The number of acidic sites on the catalyst surface and the redox capacity were enhanced. The amount of Ce3+ in the catalyst was also enhanced by the introduction of Mnn+, but the proportion of adsorbed oxygen decreased, which indicated that the introduction of Mnn+ was detrimental to the increase in the proportion of adsorbed oxygen. The reaction mechanisms of the (Ce,La)CO3F and Mn/(Ce,La)CO3F catalysts were investigated by in-situ Fourier transform infrared spectroscopy (FTIR), to provide theoretical guidance for the specific reaction pathways of bastnaesite in the NH3-SCR reaction. The results showed that catalysts followed both the E-R and L-H mechanisms throughout the reaction process. When loaded with Mn, the main reactive species in the L-H mechanism were the NH4+(ad) species on the Brønsted acidic site and the O-Ce3+-O-NO, O-Mn3+-O-NO species. The main reactive species for the E-R mechanism were NH3/NH4+(ad) species on the Brønsted/Lewis acidic sites and NO. The NH4+ (ad) species on the Brønsted acidic sites act as the main reactive NH3(g) adsorbing species, bonded to the Ce4+ in the carrier (Ce,La)CO3F to participate in the acid cycle reaction. The introduction of Mnn+ increases the number of Brønsted acidic sites on the catalyst surface, and acts as an adsorption site for NO, to react with NO to generate more monodentate nitrate species, to participate in the redox cycle reactions. The above results indicated that Mnn+ and (Ce,La)CO3F have a good mutual promotion effect, which makes the loaded catalyst have excellent performance, which provides a theoretical basis for the high value utilization of bastnaesite.